# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_500mpa
_database_code_depnum_ccdc_archive 'CCDC 2299159'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 0.646(N8), 0.167[CH2CH3OH]'
_chemical_formula_sum            'C8.34 H11 Co N9.17 O0.17'
_chemical_formula_weight         301.33
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H8 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 0.5 GPa in LN2 scs'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'y, -x, -z'
'-x, -y, z'
'-y, x, -z'
'-x, z, -y'
'x, -y, -z'
'-x, -z, y'
'-z, -y, x'
'-x, y, -z'
'z, -y, -x'
'z, x, y'
'y, z, x'
'-y, -z, x'
'z, -x, -y'
'-y, z, -x'
'-z, -x, y'
'-z, x, -y'
'y, -z, -x'
'-y, -x, z'
'y, x, z'
'x, -z, -y'
'x, z, y'
'-z, y, -x'
'z, y, x'
'x+1/2, y+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'-x+1/2, z+1/2, -y+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x+1/2, -z+1/2, y+1/2'
'-z+1/2, -y+1/2, x+1/2'
'-x+1/2, y+1/2, -z+1/2'
'z+1/2, -y+1/2, -x+1/2'
'z+1/2, x+1/2, y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-y+1/2, z+1/2, -x+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'
'x+1/2, -z+1/2, -y+1/2'
'x+1/2, z+1/2, y+1/2'
'-z+1/2, y+1/2, -x+1/2'
'z+1/2, y+1/2, x+1/2'

_cell_length_a                   17.1155(7)
_cell_length_b                   17.1155(7)
_cell_length_c                   17.1155(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5013.8(6)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1646
_cell_measurement_temperature    293
_cell_measurement_theta_max      18.3250
_cell_measurement_theta_min      3.3460
_shelx_estimated_absorpt_T_max   0.913
_shelx_estimated_absorpt_T_min   0.869
_exptl_absorpt_coefficient_mu    1.029
_exptl_absorpt_correction_T_max  0.7442
_exptl_absorpt_correction_T_min  0.4804
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1072 before and 0.0718 after correction.
The Ratio of minimum to maximum transmission is 0.6455.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.198
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1843
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0768
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            3887
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        18.354
_diffrn_reflns_theta_max         18.354
_diffrn_reflns_theta_min         3.367
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -30.00   4.00   0.50   75.00    --   24.20  52.00-177.00   68
  2  ω    -21.00  42.00   0.50   75.00    --  -24.44  58.00 -58.00  126
  3  ω     30.00  63.00   0.50   75.00    --   24.20 -99.00-120.00   66
  4  ω    -23.00  16.00   0.50   75.00    --   24.20  67.00 157.00   78
  5  ω     -4.00  18.00   0.50   75.00    --  -24.44 -57.00  30.00   44
  6  ω    -18.00   4.00   0.50   75.00    --   24.20  57.00   0.00   44
  7  ω    -30.00  10.00   0.50   75.00    --   24.20  82.00 -29.00   80
  8  ω     30.00  55.00   0.50   75.00    --   24.20 -99.00  30.00   50
  9  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 150.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, Hypix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0146957000
_diffrn_orient_matrix_UB_12      0.0072747000
_diffrn_orient_matrix_UB_13      -0.0380227000
_diffrn_orient_matrix_UB_21      0.0041925000
_diffrn_orient_matrix_UB_22      0.0407949000
_diffrn_orient_matrix_UB_23      0.0061865000
_diffrn_orient_matrix_UB_31      0.0385062000
_diffrn_orient_matrix_UB_32      -0.0016488000
_diffrn_orient_matrix_UB_33      -0.0152380000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.739
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                343
_reflns_number_total             367
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_refine_diff_density_max         0.511
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details 
;
 Flack x determined using 138 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.189
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     38
_refine_ls_number_reflns         367
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0660
_refine_ls_restrained_S_all      147.691
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1359P)²+7.6237P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1848
_refine_ls_wR_factor_ref         0.1875
_refine_special_details          SQUEEZE
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C1
 1.387 with sigma of 0.01
 C2-N1_$1
 1.337 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.02
 C2-C3
 1.55 with sigma of 0.02
3. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C2) = Uanis(N1) = Uanis(C1)
Uiso(N2) = Uiso(N3)
5. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N5(0.125) N8(0.25) N3(0.125) N9(0.25)
 N6(0.083333) N4(0.25) N7(0.083333)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.050(2) Uani 1 4 d S T P . .
N1 N 0.5888(8) 0.3201(8) 0.0309(6) 0.065(4) Uani 1 1 d D . . . .
C2 C 0.6318(8) 0.3682(8) -0.0116(13) 0.065(4) Uani 1 2 d DS T P . .
C1 C 0.6116(10) 0.3354(12) 0.1069(8) 0.065(4) Uani 1 1 d D . . . .
H1 H 0.588414 0.307174 0.158135 0.078 Uiso 1 1 calc R U . . .
C3 C 0.6252(14) 0.3748(14) -0.0996(17) 0.115(15) Uiso 1 2 d DS . P . .
H3A H 0.666474 0.417883 -0.120698 0.172 Uiso 0.5 1 calc R U P A -1
H3B H 0.638042 0.318685 -0.125994 0.172 Uiso 0.5 1 calc R U P A -1
H3C H 0.566486 0.392429 -0.115121 0.172 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.18(2) Uiso 1 8 d S . P . .
N5 N 0.500000 0.500000 -0.235(7) 0.17(4) Uiso 0.5 4 d S . P . .
N8 N 0.781(3) 0.219(3) 0.061(4) 0.12(3) Uiso 0.5 2 d S . P . .
N3 N 0.500000 0.500000 -0.046(5) 0.18(2) Uiso 0.5 4 d S . P . .
N9 N 0.781(3) 0.219(3) 0.021(6) 0.14(3) Uiso 0.5 2 d S . P . .
N6 N 0.818(5) 0.182(5) -0.182(5) 0.16(4) Uiso 0.5 6 d S . P . .
N4 N 0.500(9) 0.448(5) -0.228(5) 0.16(3) Uiso 0.25 1 d . . P . .
N7 N 0.784(6) 0.216(6) -0.216(6) 0.19(6) Uiso 0.5 6 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 2.007(13) 34 ?
Co1 N1 2.007(13) . ?
Co1 N1 2.007(13) 9_655 ?
Co1 N1 2.007(13) 32_554 ?
N1 C2 1.322(17) . ?
N1 C1 1.382(12) . ?
C2 C3 1.52(2) . ?
C1 C1 1.28(4) 19_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.78(9) . ?
N2 N3 0.78(9) 2_565 ?
N5 N4 0.90(9) 3_665 ?
N5 N4 0.90(9) 19_665 ?
N5 N4 0.90(9) . ?
N5 N4 0.90(9) 20 ?
N8 N9 0.69(10) . ?
N3 N3 1.56(18) 2_565 ?
N6 N7 1.00(18) . ?
N4 N4 1.2(2) 19_665 ?
N4 N4 1.78(17) 3_665 ?
N4 N4 1.3(2) 20 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.9(4) 34 9_655 ?
N1 Co1 N1 110.9(4) 32_554 . ?
N1 Co1 N1 106.6(8) 9_655 . ?
N1 Co1 N1 106.6(8) 34 32_554 ?
N1 Co1 N1 110.9(4) 9_655 32_554 ?
N1 Co1 N1 110.9(4) 34 . ?
C2 N1 Co1 130.4(9) . . ?
C2 N1 C1 104.0(13) . . ?
C1 N1 Co1 125.1(11) . . ?
N1 C2 N1 113.0(17) . 19_665 ?
N1 C2 C3 123.5(8) . . ?
N1 C2 C3 123.5(8) 19_665 . ?
N1 C1 H1 125.3 . . ?
C1 C1 N1 109.5(10) 19_665 . ?
C1 C1 H1 125.3 19_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.000(13) . 2_565 ?
N4 N5 N4 90(10) . 20 ?
N4 N5 N4 90(10) 19_665 3_665 ?
N4 N5 N4 165(10) . 3_665 ?
N4 N5 N4 88(10) 3_665 20 ?
N4 N5 N4 88(10) . 19_665 ?
N4 N5 N4 165(10) 19_665 20 ?
N2 N3 N3 0.000(5) . 2_565 ?
N5 N4 N4 7(10) . 3_665 ?
N5 N4 N4 46(9) . 19_665 ?
N5 N4 N4 45(10) . 20 ?
N4 N4 N4 46(9) 19_665 3_665 ?
N4 N4 N4 44(9) 20 3_665 ?
N4 N4 N4 90.00(2) 19_665 20 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.2(6) . . . 19_665 ?
Co1 N1 C2 C3 -5(3) . . . . ?
Co1 N1 C1 C1 -173.4(8) . . . 19_665 ?
C2 N1 C1 C1 -0.4(14) . . . 19_665 ?
C1 N1 C2 N1 1(2) . . . 19_665 ?
C1 N1 C2 C3 -177.7(19) . . . . ?
N4 N5 N4 N4 83(12) 3_665 . . 20 ?
N4 N5 N4 N4 165(24) 19_665 . . 20 ?
N4 N5 N4 N4 -83(13) 20 . . 3_665 ?
N4 N5 N4 N4 83(12) 19_665 . . 3_665 ?
N4 N5 N4 N4 -83(12) 3_665 . . 19_665 ?
N4 N5 N4 N4 -165(24) 20 . . 19_665 ?

_smtbx_masks_special_details     
;
A solvent mask was calculated and 48 electrons were 
found in a volume of 436Å³ in 1 void per unit cell. 
This is consistent with the presence of 
2[CH2CH3OH] per Unit Cell 
which account for 52 electrons 
per unit cell.
;
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 0.000 0.000 0.000 218.4 24.3 '1 CH2CH3OH'
2 0.500 0.500 0.500 218.4 24.3 '1 CH2CH3OH'

_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_platon_squeeze_special_details  ?
_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 8.420
_oxdiff_exptl_absorpt_empirical_full_min 0.654
# start Validation Reply Form
_vrf_THETM01_zif67_500mpa        
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading from the diamond anvil cell.
;
_vrf_PLAT090_zif67_500mpa        
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       5.55 Note  
RESPONSE: This is caused by shading from the diamond anvil cell.
;
_vrf_PLAT201_zif67_500mpa        
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          1 Report
RESPONSE: Methyl group refined without ADPs due to
high disorder at room temperature and low resolution
from diamond anvil and gasket shading reducing resolution
;
_vrf_PLAT341_zif67_500mpa        
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.035 Ang.  
RESPONSE: This is caused by low resultion due to shading from 
the diamond anvil cell.
;
_vrf_PLAT202_zif67_500mpa        
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          1 Check 
RESPONSE: Absorbate must be refined without ADPs due to
high disorder at room temperature in the diamond anvil cell
;
_vrf_PLAT242_zif67_500mpa        
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of         C2 Check 
RESPONSE: Likely caused by disorder on the methyl group.
;
_vrf_PLAT975_zif67_500mpa        
;
PROBLEM: Check Calcd Resid. Dens.  1.02Ang From N7      .       0.65 eA-3  
RESPONSE: This is unlikely to be hydrogen and is simply 
residual density from more disordered solvent.
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_1300
_database_code_depnum_ccdc_archive 'CCDC 2299161'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_1300      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_ln2_1300      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.02 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT987_zif67_ln2_1300      
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_ln2_1300      
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in olex2
;
_vrf_PLAT042_zif67_ln2_1300      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error
;
_vrf_PLAT090_zif67_ln2_1300      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       6.67 Note
RESPONSE: The sample is non-centro but shading by the diamond anvil cell prevents collection of reflections from multiple angles. This is common in high pressure experiments.
;
_vrf_PLAT094_zif67_ln2_1300      
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       2.20 Report
RESPONSE: Maximum and minimum residual denisty are low, despite ratio.
;
_vrf_PLAT202_zif67_ln2_1300      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          5 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT723_zif67_ln2_1300      
;
PROBLEM: Torsion Calc     -135.00, Rep    -138(**) Dev...       3.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_1300_2    
;
PROBLEM: Torsion Calc      135.00, Rep     138(**) Dev...       3.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 12.889(N0.5)'
_chemical_formula_sum            'C8 H10 Co N10.44'
_chemical_formula_weight         311.41
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 1.3 GPa'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.9979(6)
_cell_length_b                   16.9979(6)
_cell_length_c                   16.9979(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4911.2(5)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1983
_cell_measurement_temperature    293
_cell_measurement_theta_max      20.7810
_cell_measurement_theta_min      3.3720
_shelx_estimated_absorpt_T_max   0.911
_shelx_estimated_absorpt_T_min   0.866
_exptl_absorpt_coefficient_mu    1.054
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.4799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1078 before and 0.0816 after correction.
The Ratio of minimum to maximum transmission is 0.6446.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'bluish violet'
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1897
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0906
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5119
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        20.781
_diffrn_reflns_theta_max         20.781
_diffrn_reflns_theta_min         3.390
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -36.00  29.00   0.50   75.00    --  -24.44 -53.00  38.00  130
  2  ω    -27.00  -3.00   0.50   75.00    --   24.20  19.00-150.00   48
  3  ω    -23.00  16.00   0.50   75.00    --   24.20  67.00 -23.00   78
  4  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 150.00   40
  5  ω     -4.00  18.00   0.50   75.00    --  -24.44 -57.00  30.00   44
  6  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 -30.00   40
  7  ω    -36.00 -16.00   0.50   75.00    --   24.20  38.00  30.00   40
  8  ω     30.00  55.00   0.50   75.00    --   24.20 -99.00  30.00   50
  9  ω     30.00  71.00   0.50   75.00    --   24.20 -99.00-150.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0147531000
_diffrn_orient_matrix_UB_12      0.0070913000
_diffrn_orient_matrix_UB_13      -0.0383535000
_diffrn_orient_matrix_UB_21      0.0040678000
_diffrn_orient_matrix_UB_22      0.0411162000
_diffrn_orient_matrix_UB_23      0.0059826000
_diffrn_orient_matrix_UB_31      0.0388200000
_diffrn_orient_matrix_UB_32      -0.0016011000
_diffrn_orient_matrix_UB_33      -0.0152482000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                463
_reflns_number_total             505
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.830
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.150
_refine_ls_abs_structure_details 
;
 Flack x determined using 182 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     43
_refine_ls_number_reflns         505
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0847
_refine_ls_R_factor_gt           0.0801
_refine_ls_restrained_S_all      1.120
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1966P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2325
_refine_ls_wR_factor_ref         0.2398
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C3
 1.55 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.01
 N1-C1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
3. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C1) = Uanis(C2)
Uiso(N11) = Uiso(N10)
Uiso(N4) = Uiso(N5)
Uiso(N3) = Uiso(N2)
Uiso(N9) = Uiso(N8)
Uiso(N6) = Uiso(N7)
5. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N2(0.083333) N8(0.25) N3(0.166667)
 N9(0.25) N6(0.11111) N4(0.166667) N7(0.05556) N10(0.11112) N11(0.083333)
 N12(0.083333)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0376(18) Uani 1 4 d S T P . .
N1 N 0.5874(6) 0.3195(6) 0.0355(5) 0.040(3) Uani 1 1 d D . . . .
C2 C 0.6324(7) 0.3676(7) -0.0081(8) 0.040(3) Uani 1 2 d DS T P . .
C1 C 0.6059(8) 0.3380(10) 0.1123(6) 0.040(3) Uani 1 1 d D . . . .
H1 H 0.579842 0.311891 0.163790 0.048 Uiso 1 1 calc R U . . .
C3 C 0.6274(10) 0.3726(10) -0.0964(12) 0.050(6) Uani 1 2 d DS T P . .
H3A H 0.584599 0.330469 -0.117621 0.075 Uiso 0.5 1 calc R U P A -1
H3B H 0.609526 0.431389 -0.113282 0.075 Uiso 0.5 1 calc R U P A -1
H3C H 0.684392 0.359626 -0.121654 0.075 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.091(10) Uiso 0.6666 8 d S . P . .
N5 N 0.500000 0.500000 -0.232(5) 0.137(19) Uiso 1 4 d S . P . .
N8 N 0.7774(18) 0.2226(18) 0.070(2) 0.064(8) Uiso 0.5 2 d S . P . .
N3 N 0.500000 0.500000 -0.039(3) 0.091(10) Uiso 0.6667 4 d S . P . .
N9 N 0.770(2) 0.230(2) 0.027(2) 0.064(8) Uiso 0.5 2 d S . P . .
N6 N 0.758(3) 0.242(3) -0.242(3) 0.081(15) Uiso 0.6667 6 d S . P . .
N4 N 0.528(6) 0.472(6) -0.233(10) 0.137(19) Uiso 0.3333 2 d S . P . .
N7 N 0.742(5) 0.258(5) -0.258(5) 0.081(15) Uiso 0.3334 6 d S . P . .
N10 N 0.575(5) 0.425(5) -0.425(5) 0.10(3) Uiso 0.6667 6 d S . P . .
N11 N 0.597(14) 0.443(12) -0.443(12) 0.10(3) Uiso 0.1667 2 d S . P . .
N12 N 0.873(3) 0.127(3) -0.127(3) 0.08(3) Uiso 0.5 6 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.992(10) 46 ?
Co1 N1 1.992(10) . ?
Co1 N1 1.992(10) 3_655 ?
Co1 N1 1.992(10) 48_554 ?
N1 C2 1.342(10) . ?
N1 C1 1.379(11) . ?
C2 C3 1.50(2) . ?
C1 C1 1.35(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.66(4) 3_655 ?
N2 N3 0.66(4) . ?
N5 N4 0.67(14) . ?
N5 N4 0.67(14) 2_665 ?
N8 N9 0.76(5) . ?
N3 N3 1.32(9) 3_655 ?
N4 N4 1.3(3) 2_665 ?
N10 N11 0.6(2) 12_654 ?
N10 N11 0.6(2) . ?
N10 N11 0.6(2) 6_665 ?
N11 N11 0.9(4) 6_665 ?
N11 N11 0.9(4) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.6(3) 46 3_655 ?
N1 Co1 N1 107.2(6) 3_655 . ?
N1 Co1 N1 110.6(3) 46 . ?
N1 Co1 N1 107.2(6) 46 48_554 ?
N1 Co1 N1 110.6(3) 48_554 . ?
N1 Co1 N1 110.6(3) 3_655 48_554 ?
C2 N1 Co1 128.3(7) . . ?
C2 N1 C1 104.7(10) . . ?
C1 N1 Co1 126.3(9) . . ?
N1 C2 N1 112.9(12) 14_665 . ?
N1 C2 C3 123.5(6) . . ?
N1 C2 C3 123.5(6) 14_665 . ?
N1 C1 H1 125.6 . . ?
C1 C1 N1 108.8(7) 14_665 . ?
C1 C1 H1 125.6 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.0 3_655 . ?
N4 N5 N4 177(10) 2_665 . ?
N2 N3 N3 0.000(3) . 3_655 ?
N5 N4 N4 2(10) . 2_665 ?
N11 N10 N11 115(10) . 12_654 ?
N11 N10 N11 115(10) . 6_665 ?
N11 N10 N11 115(10) 6_665 12_654 ?
N10 N11 N11 32(10) . 6_665 ?
N10 N11 N11 32(10) . 12_654 ?
N11 N11 N11 60.00(8) 6_665 12_654 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.2(5) . . . 14_665 ?
Co1 N1 C2 C3 -5(2) . . . . ?
Co1 N1 C1 C1 -172.3(6) . . . 14_665 ?
C2 N1 C1 C1 -1.6(11) . . . 14_665 ?
C1 N1 C2 N1 2.7(19) . . . 14_665 ?
C1 N1 C2 C3 -175.1(15) . . . . ?
N11 N10 N11 N11 -138(100) 12_654 . . 6_665 ?
N11 N10 N11 N11 138(100) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.598
_oxdiff_exptl_absorpt_empirical_full_min 0.614
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ambient
_database_code_depnum_ccdc_archive 'CCDC 2299160'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 1[CH2CH3OH]'
_chemical_formula_sum            'C10 H16 Co N4 O'
_chemical_formula_weight         267.20
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C11 H20 N4 O3'
_chemical_oxdiff_usercomment     'zif67 G NO CONFIDENCE'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   17.0426(4)
_cell_length_b                   17.0426(4)
_cell_length_c                   17.0426(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4950.0(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    2137
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.2840
_cell_measurement_theta_min      2.9140
_shelx_estimated_absorpt_T_max   0.928
_shelx_estimated_absorpt_T_min   0.859
_exptl_absorpt_coefficient_mu    1.029
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.867
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.70a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.076
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1668
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-11 -2 21 0.0419
11 2 -21 0.0421
-18 9 -12 0.0357
18 -9 12 0.0442
21 -4 -10 0.0397
-21 4 10 0.0341
-15 -18 -2 0.0584
15 18 2 0.0513
6 -22 9 0.0406
-6 22 -9 0.0454
-11 20 8 0.0515
11 -20 -8 0.0456
-1 -23 -8 0.0572
1 23 8 0.0510

_exptl_crystal_size_max          0.152
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.074
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-10.8321 -2.0314 21.3424 0.2313 0.9678 -0.0996
10.8321 2.0314 -21.3424 -0.2313 -0.9678 0.0996
-18.4738 9.3403 -12.2069 -0.0127 -0.0365 0.9993
18.4738 -9.3403 12.2069 0.0127 0.0365 -0.9993
21.2115 -4.2807 -10.4440 -0.1903 -0.8070 -0.5590
-21.2115 4.2807 10.4440 0.1903 0.8070 0.5590
-15.4984 -18.2207 -2.3113 0.9613 0.0760 0.2648
15.4984 18.2207 2.3113 -0.9613 -0.0760 -0.2648
5.5381 -21.7270 8.6334 0.7111 0.0597 -0.7006
-5.5381 21.7270 -8.6334 -0.7111 -0.0597 0.7006
-11.2472 19.5273 8.3356 -0.5555 0.6516 0.5165
11.2472 -19.5273 -8.3356 0.5555 -0.6516 -0.5165
-1.3159 -22.6615 -7.8797 0.8915 -0.4230 -0.1623
1.3159 22.6615 7.8797 -0.8915 0.4230 0.1623

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            6643
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.440
_diffrn_reflns_theta_min         2.390
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.932
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -29.00  67.00   0.50  132.95    --  -15.69  23.00 112.00  192
  2  ω    -87.00 -41.00   0.50  132.95    --   15.53-178.00-180.00   92
  3  ω    -81.00 -40.00   0.50  132.95    --   15.53 -19.00 -90.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0173725000
_diffrn_orient_matrix_UB_12      -0.0377825000
_diffrn_orient_matrix_UB_13      -0.0015767000
_diffrn_orient_matrix_UB_21      -0.0186261000
_diffrn_orient_matrix_UB_22      0.0070334000
_diffrn_orient_matrix_UB_23      0.0365611000
_diffrn_orient_matrix_UB_31      -0.0329014000
_diffrn_orient_matrix_UB_32      0.0159724000
_diffrn_orient_matrix_UB_33      -0.0198453000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.869
_reflns_number_gt                679
_reflns_number_total             893
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.70a (Rigaku OD, 2023)'
_computing_data_collection       
'CrysAlisPro system (CCD 41.115a 64-bit (release 06-08-2021))'
_computing_data_reduction        'CrysAlisPro 1.171.43.70a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.256
_refine_diff_density_min         -0.144
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details 
;
 Flack x determined using 240 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.035(13)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         893
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0430
_refine_ls_restrained_S_all      1.013
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0575P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0984
_refine_special_details          SQUEEZE
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C005, C003, N002, C004
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C004) = Uanis(N002) = Uanis(C003)
4. Rigid body (RIGU) restrains
 C005, C003
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H00C(0.5) H00A(0.5) H00B(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C004(H004)
6.b Idealised Me refined as rotating group:
 C005(H00C,H00A,H00B)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co01 Co 0.250000 0.000000 0.500000 0.0702(5) Uani 1 4 d S T P . .
N002 N 0.3175(2) 0.0317(2) 0.5901(3) 0.0816(9) Uani 1 1 d . . . . .
C003 C 0.3776(2) -0.0051(6) 0.6224(2) 0.0816(9) Uani 1 2 d S T P . .
C004 C 0.3125(3) 0.1004(3) 0.6313(3) 0.0816(9) Uani 1 1 d . . . . .
H004 H 0.270897 0.146810 0.620754 0.098 Uiso 1 1 calc R U . . .
C005 C 0.4069(4) -0.0854(4) 0.5931(4) 0.099(2) Uani 1 2 d S T P . .
H00C H 0.367713 -0.107053 0.548010 0.149 Uiso 0.5 1 calc R U P A -1
H00A H 0.408225 -0.126440 0.641574 0.149 Uiso 0.5 1 calc R U P A -1
H00B H 0.465403 -0.079051 0.569074 0.149 Uiso 0.5 1 calc R U P A -1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co01 N002 1.993(4) . ?
Co01 N002 1.993(4) 42_545 ?
Co01 N002 1.993(4) 43 ?
Co01 N002 1.993(4) 4_556 ?
N002 C003 1.322(5) . ?
N002 C004 1.367(5) . ?
C003 C005 1.540(11) . ?
C004 C004 1.355(9) 23_656 ?
C004 H004 1.0770 . ?
C005 H00C 1.0831 . ?
C005 H00A 1.0831 . ?
C005 H00B 1.0831 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N002 Co01 N002 109.42(12) . 43 ?
N002 Co01 N002 109.6(2) 43 42_545 ?
N002 Co01 N002 109.43(12) . 42_545 ?
N002 Co01 N002 109.6(2) . 4_556 ?
N002 Co01 N002 109.43(12) 43 4_556 ?
N002 Co01 N002 109.43(12) 4_556 42_545 ?
C003 N002 Co01 129.7(4) . . ?
C003 N002 C004 103.9(5) . . ?
C004 N002 Co01 126.3(3) . . ?
N002 C003 N002 114.9(7) 23_656 . ?
N002 C003 C005 122.6(4) . . ?
N002 C003 C005 122.6(4) 23_656 . ?
N002 C004 H004 125.7 . . ?
C004 C004 N002 108.6(3) 23_656 . ?
C004 C004 H004 125.7 23_656 . ?
C003 C005 H00C 109.5 . . ?
C003 C005 H00A 109.5 . . ?
C003 C005 H00B 109.5 . . ?
H00C C005 H00A 109.5 . . ?
H00C C005 H00B 109.5 . . ?
H00A C005 H00B 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co01 N002 C003 N002 -179.5(2) . . . 23_656 ?
Co01 N002 C003 C005 -0.4(10) . . . . ?
Co01 N002 C004 C004 -179.5(3) . . . 23_656 ?
C003 N002 C004 C004 -1.5(5) . . . 23_656 ?
C004 N002 C003 N002 2.7(8) . . . 23_656 ?
C004 N002 C003 C005 -178.3(7) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 1 1 1.690

_platon_squeeze_details          
;
TITL zif67_ambient_a.res in I-43m
CELL   17.0426   17.0426   17.0426     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2491
# Electrons Found in S.A.V. =       294
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.316 0.316 0.316 !       1.36 eA-3
C102 0.672 0.656 0.675 !       1.09 eA-3
C103 0.172 0.156 0.175 !       1.09 eA-3
C104 0.356 0.306 0.693 !       1.03 eA-3
C105 0.215 0.218 0.168 !       0.99 eA-3
C106 0.070 0.174 0.174 !       0.98 eA-3
C107 0.861 0.801 0.114 !       0.87 eA-3
C108 0.036 0.036 0.036 !       0.84 eA-3
C109 0.116 0.866 0.133 !       0.82 eA-3
C110 0.410 0.410 0.410 !       0.82 eA-3
C111 0.716 0.650 0.353 !       0.79 eA-3
C112 0.090 0.015 0.207 !       0.78 eA-3
C113 0.297 0.376 0.292 !       0.75 eA-3
C114 0.295 0.708 0.470 !       0.73 eA-3
C115 0.702 0.482 0.482 !       0.73 eA-3
C116 0.957 0.168 0.168 !       0.69 eA-3
C117 0.084 0.209 0.077 !       0.68 eA-3
C118 0.584 0.709 0.577 !       0.68 eA-3
C119 0.584 0.577 0.709 !       0.68 eA-3
C120 0.279 0.463 0.327 !       0.67 eA-3
C121 0.916 0.197 0.921 !       0.67 eA-3
C122 0.916 0.921 0.197 !       0.67 eA-3
C123 0.360 0.687 0.453 !       0.67 eA-3
C124 0.359 0.635 0.407 !       0.67 eA-3
C125 0.859 0.135 0.907 !       0.67 eA-3
C126 0.919 0.221 0.156 !       0.67 eA-3
C127 0.711 0.699 0.302 !       0.66 eA-3
C128 0.359 0.407 0.635 !       0.66 eA-3
C129 0.172 0.890 0.162 !       0.65 eA-3
C130 0.179 0.827-0.007 !       0.64 eA-3
C131 0.402 0.294 0.397 !       0.63 eA-3
C132 0.347 0.347 0.347 !       0.62 eA-3
C133 0.783 1.002 0.780 !       0.60 eA-3
C134 0.283 0.502 0.280 !       0.60 eA-3
C135 0.217 0.784 1.002 !       0.60 eA-3
C136 0.063 0.126 0.219 !       0.57 eA-3
C137 0.562 0.685 0.466 !       0.57 eA-3
C138 0.913 0.128 0.172 !       0.57 eA-3
C139 0.565 0.737 0.426 !       0.57 eA-3
C140 0.378 0.456 0.377 !       0.56 eA-3
C141 0.514 0.625 0.341 !       0.55 eA-3
C142 0.452 0.460 0.374 !       0.54 eA-3
C143 0.242 0.045 0.045 !       0.54 eA-3
C144 0.548 0.509 0.290 !       0.53 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 304 electrons were 
found in a volume of 2464Å³ in 1 void per unit cell. 
This is consistent with the presence of 
12[C2H5OH] per Unit Cell 
which account for 312 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.012 -0.006 -0.004 2464 304 ' '

_platon_squeeze_void_probe_radius 1.20

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.129
_oxdiff_exptl_absorpt_empirical_full_min 0.895

# start Validation Reply Form
_vrf_PLAT341_zif67_ambient       
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.009 Ang.  
RESPONSE: ZIF-67 has large pore volume with significant 
disordered solvent, which reduces resolution 
and thus precision.
;
_vrf_PLAT911_zif67_ambient       
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.600          7 Report
RESPONSE: These reflections are excluded during reduction due to
overexposure.
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_2000
_database_code_depnum_ccdc_archive 'CCDC 2299163'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_2000      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT090_zif67_ln2_2000      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       5.83 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments
;
_vrf_PLAT341_zif67_ln2_2000      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.019 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell
;
_vrf_PLAT430_zif67_ln2_2000      
;
PROBLEM: Short Inter D...A Contact  N4       ..N10      .       2.70 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2000_2    
;
PROBLEM: Short Inter D...A Contact  N11      ..N10      .       2.65 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2000_3    
;
PROBLEM: Short Inter D...A Contact  N11      ..N10      .       2.65 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2000_4    
;
PROBLEM: Short Inter D...A Contact  N11      ..N10      .       2.65 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT018_zif67_ln2_2000      
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_2000      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers, causing this particular error.
;
_vrf_PLAT202_zif67_ln2_2000      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          7 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT723_zif67_ln2_2000      
;
PROBLEM: Torsion Calc      146.00, Rep     144(70) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_2000_2    
;
PROBLEM: Torsion Calc     -146.00, Rep    -144(70) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 2.433(N4)'
_chemical_formula_sum            'C8 H10 Co N13.73'
_chemical_formula_weight         357.49
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 2.0 GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.8057(4)
_cell_length_b                   16.8057(4)
_cell_length_c                   16.8057(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4746.5(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    3783
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.6390
_cell_measurement_theta_min      3.4150
_shelx_estimated_absorpt_T_max   0.907
_shelx_estimated_absorpt_T_min   0.860
_exptl_absorpt_coefficient_mu    1.107
_exptl_absorpt_correction_T_max  0.7061
_exptl_absorpt_correction_T_min  0.6351
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0984 before and 0.0867 after correction.
The Ratio of minimum to maximum transmission is 0.8994.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.501
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2174
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0763
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            9257
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        20.799
_diffrn_reflns_theta_max         20.799
_diffrn_reflns_theta_min         3.429
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω      8.00  73.00   0.50   60.00    --   13.12 -93.00-167.00  130
  2  ω    -43.00 -18.00   0.50   60.00    --   13.12  93.00 -56.00   50
  3  ω    -50.00 -25.00   0.50   60.00    --  -13.27  93.00 -56.00   50
  4  ω     13.00  38.00   0.50   60.00    --  -13.27 -93.00-167.00   50
  5  ω     59.00  84.00   0.50   60.00    --   13.12 178.00 -90.00   50
  6  ω    -94.00 -69.00   0.50   60.00    --   13.12-178.00 -90.00   50
  7  ω    -59.00 -31.00   0.50   60.00    --   13.12 114.00 -45.00   56
  8  ω    -40.00  -5.00   0.50   60.00    --   13.12 114.00 135.00   70
  9  ω    -34.00  -4.00   0.50   60.00    --   13.12  82.00 151.00   60
 10  ω   -121.00 -90.00   0.50   60.00    --  -13.27-178.00 -90.00   62
 11  ω      8.00  34.00   0.50   60.00    --  -13.27 -53.00  17.00   52
 12  ω      9.00  40.00   0.50   60.00    --  -13.27 -82.00  29.00   62
 13  ω    -55.00  -4.00   0.50   60.00    --  -13.27  82.00 151.00  102
 14  ω    -36.00 -16.00   0.50   60.00    --  -13.27  38.00 -30.00   40
 15  ω     24.00  51.00   0.50   60.00    --  -13.27 -40.00  12.00   54
 16  ω    -45.00 -15.00   0.50   60.00    --  -13.27  97.00 143.00   60
 17  ω    -36.00 -16.00   0.50   60.00    --  -13.27  38.00 150.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0145531000
_diffrn_orient_matrix_UB_12      0.0073725000
_diffrn_orient_matrix_UB_13      0.0388774000
_diffrn_orient_matrix_UB_21      0.0362313000
_diffrn_orient_matrix_UB_22      -0.0192877000
_diffrn_orient_matrix_UB_23      -0.0099340000
_diffrn_orient_matrix_UB_31      0.0160332000
_diffrn_orient_matrix_UB_32      0.0368259000
_diffrn_orient_matrix_UB_33      -0.0130313000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                455
_reflns_number_total             496
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.790
_refine_diff_density_min         -0.677
_refine_diff_density_rms         0.132
_refine_ls_abs_structure_details 
;
 Flack x determined using 181 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     48
_refine_ls_number_reflns         496
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0721
_refine_ls_restrained_S_all      1.148
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1592P)²+0.3076P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1893
_refine_ls_wR_factor_ref         0.1947
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C3
 1.55 with sigma of 0.02
 N1-C1
 1.387 with sigma of 0.01
 N1-C2
 1.337 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N9-N8
 1.08 with sigma of 0.02
 N5-N4
 1.08 with sigma of 0.02
3. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C2) = Uanis(N1)
Uiso(N2) = Uiso(N7)
Uiso(N10) = Uiso(N11)
Uiso(N9) = Uiso(N8)
Uiso(N3) = Uiso(N2)
Uiso(N5) = Uiso(N4)
5. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N3(0.166667) N4(0.25) N11(0.083333)
 N12(0.125) N13(0.125) N10(0.083333) N15(0.1) N2(0.083333)
7.a Aromatic/amide H refined with riding coordinates:
 C1(H1)
7.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0341(15) Uani 1 4 d S T P . .
N1 N 0.5863(5) 0.3199(5) 0.0380(5) 0.036(2) Uani 1 1 d D . . . .
C2 C 0.6327(6) 0.3673(6) -0.0052(7) 0.036(2) Uani 1 2 d DS T P . .
C1 C 0.6041(7) 0.3372(8) 0.1164(5) 0.036(2) Uani 1 1 d D . . . .
H1 H 0.577535 0.310249 0.168083 0.043 Uiso 1 1 calc R U . . .
C3 C 0.6279(8) 0.3721(8) -0.0953(11) 0.048(5) Uani 1 2 d DS T P . .
H3A H 0.662054 0.323957 -0.121218 0.072 Uiso 0.5 1 calc R U P A -1
H3B H 0.651887 0.428536 -0.115142 0.072 Uiso 0.5 1 calc R U P A -1
H3C H 0.566378 0.367188 -0.113862 0.072 Uiso 0.5 1 calc R U P A -1
N5 N 0.500000 0.500000 -0.233(2) 0.122(11) Uiso 1 4 d DS . P . .
N8 N 0.7824(12) 0.2176(12) 0.0729(16) 0.128(7) Uiso 1 2 d DS . P . .
N3 N 0.500000 0.500000 -0.0366(18) 0.075(6) Uiso 0.6667 4 d S . P . .
N9 N 0.7643(13) 0.2357(13) 0.0221(17) 0.128(7) Uiso 1 2 d DS . P . .
N4 N 0.5440(11) 0.4560(11) -0.230(4) 0.122(11) Uiso 0.5 2 d DS . P . .
N11 N 0.568(7) 0.432(7) -0.432(7) 0.12(5) Uiso 0.5 6 d S . P . .
N12 N 0.593(4) 0.407(4) -0.443(4) 0.06(3) Uiso 0.25 2 d S . P . 1
N7 N 0.7570(13) 0.2430(13) -0.2430(13) 0.075(6) Uiso 1 6 d S . P . .
N13 N 0.876(2) 0.124(2) -0.124(2) 0.11(2) Uiso 0.75 6 d S . P . .
N10 N 0.540(8) 0.460(8) -0.393(12) 0.12(5) Uiso 0.1667 2 d S . P . 2
N15 N 0.823(8) 0.111(5) -0.111(5) 0.10(3) Uiso 0.2 2 d S . P . .
N2 N 0.500000 0.500000 0.000000 0.075(6) Uiso 0.6666 8 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.972(9) 46 ?
Co1 N1 1.972(9) 48_554 ?
Co1 N1 1.972(9) 3_655 ?
Co1 N1 1.972(9) . ?
N1 C2 1.331(9) . ?
N1 C1 1.382(10) . ?
C2 C3 1.52(2) . ?
C1 C1 1.39(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0831 . ?
C3 H3B 1.0831 . ?
C3 H3C 1.0831 . ?
N5 N4 1.05(3) 2_665 ?
N5 N4 1.05(3) . ?
N8 N9 0.96(2) . ?
N3 N3 1.23(6) 3_655 ?
N3 N2 0.62(3) . ?
N11 N12 0.63(14) 12_654 ?
N11 N12 0.63(14) 6_665 ?
N11 N12 0.63(14) . ?
N11 N10 0.93(17) 12_654 ?
N11 N10 0.93(17) 6_665 ?
N11 N10 0.93(17) . ?
N12 N12 0.86(14) 12_654 ?
N12 N12 0.86(14) 6_665 ?
N13 N15 0.94(13) 6_665 ?
N13 N15 0.94(13) 12_654 ?
N13 N15 0.94(13) . ?
N10 N10 1.6(3) 6_665 ?
N10 N10 1.9(4) 2_665 ?
N10 N10 1.6(3) 12_654 ?
N15 N15 1.6(2) 6_665 ?
N15 N15 1.6(2) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.8(3) 46 3_655 ?
N1 Co1 N1 106.9(5) 3_655 . ?
N1 Co1 N1 110.8(3) 46 . ?
N1 Co1 N1 106.9(5) 46 48_554 ?
N1 Co1 N1 110.8(3) 3_655 48_554 ?
N1 Co1 N1 110.8(3) 48_554 . ?
C2 N1 Co1 127.7(6) . . ?
C2 N1 C1 105.5(9) . . ?
C1 N1 Co1 126.4(8) . . ?
N1 C2 N1 113.9(11) 14_665 . ?
N1 C2 C3 123.0(5) . . ?
N1 C2 C3 123.0(5) 14_665 . ?
N1 C1 C1 107.6(7) . 14_665 ?
N1 C1 H1 126.2 . . ?
C1 C1 H1 126.2 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N4 N5 N4 173(9) 2_665 . ?
N2 N3 N3 0.000(3) . 3_655 ?
N12 N11 N12 86(10) 12_654 . ?
N12 N11 N12 86(10) 12_654 6_665 ?
N12 N11 N12 86(10) 6_665 . ?
N12 N11 N10 152(10) 12_654 12_654 ?
N12 N11 N10 152(10) 6_665 6_665 ?
N12 N11 N10 74(10) 12_654 6_665 ?
N12 N11 N10 74(10) 6_665 12_654 ?
N12 N11 N10 74(10) . 12_654 ?
N12 N11 N10 74(10) . 6_665 ?
N10 N11 N10 117(10) . 6_665 ?
N10 N11 N10 117(10) . 12_654 ?
N10 N11 N10 117(10) 12_654 6_665 ?
N11 N12 N12 47(10) . 6_665 ?
N11 N12 N12 47(10) . 12_654 ?
N12 N12 N12 59.99(3) 12_654 6_665 ?
N15 N13 N15 112(9) 12_654 . ?
N15 N13 N15 112(9) 6_665 . ?
N15 N13 N15 112(9) 6_665 12_654 ?
N11 N10 N10 32(7) . 12_654 ?
N11 N10 N10 136(10) . 2_665 ?
N11 N10 N10 32(7) . 6_665 ?
N10 N10 N10 119.998(12) 6_665 2_665 ?
N10 N10 N10 60.000(16) 12_654 6_665 ?
N10 N10 N10 119.998(15) 12_654 2_665 ?
N13 N15 N15 34(5) . 6_665 ?
N13 N15 N15 34(5) . 12_654 ?
N15 N15 N15 60.000(14) 6_665 12_654 ?
N3 N2 N3 180.000(17) . 3_655 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.2(5) . . . 14_665 ?
Co1 N1 C2 C3 -2.9(18) . . . . ?
Co1 N1 C1 C1 -173.0(6) . . . 14_665 ?
C2 N1 C1 C1 -0.4(9) . . . 14_665 ?
C1 N1 C2 N1 0.7(16) . . . 14_665 ?
C1 N1 C2 C3 -175.4(13) . . . . ?
N12 N11 N12 N12 86(24) 12_654 . . 6_665 ?
N12 N11 N12 N12 -86(24) 6_665 . . 12_654 ?
N10 N11 N10 N10 144(70) 6_665 . . 12_654 ?
N10 N11 N10 N10 72(35) 6_665 . . 2_665 ?
N10 N11 N10 N10 -144(70) 12_654 . . 6_665 ?
N10 N11 N10 N10 -72(35) 12_654 . . 2_665 ?
N15 N13 N15 N15 -126(27) 12_654 . . 6_665 ?
N15 N13 N15 N15 126(27) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 40.717
_oxdiff_exptl_absorpt_empirical_full_min 0.408
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_1600
_database_code_depnum_ccdc_archive 'CCDC 2299162'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_1600      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_ln2_1600      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.02 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_1600      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error.
;
_vrf_PLAT090_zif67_ln2_1600      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       6.33 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments.
;
_vrf_PLAT202_zif67_ln2_1600      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          7 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT723_zif67_ln2_1600      
;
PROBLEM: Torsion Calc     -139.00, Rep    -137(63) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_1600_2    
;
PROBLEM: Torsion Calc      139.00, Rep     137(63) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 18(N0.5)'
_chemical_formula_sum            'C8 H10 Co N13'
_chemical_formula_weight         347.22
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 1.59 GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.9247(6)
_cell_length_b                   16.9247(6)
_cell_length_c                   16.9247(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4848.0(5)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1908
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.7650
_cell_measurement_theta_min      3.3910
_shelx_estimated_absorpt_T_max   0.909
_shelx_estimated_absorpt_T_min   0.864
_exptl_absorpt_coefficient_mu    1.080
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.5158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1139 before and 0.0835 after correction.
The Ratio of minimum to maximum transmission is 0.6928.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2112
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0942
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5113
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        20.799
_diffrn_reflns_theta_max         20.799
_diffrn_reflns_theta_min         3.405
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -37.00  29.00   0.50   75.00    --  -24.44 -52.00  38.00  132
  2  ω    -27.00  -3.00   0.50   75.00    --   24.20  19.00-150.00   48
  3  ω    -23.00  16.00   0.50   75.00    --   24.20  67.00 -23.00   78
  4  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 150.00   40
  5  ω     -4.00  18.00   0.50   75.00    --  -24.44 -57.00  30.00   44
  6  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 -30.00   40
  7  ω    -36.00 -16.00   0.50   75.00    --   24.20  38.00  30.00   40
  8  ω     30.00  55.00   0.50   75.00    --   24.20 -99.00  30.00   50
  9  ω     30.00  71.00   0.50   75.00    --   24.20 -99.00-150.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0150047000
_diffrn_orient_matrix_UB_12      0.0070899000
_diffrn_orient_matrix_UB_13      -0.0384553000
_diffrn_orient_matrix_UB_21      0.0041370000
_diffrn_orient_matrix_UB_22      0.0412825000
_diffrn_orient_matrix_UB_23      0.0059706000
_diffrn_orient_matrix_UB_31      0.0389285000
_diffrn_orient_matrix_UB_32      -0.0016528000
_diffrn_orient_matrix_UB_33      -0.0154844000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                458
_reflns_number_total             501
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.730
_refine_diff_density_min         -0.831
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details 
;
 Flack x determined using 172 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     45
_refine_ls_number_reflns         501
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0867
_refine_ls_R_factor_gt           0.0816
_refine_ls_restrained_S_all      1.149
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1666P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2091
_refine_ls_wR_factor_ref         0.2136
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C3
 1.55 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.01
 N1-C1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N4-N5
 1.08 with sigma of 0.02
 N9-N8
 1.09 with sigma of 0.02
3. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C1) = Uanis(C2)
Uiso(N11) = Uiso(N10)
Uiso(N6) = Uiso(N7)
Uiso(N4) = Uiso(N5)
5. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N2(0.083333) N3(0.166667) N6(0.041667)
 N4(0.25) N7(0.125) N10(0.083333) N11(0.083333)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0353(16) Uani 1 4 d S T P . .
N1 N 0.5869(6) 0.3198(6) 0.0361(5) 0.038(2) Uani 1 1 d D . . . .
C2 C 0.6326(6) 0.3674(6) -0.0070(8) 0.038(2) Uani 1 2 d DS T P . .
C1 C 0.6045(8) 0.3380(9) 0.1139(6) 0.038(2) Uani 1 1 d D . . . .
H1 H 0.577882 0.311749 0.165415 0.045 Uiso 1 1 calc R U . . .
C3 C 0.6275(9) 0.3725(9) -0.0953(12) 0.043(6) Uani 1 2 d DS T P . .
H3A H 0.670278 0.414994 -0.116748 0.065 Uiso 0.5 1 calc R U P A -1
H3B H 0.639801 0.315125 -0.120776 0.065 Uiso 0.5 1 calc R U P A -1
H3C H 0.568639 0.391163 -0.112232 0.065 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.061(19) Uiso 0.6666 8 d S . P . .
N5 N 0.500000 0.500000 -0.232(2) 0.117(11) Uiso 1 4 d DS . P . .
N8 N 0.7794(13) 0.2206(13) 0.0709(19) 0.131(11) Uiso 1 2 d DS . P . .
N3 N 0.500000 0.500000 -0.036(3) 0.078(11) Uiso 0.6667 4 d S . P . .
N9 N 0.7648(14) 0.2352(14) 0.017(2) 0.130(12) Uiso 1 2 d DS . P . .
N6 N 0.768(6) 0.232(6) -0.232(6) 0.074(14) Uiso 0.25 6 d S . P . .
N4 N 0.5439(11) 0.4561(11) -0.229(4) 0.117(11) Uiso 0.5 2 d DS . P . .
N7 N 0.749(3) 0.251(3) -0.251(3) 0.074(14) Uiso 0.75 6 d S . P . .
N10 N 0.576(4) 0.424(4) -0.424(4) 0.07(3) Uiso 0.5 6 d S . P . .
N11 N 0.603(9) 0.445(7) -0.445(7) 0.07(3) Uiso 0.1667 2 d S . P . .
N12 N 0.8758(19) 0.1242(19) -0.1242(19) 0.14(2) Uiso 1 6 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.984(9) 46 ?
Co1 N1 1.984(9) . ?
Co1 N1 1.984(9) 48_554 ?
Co1 N1 1.984(9) 3_655 ?
N1 C2 1.333(10) . ?
N1 C1 1.385(11) . ?
C2 C3 1.50(2) . ?
C1 C1 1.38(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.61(5) 3_655 ?
N2 N3 0.61(5) . ?
N5 N4 1.05(3) . ?
N5 N4 1.05(3) 2_665 ?
N8 N9 0.98(2) . ?
N3 N3 1.22(10) 3_655 ?
N6 N7 0.57(19) . ?
N10 N11 0.67(15) . ?
N10 N11 0.67(15) 6_665 ?
N10 N11 0.67(15) 12_654 ?
N11 N11 1.1(2) 6_665 ?
N11 N11 1.1(2) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 106.9(6) 46 48_554 ?
N1 Co1 N1 110.8(3) 48_554 . ?
N1 Co1 N1 110.8(3) 46 . ?
N1 Co1 N1 110.8(3) 46 3_655 ?
N1 Co1 N1 110.8(3) 48_554 3_655 ?
N1 Co1 N1 106.9(6) 3_655 . ?
C2 N1 Co1 128.4(7) . . ?
C2 N1 C1 105.2(9) . . ?
C1 N1 Co1 125.8(8) . . ?
N1 C2 N1 113.6(11) . 14_665 ?
N1 C2 C3 123.1(6) 14_665 . ?
N1 C2 C3 123.1(6) . . ?
N1 C1 H1 126.0 . . ?
C1 C1 N1 108.0(7) 14_665 . ?
C1 C1 H1 126.0 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.0 3_655 . ?
N4 N5 N4 175(10) 2_665 . ?
N2 N3 N3 0.000(4) . 3_655 ?
N11 N10 N11 115(10) 6_665 12_654 ?
N11 N10 N11 115(10) 12_654 . ?
N11 N10 N11 115(10) 6_665 . ?
N10 N11 N11 32(8) . 6_665 ?
N10 N11 N11 32(8) . 12_654 ?
N11 N11 N11 60.00(3) 6_665 12_654 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.1(5) . . . 14_665 ?
Co1 N1 C2 C3 -3(2) . . . . ?
Co1 N1 C1 C1 -172.6(6) . . . 14_665 ?
C2 N1 C1 C1 -1.2(10) . . . 14_665 ?
C1 N1 C2 N1 2.1(18) . . . 14_665 ?
C1 N1 C2 C3 -174.5(13) . . . . ?
N11 N10 N11 N11 -137(63) 12_654 . . 6_665 ?
N11 N10 N11 N11 137(63) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 7.228
_oxdiff_exptl_absorpt_empirical_full_min 0.666
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_2750
_database_code_depnum_ccdc_archive 'CCDC 2299165'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_2750      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_ln2_2750      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0195 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT430_zif67_ln2_2750      
;
PROBLEM: Short Inter D...A Contact  N4       ..N10      .       2.68 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2750_2    
;
PROBLEM: Short Inter D...A Contact  N8       ..N6       .       2.86 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT987_zif67_ln2_2750      
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_PLAT018_zif67_ln2_2750      
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_ln2_2750      
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.978 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_2750      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error
;
_vrf_PLAT090_zif67_ln2_2750      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       7.35 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments.
;
_vrf_PLAT202_zif67_ln2_2750      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          6 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically
;
_vrf_PLAT723_zif67_ln2_2750      
;
PROBLEM: Torsion Calc      113.00, Rep     115(40) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 18.667(N0.5)'
_chemical_formula_sum            'C8 H10 Co N13.33'
_chemical_formula_weight         351.89
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 2.75GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.6284(4)
_cell_length_b                   16.6284(4)
_cell_length_c                   16.6284(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4597.8(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    3710
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.0470
_cell_measurement_theta_min      3.4470
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.140
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0907 before and 0.0782 after correction.
The Ratio of minimum to maximum transmission is 0.8509.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2140
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0743
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8667
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        23.207
_diffrn_reflns_theta_max         23.207
_diffrn_reflns_theta_min         3.465
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -47.00  32.00   0.50   60.00    --   13.12  26.00  -8.00  158
  2  ω    -96.00 -68.00   0.50   60.00    --   13.12-178.00  90.00   56
  3  ω    -22.00  57.00   0.50   60.00    --   13.12 -53.00-162.00  158
  4  ω     -3.00  76.00   0.50   60.00    --   13.12 -97.00-143.00  158
  5  ω    -27.00  -3.00   0.50   60.00    --   13.12  19.00-150.00   48
  6  ω    -96.00 -68.00   0.50   60.00    --   13.12-178.00 -90.00   56
  7  ω    -61.00  16.00   0.50   60.00    --  -13.27  67.00 -23.00  154
  8  ω    -12.00  40.00   0.50   60.00    --  -13.27 -53.00-162.00  104
  9  ω     32.00  58.00   0.50   60.00    --  -13.27-114.00-135.00   52
 10  ω    -38.00 -13.00   0.50   60.00    --  -13.27  77.00 -30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0390816000
_diffrn_orient_matrix_UB_12      0.0152303000
_diffrn_orient_matrix_UB_13      0.0076773000
_diffrn_orient_matrix_UB_21      -0.0065473000
_diffrn_orient_matrix_UB_22      -0.0043421000
_diffrn_orient_matrix_UB_23      0.0419340000
_diffrn_orient_matrix_UB_31      0.0157898000
_diffrn_orient_matrix_UB_32      -0.0395993000
_diffrn_orient_matrix_UB_33      -0.0016444000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.754
_reflns_Friedel_fraction_full    0.940
_reflns_Friedel_fraction_max     0.940
_reflns_number_gt                491
_reflns_number_total             619
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.848
_refine_diff_density_min         -0.811
_refine_diff_density_rms         0.153
_refine_ls_abs_structure_details 
;
 Flack x determined using 180 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.178
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     49
_refine_ls_number_reflns         619
_refine_ls_number_restraints     11
_refine_ls_R_factor_all          0.1064
_refine_ls_R_factor_gt           0.0871
_refine_ls_restrained_S_all      1.207
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1508P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2123
_refine_ls_wR_factor_ref         0.2224
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-C2
 1.55 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.01
 C1-N1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N9-N8
 1.08 with sigma of 0.02
 N4-N5
 1.08 with sigma of 0.02
 N8-N9
 1.09 with sigma of 0.02
3. Restrained planarity
 C1, C2, N1, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C2) = Uanis(N1)
Uiso(N15) = Uiso(N13)
Uiso(N4) = Uiso(N5)
Uiso(N3) = Uiso(N2)
Uiso(N6) = Uiso(N7)
Uiso(N9) = Uiso(N8)
5. Rigid body (RIGU) restrains
 C3, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N2(0.083333) N3(0.166667) N6(0.05555)
 N4(0.25) N11(0.083333) N12(0.083333) N7(0.11112) N13(0.083333) N10(0.083333)
 N15(0.08335)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0361(14) Uani 1 4 d S T P . .
N1 N 0.5855(6) 0.3196(6) 0.0409(5) 0.037(2) Uani 1 1 d D . . . .
C2 C 0.6326(6) 0.3674(6) -0.0033(8) 0.037(2) Uani 1 2 d DS T P . .
C1 C 0.6027(8) 0.3383(8) 0.1199(6) 0.037(2) Uani 1 1 d D . . . .
H1 H 0.575226 0.311805 0.172268 0.044 Uiso 1 1 calc R U . . .
C3 C 0.6284(8) 0.3716(8) -0.0945(11) 0.046(5) Uani 1 2 d DS T P . .
H3A H 0.672321 0.414466 -0.116286 0.068 Uiso 0.5 1 calc R U P A -1
H3B H 0.641197 0.312818 -0.119508 0.068 Uiso 0.5 1 calc R U P A -1
H3C H 0.568785 0.390413 -0.112655 0.068 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.060(7) Uiso 0.6666 8 d S . P . .
N5 N 0.500000 0.500000 -0.232(2) 0.122(11) Uiso 1 4 d DS . P . .
N8 N 0.7839(12) 0.2161(12) 0.0779(17) 0.122(7) Uiso 1 2 d DS . P . .
N3 N 0.500000 0.500000 -0.0393(17) 0.060(7) Uiso 0.6667 4 d S . P . .
N9 N 0.7631(12) 0.2369(12) 0.0249(17) 0.122(7) Uiso 1 2 d DS . P . .
N6 N 0.745(4) 0.255(4) -0.255(4) 0.064(11) Uiso 0.3333 6 d S . P . .
N4 N 0.5441(11) 0.4559(11) -0.229(4) 0.122(11) Uiso 0.5 2 d DS . P . .
N11 N 0.585(5) 0.415(5) -0.415(5) 0.09(4) Uiso 0.5 6 d S . P . .
N12 N 0.576(3) 0.424(3) -0.461(6) 0.04(3) Uiso 0.1667 2 d S . P B 2
N7 N 0.7643(17) 0.2357(17) -0.2357(17) 0.064(11) Uiso 0.6667 6 d S . P . .
N13 N 0.876(3) 0.124(3) -0.124(3) 0.07(2) Uiso 0.5 6 d S . P . .
N10 N 0.556(7) 0.444(7) -0.389(10) 0.08(4) Uiso 0.1667 2 d S . P B 1
N15 N 0.835(8) 0.116(6) -0.116(6) 0.07(2) Uiso 0.1667 2 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.955(9) 46 ?
Co1 N1 1.955(9) 48_554 ?
Co1 N1 1.955(9) 3_655 ?
Co1 N1 1.955(9) . ?
N1 C2 1.336(9) . ?
N1 C1 1.380(10) . ?
C2 C3 1.52(2) . ?
C1 C1 1.39(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.65(3) 3_655 ?
N2 N3 0.65(3) . ?
N5 N4 1.04(3) . ?
N5 N4 1.04(3) 2_665 ?
N8 N9 1.009(18) . ?
N3 N3 1.31(6) 3_655 ?
N6 N7 0.56(12) . ?
N11 N12 0.79(10) 20 ?
N11 N12 0.79(10) 6_665 ?
N11 N12 0.79(10) 14_665 ?
N11 N12 0.79(10) 12_654 ?
N11 N12 0.79(10) . ?
N11 N12 0.79(10) 21_654 ?
N11 N10 0.80(18) 12_654 ?
N11 N10 0.80(17) 6_665 ?
N11 N10 0.80(17) 14_665 ?
N11 N10 0.80(17) . ?
N13 N15 0.70(13) 6_665 ?
N13 N15 0.70(13) 12_654 ?
N13 N15 0.70(13) . ?
N10 N10 1.3(3) 12_654 ?
N15 N15 1.1(2) 12_654 ?
N15 N15 1.1(2) 6_665 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.5(3) 46 3_655 ?
N1 Co1 N1 107.4(6) 3_655 . ?
N1 Co1 N1 110.5(3) 46 . ?
N1 Co1 N1 107.4(6) 46 48_554 ?
N1 Co1 N1 110.5(3) 48_554 . ?
N1 Co1 N1 110.5(3) 3_655 48_554 ?
C2 N1 Co1 125.9(6) . . ?
C2 N1 C1 105.6(9) . . ?
C1 N1 Co1 128.0(8) . . ?
N1 C2 N1 113.2(11) . 14_665 ?
N1 C2 C3 123.3(6) . . ?
N1 C2 C3 123.3(6) 14_665 . ?
N1 C1 C1 107.8(7) . 14_665 ?
N1 C1 H1 126.1 . . ?
C1 C1 H1 126.1 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.0 . 3_655 ?
N4 N5 N4 174(9) . 2_665 ?
N2 N3 N3 0.000(2) . 3_655 ?
N12 N11 N12 67(10) . 20 ?
N12 N11 N12 67(10) . 21_654 ?
N12 N11 N12 67(10) 14_665 20 ?
N12 N11 N12 67(10) 14_665 6_665 ?
N12 N11 N12 0(10) 6_665 21_654 ?
N12 N11 N12 67(10) . 6_665 ?
N12 N11 N12 67(10) 14_665 21_654 ?
N12 N11 N12 67(10) 21_654 20 ?
N12 N11 N12 0(10) 14_665 . ?
N12 N11 N12 67(10) 6_665 20 ?
N12 N11 N10 55(10) 14_665 12_654 ?
N12 N11 N10 55(10) 12_654 6_665 ?
N12 N11 N10 55(10) . 6_665 ?
N12 N11 N10 55(10) . 12_654 ?
N12 N11 N10 55(10) 20 14_665 ?
N12 N11 N10 55(10) 6_665 12_654 ?
N12 N11 N10 108(10) 21_654 6_665 ?
N12 N11 N10 55(10) 21_654 12_654 ?
N12 N11 N10 55(10) 21_654 14_665 ?
N12 N11 N10 108(10) 20 12_654 ?
N12 N11 N10 55(10) 12_654 14_665 ?
N12 N11 N10 108(10) 12_654 12_654 ?
N12 N11 N10 108(10) 6_665 6_665 ?
N12 N11 N10 108(10) 14_665 14_665 ?
N12 N11 N10 55(10) 20 6_665 ?
N12 N11 N10 108(10) . 14_665 ?
N12 N11 N10 55(10) 6_665 14_665 ?
N12 N11 N10 55(10) 14_665 6_665 ?
N10 N11 N10 0(10) . 14_665 ?
N10 N11 N10 107(10) 12_654 14_665 ?
N10 N11 N10 107(10) 14_665 6_665 ?
N10 N11 N10 107(10) 12_654 . ?
N10 N11 N10 107(10) 12_654 6_665 ?
N10 N11 N10 107(10) . 6_665 ?
N15 N13 N15 110(10) 6_665 . ?
N15 N13 N15 110(10) 12_654 . ?
N15 N13 N15 110(10) 6_665 12_654 ?
N11 N10 N10 36(9) . 12_654 ?
N13 N15 N15 35(8) . 12_654 ?
N13 N15 N15 35(8) . 6_665 ?
N15 N15 N15 60.00(2) 6_665 12_654 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.5(5) . . . 14_665 ?
Co1 N1 C2 C3 -2.9(18) . . . . ?
Co1 N1 C1 C1 -172.7(6) . . . 14_665 ?
C2 N1 C1 C1 -0.8(9) . . . 14_665 ?
C1 N1 C2 N1 1.5(16) . . . 14_665 ?
C1 N1 C2 C3 -175.0(12) . . . . ?
N10 N11 N10 N10 115(40) 6_665 . . 12_654 ?
N10 N11 N10 N10 0(100) 14_665 . . 12_654 ?
N15 N13 N15 N15 -120(42) 12_654 . . 6_665 ?
N15 N13 N15 N15 120(42) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.631
_oxdiff_exptl_absorpt_empirical_full_min 0.666
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_700p
_database_code_depnum_ccdc_archive 'CCDC 2299168'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 1.521(N4)'
_chemical_formula_sum            'C8 H10 Co N10.08'
_chemical_formula_weight         306.36
_chemical_absolute_configuration .
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 0.7 GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   17.0740(4)
_cell_length_b                   17.0740(4)
_cell_length_c                   17.0740(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4977.4(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    2043
_cell_measurement_temperature    293
_cell_measurement_theta_max      23.2390
_cell_measurement_theta_min      3.3520
_shelx_estimated_absorpt_T_max   0.912
_shelx_estimated_absorpt_T_min   0.868
_exptl_absorpt_coefficient_mu    1.038
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.4402
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1171 before and 0.0857 after correction.
The Ratio of minimum to maximum transmission is 0.5910.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1867
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0825
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4014
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        18.729
_diffrn_reflns_theta_max         18.729
_diffrn_reflns_theta_min         3.375
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -37.00  29.00   0.50   75.00    --  -24.44 -53.00  39.00  132
  2  ω     68.00 106.00   0.50   75.00    --   24.20-178.00  90.00   76
  3  ω     -4.00  18.00   0.50   75.00    --   24.20 -57.00  60.00   44
  4  ω    -18.00   4.00   0.50   75.00    --   24.20  57.00   0.00   44
  5  ω     -4.00  18.00   0.50   75.00    --  -24.44 -57.00  30.00   44
  6  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 -30.00   40
  7  ω    -30.00  10.00   0.50   75.00    --   24.20  82.00 -29.00   80
  8  ω     30.00  55.00   0.50   75.00    --   24.20 -99.00-150.00   50
  9  ω    -36.00 -16.00   0.50   75.00    --  -24.44  38.00 150.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0382768000
_diffrn_orient_matrix_UB_12      -0.0067060000
_diffrn_orient_matrix_UB_13      -0.0147251000
_diffrn_orient_matrix_UB_21      0.0056949000
_diffrn_orient_matrix_UB_22      -0.0409565000
_diffrn_orient_matrix_UB_23      0.0039480000
_diffrn_orient_matrix_UB_31      -0.0152184000
_diffrn_orient_matrix_UB_32      0.0015992000
_diffrn_orient_matrix_UB_33      0.0386108000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                373
_reflns_number_total             391
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.624
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details 
;
 Flack x determined using 153 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.249
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     47
_refine_ls_number_reflns         391
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0707
_refine_ls_R_factor_gt           0.0675
_refine_ls_restrained_S_all      1.248
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1473P)²+11.5625P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2079
_refine_ls_wR_factor_ref         0.2103
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C3
 1.55 with sigma of 0.02
 N1-C1
 1.387 with sigma of 0.01
 N1-C2
 1.337 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
3. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C1) = Uanis(C2)
5. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N5(0.1875) N8(0.25) N3(0.125) N9(0.25)
 N6(0.05556) N4(0.25) N7(0.11112) N10(0.083333) N11(0.083333)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.042(2) Uani 1 4 d S T P . .
N1 N 0.5873(7) 0.3195(8) 0.0331(6) 0.051(4) Uani 1 1 d D . . . .
C2 C 0.6322(8) 0.3678(8) -0.0098(9) 0.051(4) Uani 1 2 d DS T P . .
C1 C 0.6071(11) 0.3366(12) 0.1100(7) 0.051(4) Uani 1 1 d D . . . .
H1 H 0.582048 0.309636 0.161219 0.062 Uiso 1 1 calc R U . . .
C3 C 0.6283(15) 0.3717(15) -0.0984(14) 0.075(11) Uani 1 2 d DS T P . .
H3A H 0.669805 0.414767 -0.119477 0.113 Uiso 0.5 1 calc R U P A -1
H3B H 0.642523 0.314896 -0.122665 0.113 Uiso 0.5 1 calc R U P A -1
H3C H 0.569718 0.388291 -0.116244 0.113 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.17(4) Uiso 1 8 d S . P . .
N5 N 0.500000 0.500000 -0.233(6) 0.15(4) Uiso 0.75 4 d S . P . .
N8 N 0.781(3) 0.219(3) 0.070(4) 0.10(2) Uiso 0.5 2 d S . P . .
N3 N 0.500000 0.500000 -0.046(5) 0.10(2) Uiso 0.5 4 d S . P . .
N9 N 0.779(2) 0.221(2) 0.028(4) 0.09(2) Uiso 0.5 2 d S . P . .
N6 N 0.818(6) 0.182(6) -0.182(6) 0.12(5) Uiso 0.3334 6 d S . P . .
N4 N 0.508(8) 0.454(5) -0.233(6) 0.13(3) Uiso 0.25 1 d . . P . .
N7 N 0.766(4) 0.234(4) -0.234(4) 0.15(4) Uiso 0.6667 6 d S . P . .
N10 N 0.927(6) 0.073(6) 0.073(6) 0.13(6) Uiso 0.5 6 d S . P . .
N11 N 0.916(9) 0.084(9) 0.033(12) 0.10(7) Uiso 0.1667 2 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.987(11) 46 ?
Co1 N1 1.987(11) . ?
Co1 N1 1.987(11) 3_655 ?
Co1 N1 1.987(11) 48_554 ?
N1 C2 1.344(11) . ?
N1 C1 1.386(13) . ?
C2 C3 1.51(2) . ?
C1 C1 1.36(4) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.79(8) . ?
N2 N3 0.79(8) 3_655 ?
N5 N4 0.80(10) 13 ?
N5 N4 0.80(10) 14_665 ?
N5 N4 0.80(10) . ?
N5 N4 0.80(10) 2_665 ?
N8 N9 0.72(7) . ?
N3 N3 1.58(17) 3_655 ?
N6 N7 1.53(18) . ?
N10 N11 0.7(2) 7_665 ?
N10 N11 0.7(2) . ?
N10 N11 0.7(2) 10_656 ?
N10 N11 0.7(2) 23_656 ?
N10 N11 0.7(2) 17 ?
N10 N11 0.7(2) 14_665 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.9(4) 46 3_655 ?
N1 Co1 N1 106.6(8) 3_655 . ?
N1 Co1 N1 110.9(4) 46 . ?
N1 Co1 N1 106.6(8) 46 48_554 ?
N1 Co1 N1 110.9(4) 3_655 48_554 ?
N1 Co1 N1 110.9(4) 48_554 . ?
C2 N1 Co1 129.7(8) . . ?
C2 N1 C1 104.4(11) . . ?
C1 N1 Co1 125.3(10) . . ?
N1 C2 N1 113.7(14) . 14_665 ?
N1 C2 C3 123.1(7) 14_665 . ?
N1 C2 C3 123.1(7) . . ?
N1 C1 H1 125.6 . . ?
C1 C1 N1 108.7(9) 14_665 . ?
C1 C1 H1 125.6 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.000(12) . 3_655 ?
N4 N5 N4 109(10) 13 . ?
N4 N5 N4 71(10) . 14_665 ?
N4 N5 N4 179(10) 13 14_665 ?
N4 N5 N4 71(10) 13 2_665 ?
N4 N5 N4 109(10) 2_665 14_665 ?
N4 N5 N4 179(10) . 2_665 ?
N2 N3 N3 0.000(5) . 3_655 ?
N11 N10 N11 115(10) 23_656 . ?
N11 N10 N11 115(10) 23_656 10_656 ?
N11 N10 N11 115(10) 7_665 . ?
N11 N10 N11 115(10) 10_656 . ?
N11 N10 N11 115(10) 14_665 10_656 ?
N11 N10 N11 115(10) 23_656 17 ?
N11 N10 N11 0(10) 10_656 17 ?
N11 N10 N11 0(10) 14_665 . ?
N11 N10 N11 0(10) 7_665 23_656 ?
N11 N10 N11 115(10) 7_665 17 ?
N11 N10 N11 115(10) 7_665 14_665 ?
N11 N10 N11 115(10) 14_665 17 ?
N11 N10 N11 115(10) 23_656 14_665 ?
N11 N10 N11 115(10) . 17 ?
N11 N10 N11 115(10) 7_665 10_656 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.2(6) . . . 14_665 ?
Co1 N1 C2 C3 -6(3) . . . . ?
Co1 N1 C1 C1 -172.9(8) . . . 14_665 ?
C2 N1 C1 C1 -1.0(14) . . . 14_665 ?
C1 N1 C2 N1 2(2) . . . 14_665 ?
C1 N1 C2 C3 -177.9(18) . . . . ?

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.026
_oxdiff_exptl_absorpt_empirical_full_min 0.617

# start Validation Reply Form
_vrf_THETM01_zif67_ln2_700p      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT090_zif67_ln2_700p      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       4.72 Note  
RESPONSE: The sample is shaded by the diamond anvil cell
preventing collection of reflections from multiple angles.
This is common in high pressure experiments.
;
_vrf_PLAT341_zif67_ln2_700p      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.03 Ang.  
RESPONSE: ZIF-67 has large pore volume which reduces resolution,
and is further shaded by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_700p      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check 
RESPONSE: Occupancy of N in pores are in different, disordered positions 
and do not add to integers,causing this particular error
;
_vrf_PLAT202_zif67_ln2_700p      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          3 Check 
RESPONSE: N atoms are too disordered to model with thermal parameters,
it is more appropriate to model them isotropically.
;
# end Validation Reply Form
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p1_w1_70s_00
_database_code_depnum_ccdc_archive 'CCDC 2299169'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p1_w1_70s_00  
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_p1_w1_70s_00  
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p1_w1_70s_00  
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in Olex2
;
_vrf_PLAT018_zif67_p1_w1_70s_00  
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p1_w1_70s_00  
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.962 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ZIF-67
_chemical_formula_moiety         'C8 H10 Co N4, 2.917[CH3OH]'
_chemical_formula_sum            'C10.92 H21.67 Co N4 O2.92'
_chemical_formula_weight         314.15
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H20 Co N4 O4'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   17.2086(4)
_cell_length_b                   17.2086(4)
_cell_length_c                   17.2086(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5096.1(4)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    676
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.1940
_cell_measurement_theta_min      1.6780
_shelx_estimated_absorpt_T_max   0.905
_shelx_estimated_absorpt_T_min   0.862
_exptl_absorpt_coefficient_mu    1.018
_exptl_absorpt_correction_T_max  0.7446
_exptl_absorpt_correction_T_min  0.6956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0591 before and 0.0472 after correction.
The Ratio of minimum to maximum transmission is 0.9342.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             1983
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0239
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            2148
_diffrn_reflns_point_group_measured_fraction_full 0.923
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        21.176
_diffrn_reflns_theta_max         21.176
_diffrn_reflns_theta_min         1.674
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -35.00  35.00   0.10    0.10   0.00   0.00   0.00    --   700
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0304634000
_diffrn_orient_matrix_UB_12      -0.0272955000
_diffrn_orient_matrix_UB_13      -0.0050157000
_diffrn_orient_matrix_UB_21      0.0114707000
_diffrn_orient_matrix_UB_22      -0.0055476000
_diffrn_orient_matrix_UB_23      -0.0392540000
_diffrn_orient_matrix_UB_31      0.0253010000
_diffrn_orient_matrix_UB_32      -0.0304516000
_diffrn_orient_matrix_UB_33      0.0116900000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    0.872
_reflns_Friedel_fraction_max     0.870
_reflns_number_gt                507
_reflns_number_total             515
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.129
_refine_diff_density_min         -0.097
_refine_diff_density_rms         0.020
_refine_ls_abs_structure_details 
;
 Flack x determined using 203 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.113(16)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         515
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0191
_refine_ls_R_factor_gt           0.0185
_refine_ls_restrained_S_all      1.123
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0294P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0516
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.34 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.16 with sigma of 0.01
 N1-C2
 1.34 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(N1) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0582(3) Uani 1 4 d S T P . .
N1 N 0.02852(14) -0.59079(16) -0.31671(14) 0.0682(6) Uani 1 1 d D . . . .
C2 C -0.0087(3) -0.62197(16) -0.37803(16) 0.0682(6) Uani 1 2 d DS T P . .
C1 C -0.0844(3) -0.5904(2) -0.4096(2) 0.0835(14) Uani 1 2 d DS T P . .
H1A H -0.104282 -0.626915 -0.456855 0.125 Uiso 0.5 1 calc R U P A -1
H1B H -0.075505 -0.531769 -0.430711 0.125 Uiso 0.5 1 calc R U P A -1
H1C H -0.127627 -0.589892 -0.363857 0.125 Uiso 0.5 1 calc R U P A -1
C3 C 0.09478(18) -0.63420(19) -0.30947(19) 0.0682(6) Uani 1 1 d D . . . .
H3 H 0.139535 -0.625524 -0.266590 0.082 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 2.000(2) 40_444 ?
Co1 N1 2.000(2) . ?
Co1 N1 2.000(2) 39_544 ?
Co1 N1 2.000(2) 2_545 ?
N1 C2 1.346(3) . ?
N1 C3 1.369(4) . ?
C2 C1 1.513(6) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.371(6) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 109.93(15) 40_444 39_544 ?
N1 Co1 N1 109.24(7) 39_544 . ?
N1 Co1 N1 109.24(7) 40_444 . ?
N1 Co1 N1 109.24(7) 40_444 2_545 ?
N1 Co1 N1 109.24(7) 39_544 2_545 ?
N1 Co1 N1 109.93(15) 2_545 . ?
C2 N1 Co1 130.2(2) . . ?
C2 N1 C3 104.5(3) . . ?
C3 N1 Co1 125.3(2) . . ?
N1 C2 N1 113.5(4) . 20_544 ?
N1 C2 C1 123.24(18) 20_544 . ?
N1 C2 C1 123.24(18) . . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 C3 108.75(18) . 20_544 ?
N1 C3 H3 125.6 . . ?
C3 C3 H3 125.6 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 179.61(13) . . . 20_544 ?
Co1 N1 C2 C1 0.5(6) . . . . ?
Co1 N1 C3 C3 -179.14(16) . . . 20_544 ?
C2 N1 C3 C3 -0.8(3) . . . 20_544 ?
C3 N1 C2 N1 1.4(5) . . . 20_544 ?
C3 N1 C2 C1 -177.7(4) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 3 7 9.048

_platon_squeeze_details          
;
TITL zif67_p1_w1_70s_00_a.res in I-43m
CELL   17.2086   17.2086   17.2086     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2628
# Electrons Found in S.A.V. =       617
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.202 0.796 0.205 !       1.52 eA-3
C102 1.000 1.000 0.000 !       1.50 eA-3
C103 0.793 0.961 0.222 !       1.05 eA-3
C104 0.491 0.313 0.313 !       0.87 eA-3
C105 0.709 0.657 0.342 !       0.85 eA-3
C106 1.000 1.001 0.234 !       0.78 eA-3
C107 0.837 1.007 0.154 !       0.77 eA-3
C108 0.261 0.730 0.270 !       0.65 eA-3
C109 0.356 0.356 0.356 !       0.62 eA-3
C110 0.221 0.045-0.003 !       0.62 eA-3
C111 0.010 0.016 0.182 !       0.56 eA-3
C112 0.843 0.845 0.155 !       0.54 eA-3
C113 0.139 0.139 0.139 !       0.52 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 618 electrons were 
found in a volume of 2607Å³ in 1 void per unit cell. 
This is consistent with the presence of 
2.917[CH3OH] per Unit Cell 
which account for 630 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.012 -0.007 -0.004 2607 618 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.272
_oxdiff_exptl_absorpt_empirical_full_min 0.612
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p2_w1_70s_0053
_database_code_depnum_ccdc_archive 'CCDC 2299170'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p2_w1_70s_0053 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p2_w1_70s_0053 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.940 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_p2_w1_70s_0053 
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p2_w1_70s_0053 
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in olex2
;
_vrf_PLAT341_zif67_p2_w1_70s_0053 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.012 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ZIF-67
_chemical_formula_moiety         'C8 H10 Co N4, 3.417[CH3OH]'
_chemical_formula_sum            'C11.75 H25 Co N4 O3.75'
_chemical_formula_weight         341.28
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H20 N4 Co O4'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   17.2230(4)
_cell_length_b                   17.2230(4)
_cell_length_c                   17.2230(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5108.9(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1304
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      21.6840
_cell_measurement_theta_min      2.3610
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.024
_exptl_absorpt_correction_T_max  0.7447
_exptl_absorpt_correction_T_min  0.4409
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1006 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.5921.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             2166
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.940
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            2030
_diffrn_reflns_point_group_measured_fraction_full 0.895
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        21.660
_diffrn_reflns_theta_max         21.660
_diffrn_reflns_theta_min         1.672
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.940
_diffrn_measured_fraction_theta_max 0.940
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0304342000
_diffrn_orient_matrix_UB_12      -0.0271846000
_diffrn_orient_matrix_UB_13      -0.0047920000
_diffrn_orient_matrix_UB_21      0.0114378000
_diffrn_orient_matrix_UB_22      -0.0058135000
_diffrn_orient_matrix_UB_23      -0.0391778000
_diffrn_orient_matrix_UB_31      0.0252057000
_diffrn_orient_matrix_UB_32      -0.0304046000
_diffrn_orient_matrix_UB_33      0.0118633000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    0.838
_reflns_Friedel_fraction_max     0.838
_reflns_number_gt                495
_reflns_number_total             531
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details 
;
 Flack x determined using 178 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.168
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         531
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0415
_refine_ls_restrained_S_all      1.183
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0651P)²+2.9959P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1183
_refine_ls_wR_factor_ref         0.1245
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.34 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.16 with sigma of 0.01
 N1-C2
 1.34 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(N1) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0803(8) Uani 1 4 d S T P . .
N1 N 0.0281(3) -0.5895(4) -0.3170(3) 0.0893(14) Uani 1 1 d D . . . .
C2 C -0.0097(6) -0.6210(3) -0.3790(3) 0.0893(14) Uani 1 2 d DS T P . .
C1 C -0.0841(6) -0.5889(6) -0.4111(6) 0.110(4) Uani 1 2 d DS T P . .
H1A H -0.128443 -0.590116 -0.366582 0.165 Uiso 0.5 1 calc R U P A -1
H1B H -0.102544 -0.623736 -0.460101 0.165 Uiso 0.5 1 calc R U P A -1
H1C H -0.074877 -0.529557 -0.429907 0.165 Uiso 0.5 1 calc R U P A -1
C3 C 0.0932(4) -0.6346(4) -0.3078(4) 0.0893(14) Uani 1 1 d D . . . .
H3 H 0.136991 -0.626960 -0.263791 0.107 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.985(6) 40_444 ?
Co1 N1 1.985(6) . ?
Co1 N1 1.985(6) 39_544 ?
Co1 N1 1.985(6) 2_545 ?
N1 C2 1.364(6) . ?
N1 C3 1.373(7) . ?
C2 C1 1.502(10) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.404(15) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 109.0(3) 40_444 39_544 ?
N1 Co1 N1 109.72(17) 39_544 . ?
N1 Co1 N1 109.72(17) 40_444 . ?
N1 Co1 N1 109.72(17) 40_444 2_545 ?
N1 Co1 N1 109.72(17) 39_544 2_545 ?
N1 Co1 N1 109.0(3) 2_545 . ?
C2 N1 Co1 130.4(4) . . ?
C2 N1 C3 104.8(6) . . ?
C3 N1 Co1 124.9(5) . . ?
N1 C2 N1 113.3(7) 20_544 . ?
N1 C2 C1 123.3(4) . . ?
N1 C2 C1 123.3(4) 20_544 . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 C3 108.6(4) . 20_544 ?
N1 C3 H3 125.7 . . ?
C3 C3 H3 125.7 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 -179.9(3) . . . 20_544 ?
Co1 N1 C2 C1 2.2(14) . . . . ?
Co1 N1 C3 C3 179.7(4) . . . 20_544 ?
C2 N1 C3 C3 0.5(6) . . . 20_544 ?
C3 N1 C2 N1 -0.8(11) . . . 20_544 ?
C3 N1 C2 C1 -178.7(10) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 0 4 4.734

_platon_squeeze_details          
;
TITL zif67_p2_w1_70s_0053_a.res in I-43m
CELL   17.2230   17.2230   17.2230     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2643
# Electrons Found in S.A.V. =       791
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.795 0.205 0.205 !       1.43 eA-3
C102 0.206 0.222 0.009 !       1.39 eA-3
C103 1.000 1.000 0.000 !       1.34 eA-3
C104 0.717 0.661 0.339 !       1.08 eA-3
C105 0.203 0.201 0.109 !       1.00 eA-3
C106 0.500 0.500 0.235 !       0.99 eA-3
C107 0.029 0.232 0.040 !       0.97 eA-3
C108 0.973 0.231 0.027 !       0.95 eA-3
C109 0.337 0.307 0.468 !       0.89 eA-3
C110 0.640 0.360 0.360 !       0.88 eA-3
C111 0.355 0.538 0.292 !       0.88 eA-3
C112 0.803 0.027 0.854 !       0.88 eA-3
C113 0.519 0.662 0.687 !       0.86 eA-3
C114 0.812 0.809 0.078 !       0.83 eA-3
C115 0.195 0.852 0.202 !       0.81 eA-3
C116 0.908 0.796 0.012 !       0.80 eA-3
C117 1.000 1.007 0.188 !       0.75 eA-3
C118 0.183 0.063 0.062 !       0.72 eA-3
C119 0.271 0.740 0.261 !       0.71 eA-3
Q120 1.007 0.282 0.060 !       0.69 eA-3
C121 0.292 0.059 0.059 !       0.69 eA-3
C122 0.349 0.662 0.338 !       0.66 eA-3
C123 0.250 0.258 0.031 !       0.63 eA-3
C124 0.331 0.324 0.409 !       0.63 eA-3
Q125 0.202 0.315 0.315 !       0.58 eA-3
C126 0.531 0.525 0.390 !       0.58 eA-3
C127 0.079 0.847 0.232 !       0.54 eA-3
C128 0.359 0.702 0.359 !       0.53 eA-3
C129 0.672 0.593 0.396 !       0.52 eA-3
C130 0.240 0.530 0.374 !       0.52 eA-3
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.012 -0.006 -0.003 2623 794 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.269
_oxdiff_exptl_absorpt_empirical_full_min 0.479
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_2300
_database_code_depnum_ccdc_archive 'CCDC 2299164'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_2300      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT090_zif67_ln2_2300      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       5.71 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments
;
_vrf_PLAT341_zif67_ln2_2300      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.019 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT430_zif67_ln2_2300      
;
PROBLEM: Short Inter D...A Contact  N4       ..N10      .       2.60 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2300_2    
;
PROBLEM: Short Inter D...A Contact  N5       ..N10      .       2.70 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2300_3    
;
PROBLEM: Short Inter D...A Contact  N5       ..N10      .       2.70 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT018_zif67_ln2_2300      
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_2300      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error
;
_vrf_PLAT202_zif67_ln2_2300      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          7 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT723_zif67_ln2_2300      
;
PROBLEM: Torsion Calc     -104.00, Rep    -106(51) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_2300_2    
;
PROBLEM: Torsion Calc      104.00, Rep     106(51) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 2.458(N4)'
_chemical_formula_sum            'C8 H10 Co N13.83'
_chemical_formula_weight         358.89
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 2.3 GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.7265(4)
_cell_length_b                   16.7265(4)
_cell_length_c                   16.7265(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4679.7(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    4140
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.7590
_cell_measurement_theta_min      3.4170
_shelx_estimated_absorpt_T_max   0.906
_shelx_estimated_absorpt_T_min   0.859
_exptl_absorpt_coefficient_mu    1.123
_exptl_absorpt_correction_T_max  0.7446
_exptl_absorpt_correction_T_min  0.6284
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1012 before and 0.0855 after correction.
The Ratio of minimum to maximum transmission is 0.8439.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2182
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0856
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            11050
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        20.825
_diffrn_reflns_theta_max         20.825
_diffrn_reflns_theta_min         3.445
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -73.00 -34.00   0.50   58.04    --   24.20 -28.00 -95.00   78
  2  ω     63.00  88.00   0.50   58.04    --   24.20  28.00  65.00   50
  3  ω    -89.00 -64.00   0.50   58.04    --  -24.44 -28.00 -95.00   50
  4  ω     74.00 104.00   0.50   58.04    --   24.20 178.00  90.00   60
  5  ω     33.00  63.00   0.50   58.04    --   24.20 -99.00-150.00   60
  6  ω     73.00 104.00   0.50   58.04    --   24.20 178.00 -90.00   62
  7  ω    -29.00  -9.00   0.50   58.04    --   24.20  77.00-180.00   40
  8  ω    -29.00  -9.00   0.50   58.04    --   24.20  77.00 -30.00   40
  9  ω    -40.00  -5.00   0.50   58.04    --   24.20 114.00 -45.00   70
 10  ω     -2.00  32.00   0.50   58.04    --   24.20  26.00  -8.00   68
 11  ω   -128.00-104.00   0.50   58.04    --  -24.44 -77.00-180.00   48
 12  ω     20.00  46.00   0.50   58.04    --  -24.44 -40.00-167.00   52
 13  ω    -36.00  -5.00   0.50   58.04    --  -24.44  97.00 -35.00   62
 14  ω    -76.00 -48.00   0.50   58.04    --  -24.44  97.00 -35.00   56
 15  ω    -26.00   0.00   0.50   58.04    --  -24.44 -26.00-171.00   52
 16  ω      0.00  26.00   0.50   58.04    --  -24.44 -82.00-151.00   52
 17  ω    -56.00  12.00   0.50   58.04    --  -24.44  53.00 -17.00  136
 18  ω    -72.00 -46.00   0.50   58.04    --  -24.44  77.00-180.00   52
 19  ω    -57.00 -31.00   0.50   58.04    --  -24.44  57.00-180.00   52
 20  ω    -18.00  28.00   0.50   58.04    --  -24.44 -53.00-162.00   92
 21  ω    -39.00 -13.00   0.50   58.04    --  -24.44  13.00  -3.00   52
 22  ω     21.00  48.00   0.50   58.04    --  -24.44-114.00-135.00   54
 23  ω      9.00  35.00   0.50   58.04    --  -24.44-114.00  45.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0150193000
_diffrn_orient_matrix_UB_12      0.0071976000
_diffrn_orient_matrix_UB_13      0.0389868000
_diffrn_orient_matrix_UB_21      -0.0041016000
_diffrn_orient_matrix_UB_22      0.0417617000
_diffrn_orient_matrix_UB_23      -0.0061245000
_diffrn_orient_matrix_UB_31      -0.0394224000
_diffrn_orient_matrix_UB_32      -0.0016049000
_diffrn_orient_matrix_UB_33      0.0155629000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.773
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                458
_reflns_number_total             491
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.895
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details 
;
 Flack x determined using 192 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     49
_refine_ls_number_reflns         491
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0788
_refine_ls_R_factor_gt           0.0744
_refine_ls_restrained_S_all      1.210
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1547P)²+0.2984P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1887
_refine_ls_wR_factor_ref         0.1935
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-C2
 1.55 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.01
 C1-N1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N9-N8
 1.08 with sigma of 0.02
 N4-N5
 1.08 with sigma of 0.02
3. Restrained planarity
 C1, C2, N1, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C2) = Uanis(N1)
Uiso(N15) = Uiso(N13)
Uiso(N4) = Uiso(N5)
Uiso(N3) = Uiso(N2)
5. Rigid body (RIGU) restrains
 C3, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N3(0.166667) N4(0.25) N11(0.083333)
 N12(0.125) N13(0.125) N10(0.083333) N15(0.125) N2(0.08334)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0321(14) Uani 1 4 d S T P . .
N1 N 0.5864(6) 0.3199(6) 0.0388(5) 0.035(2) Uani 1 1 d D . . . .
C2 C 0.6324(6) 0.3676(6) -0.0051(7) 0.035(2) Uani 1 2 d DS T P . .
C1 C 0.6037(7) 0.3379(8) 0.1176(5) 0.035(2) Uani 1 1 d D . . . .
H1 H 0.576532 0.311162 0.169540 0.042 Uiso 1 1 calc R U . . .
C3 C 0.6286(8) 0.3714(8) -0.0955(11) 0.043(5) Uani 1 2 d DS T P . .
H3A H 0.585538 0.328154 -0.117151 0.065 Uiso 0.5 1 calc R U P A -1
H3B H 0.610702 0.430796 -0.113911 0.065 Uiso 0.5 1 calc R U P A -1
H3C H 0.686972 0.357838 -0.120152 0.065 Uiso 0.5 1 calc R U P A -1
N5 N 0.500000 0.500000 -0.233(2) 0.116(11) Uiso 1 4 d DS . P . .
N8 N 0.7824(12) 0.2176(12) 0.0744(17) 0.122(9) Uiso 1 2 d DS . P . .
N3 N 0.500000 0.500000 -0.0388(19) 0.066(7) Uiso 0.6667 4 d S . P . .
N9 N 0.7636(13) 0.2364(13) 0.0238(18) 0.120(9) Uiso 1 2 d DS . P . .
N4 N 0.5436(11) 0.4564(11) -0.229(4) 0.116(11) Uiso 0.5 2 d DS . P . .
N11 N 0.582(5) 0.418(5) -0.418(5) 0.10(4) Uiso 0.5 6 d S . P . .
N12 N 0.586(7) 0.414(7) -0.456(9) 0.12(6) Uiso 0.25 2 d S . P . 2
N7 N 0.7572(15) 0.2428(15) -0.2428(15) 0.089(11) Uiso 1 6 d S . P . .
N13 N 0.876(3) 0.124(3) -0.124(3) 0.11(2) Uiso 0.75 6 d S . P . .
N10 N 0.540(8) 0.460(8) -0.386(12) 0.13(6) Uiso 0.1667 2 d S . P . 1
N15 N 0.827(7) 0.111(5) -0.111(5) 0.11(2) Uiso 0.25 2 d S . P . .
N2 N 0.500000 0.500000 0.000000 0.066(7) Uiso 0.6667 8 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.969(9) . ?
Co1 N1 1.969(9) 48_554 ?
Co1 N1 1.969(9) 46 ?
Co1 N1 1.969(9) 3_655 ?
N1 C2 1.330(9) . ?
N1 C1 1.382(10) . ?
C2 C3 1.52(2) . ?
C1 C1 1.38(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N5 N4 1.03(3) 2_665 ?
N5 N4 1.03(3) . ?
N8 N9 0.96(2) . ?
N3 N3 1.30(6) 3_655 ?
N3 N2 0.65(3) . ?
N11 N12 0.64(16) . ?
N11 N12 0.64(16) 12_654 ?
N11 N12 0.64(16) 6_665 ?
N11 N10 1.1(2) 6_665 ?
N11 N10 1.1(2) . ?
N11 N10 1.1(2) 12_654 ?
N12 N12 1.0(3) 12_654 ?
N12 N12 1.0(3) 6_665 ?
N13 N15 0.87(11) 6_665 ?
N13 N15 0.87(11) 12_654 ?
N13 N15 0.87(11) . ?
N10 N10 1.8(3) 6_665 ?
N10 N10 1.9(4) 2_665 ?
N10 N10 1.8(3) 12_654 ?
N15 N15 1.46(19) 6_665 ?
N15 N15 1.46(19) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.7(3) . 46 ?
N1 Co1 N1 110.7(3) 46 3_655 ?
N1 Co1 N1 107.1(6) . 3_655 ?
N1 Co1 N1 110.7(3) . 48_554 ?
N1 Co1 N1 107.1(6) 46 48_554 ?
N1 Co1 N1 110.7(3) 48_554 3_655 ?
C2 N1 Co1 126.8(6) . . ?
C2 N1 C1 106.0(9) . . ?
C1 N1 Co1 126.7(7) . . ?
N1 C2 N1 112.9(11) 14_665 . ?
N1 C2 C3 123.5(5) 14_665 . ?
N1 C2 C3 123.5(5) . . ?
N1 C1 C1 107.5(7) . 14_665 ?
N1 C1 H1 126.2 . . ?
C1 C1 H1 126.2 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N4 N5 N4 174(9) 2_665 . ?
N2 N3 N3 0.000(3) . 3_655 ?
N12 N11 N12 103(10) . 6_665 ?
N12 N11 N12 103(10) 12_654 6_665 ?
N12 N11 N10 53(7) . 12_654 ?
N12 N11 N10 128(10) 6_665 6_665 ?
N12 N11 N10 53(7) 12_654 6_665 ?
N12 N11 N10 128(10) 12_654 12_654 ?
N12 N11 N10 53(7) 6_665 12_654 ?
N12 N11 N10 53(7) . 6_665 ?
N10 N11 N10 102(10) 12_654 . ?
N10 N11 N10 102(10) 6_665 . ?
N10 N11 N10 102(10) 12_654 6_665 ?
N11 N12 N12 39(10) . 12_654 ?
N11 N12 N12 39(10) . 6_665 ?
N12 N12 N12 60.00(4) 12_654 6_665 ?
N15 N13 N15 114(9) 6_665 . ?
N15 N13 N15 114(9) 12_654 . ?
N15 N13 N15 114(9) 6_665 12_654 ?
N11 N10 N10 39(7) . 12_654 ?
N11 N10 N10 151(10) . 2_665 ?
N11 N10 N10 39(7) . 6_665 ?
N10 N10 N10 119.998(16) 6_665 2_665 ?
N10 N10 N10 59.998(15) 12_654 6_665 ?
N10 N10 N10 119.998(13) 12_654 2_665 ?
N13 N15 N15 33(5) . 6_665 ?
N13 N15 N15 33(5) . 12_654 ?
N15 N15 N15 59.999(12) 6_665 12_654 ?
N3 N2 N3 180.0 3_655 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 173.5(5) . . . 14_665 ?
Co1 N1 C2 C3 -4.2(18) . . . . ?
Co1 N1 C1 C1 -172.8(6) . . . 14_665 ?
C2 N1 C1 C1 -1.0(9) . . . 14_665 ?
C1 N1 C2 N1 1.8(16) . . . 14_665 ?
C1 N1 C2 C3 -175.9(12) . . . . ?
N12 N11 N12 N12 -106(51) 12_654 . . 6_665 ?
N12 N11 N12 N12 106(51) 6_665 . . 12_654 ?
N10 N11 N10 N10 105(23) 6_665 . . 12_654 ?
N10 N11 N10 N10 53(11) 6_665 . . 2_665 ?
N10 N11 N10 N10 -105(23) 12_654 . . 6_665 ?
N10 N11 N10 N10 -53(11) 12_654 . . 2_665 ?
N15 N13 N15 N15 -133(32) 12_654 . . 6_665 ?
N15 N13 N15 N15 133(32) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.962
_oxdiff_exptl_absorpt_empirical_full_min 0.718
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_3490
_database_code_depnum_ccdc_archive 'CCDC 2299167'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_3490      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT090_zif67_ln2_3490      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       5.49 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments
;
_vrf_PLAT341_zif67_ln2_3490      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.025 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT430_zif67_ln2_3490      
;
PROBLEM: Short Inter D...A Contact  N4       ..N10      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_3490_2    
;
PROBLEM: Short Inter D...A Contact  N8       ..N6       .       2.88 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_3490_3    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_3490_4    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_3490_5    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT987_zif67_ln2_3490      
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_PLAT018_zif67_ln2_3490      
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT042_zif67_ln2_3490      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error
;
_vrf_PLAT202_zif67_ln2_3490      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          6 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT722_zif67_ln2_3490      
;
PROBLEM: Angle   Calc      122.00, Rep     124(10) Dev...       2.00 Degree
RESPONSE: Not a real angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT722_zif67_ln2_3490_2    
;
PROBLEM: Angle   Calc      122.00, Rep     124(10) Dev...       2.00 Degree
RESPONSE: Not a real angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_3490      
;
PROBLEM: Torsion Calc     -137.00, Rep    -140(70) Dev...       3.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_3490_2    
;
PROBLEM: Torsion Calc      137.00, Rep     140(70) Dev...       3.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 18.667(N0.5)'
_chemical_formula_sum            'C8 H10 Co N13.33'
_chemical_formula_weight         351.89
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co N4 C8 H10'
_chemical_oxdiff_usercomment     'ZIF-67 in LN2 at 3.49 GPa'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.4992(4)
_cell_length_b                   16.4992(4)
_cell_length_c                   16.4992(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4491.4(4)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    2697
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.8270
_cell_measurement_theta_min      3.4740
_shelx_estimated_absorpt_T_max   0.902
_shelx_estimated_absorpt_T_min   0.854
_exptl_absorpt_coefficient_mu    1.167
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.6047
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1018 before and 0.0855 after correction.
The Ratio of minimum to maximum transmission is 0.8122.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2140
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0916
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            7385
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        20.807
_diffrn_reflns_theta_max         20.807
_diffrn_reflns_theta_min         3.493
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     28.00  99.00   0.50   50.00    --   24.20-140.00-128.00  142
  2  ω    -36.00  29.00   0.50   50.00    --  -24.44 -53.00  38.00  130
  3  ω    -18.00   4.00   0.50   50.00    --   24.20  57.00   0.00   44
  4  ω      9.00  65.00   0.50   50.00    --   24.20 -77.00-150.00  112
  5  ω    -29.00  -9.00   0.50   50.00    --   24.20  77.00-180.00   40
  6  ω    -23.00  16.00   0.50   50.00    --   24.20  67.00 -23.00   78
  7  ω    -36.00 -16.00   0.50   50.00    --  -24.44  38.00 150.00   40
  8  ω    -36.00 -16.00   0.50   50.00    --  -24.44  38.00 -30.00   40
  9  ω     -4.00  18.00   0.50   50.00    --   24.20 -57.00  60.00   44
 10  ω    -27.00  -3.00   0.50   50.00    --   24.20  19.00-150.00   48
 11  ω    -36.00 -16.00   0.50   50.00    --   24.20  38.00   0.00   40
 12  ω      9.00  38.00   0.50   50.00    --   24.20 -77.00  30.00   58
 13  ω      5.00  48.00   0.50   50.00    --  -24.44-114.00-135.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0153838000
_diffrn_orient_matrix_UB_12      0.0072945000
_diffrn_orient_matrix_UB_13      -0.0394503000
_diffrn_orient_matrix_UB_21      0.0041642000
_diffrn_orient_matrix_UB_22      0.0423571000
_diffrn_orient_matrix_UB_23      0.0061772000
_diffrn_orient_matrix_UB_31      0.0399229000
_diffrn_orient_matrix_UB_32      -0.0015992000
_diffrn_orient_matrix_UB_33      -0.0158817000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                409
_reflns_number_total             470
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.828
_refine_diff_density_min         -0.793
_refine_diff_density_rms         0.139
_refine_ls_abs_structure_details 
;
 Flack x determined using 158 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     49
_refine_ls_number_reflns         470
_refine_ls_number_restraints     11
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0849
_refine_ls_restrained_S_all      1.155
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1771P)²+5.5828P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2206
_refine_ls_wR_factor_ref         0.2320
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-C2
 1.55 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.01
 C1-N1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N9-N8
 1.08 with sigma of 0.02
 N4-N5
 1.08 with sigma of 0.02
 N8-N9
 1.09 with sigma of 0.02
3. Restrained planarity
 C1, C2, N1, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C2) = Uanis(N1)
Uiso(N15) = Uiso(N13)
Uiso(N4) = Uiso(N5)
Uiso(N3) = Uiso(N2)
Uiso(N6) = Uiso(N7)
Uiso(N9) = Uiso(N8)
5. Rigid body (RIGU) restrains
 C3, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N2(0.083333) N3(0.166667) N6(0.05555)
 N4(0.25) N11(0.083333) N12(0.083333) N7(0.11112) N13(0.083333) N10(0.083333)
 N15(0.08335)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.0410(18) Uani 1 4 d S T P . .
N1 N 0.5847(7) 0.3196(7) 0.0432(6) 0.040(3) Uani 1 1 d D . . . .
C2 C 0.6321(7) 0.3679(7) -0.0017(9) 0.040(3) Uani 1 2 d DS T P . .
C1 C 0.6023(9) 0.3389(10) 0.1229(7) 0.040(3) Uani 1 1 d D . . . .
H1 H 0.574586 0.312414 0.175777 0.048 Uiso 1 1 calc R U . . .
C3 C 0.6290(11) 0.3710(11) -0.0933(13) 0.054(7) Uani 1 2 d DS T P . .
H3A H 0.585374 0.327125 -0.115246 0.081 Uiso 0.5 1 calc R U P A -1
H3B H 0.611053 0.431158 -0.112614 0.081 Uiso 0.5 1 calc R U P A -1
H3C H 0.688284 0.357005 -0.117700 0.081 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.068(9) Uiso 0.6666 8 d S . P . .
N5 N 0.500000 0.500000 -0.234(3) 0.116(12) Uiso 1 4 d DS . P . .
N8 N 0.7868(15) 0.2132(15) 0.079(2) 0.128(9) Uiso 1 2 d DS . P . .
N3 N 0.500000 0.500000 -0.039(2) 0.068(9) Uiso 0.6667 4 d S . P . .
N9 N 0.7623(15) 0.2377(15) 0.028(2) 0.128(9) Uiso 1 2 d DS . P . .
N6 N 0.747(5) 0.253(5) -0.253(5) 0.061(13) Uiso 0.3333 6 d S . P . .
N4 N 0.5448(12) 0.4552(12) -0.230(4) 0.116(12) Uiso 0.5 2 d DS . P . .
N11 N 0.566(7) 0.434(7) -0.434(7) 0.10(6) Uiso 0.5 6 d S . P . .
N12 N 0.589(8) 0.411(8) -0.463(12) 0.07(6) Uiso 0.1667 2 d S . P . 2
N7 N 0.7637(18) 0.2363(18) -0.2363(18) 0.061(13) Uiso 0.6667 6 d S . P . .
N13 N 0.875(5) 0.125(5) -0.125(5) 0.08(3) Uiso 0.5 6 d S . P . .
N10 N 0.571(6) 0.429(6) -0.394(12) 0.07(9) Uiso 0.1667 2 d S . P . 1
N15 N 0.840(11) 0.117(8) -0.117(8) 0.08(3) Uiso 0.1667 2 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.944(10) . ?
Co1 N1 1.944(10) 3_655 ?
Co1 N1 1.944(10) 46 ?
Co1 N1 1.944(10) 48_554 ?
N1 C2 1.340(10) . ?
N1 C1 1.384(11) . ?
C2 C3 1.51(2) . ?
C1 C1 1.37(3) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.64(4) 3_655 ?
N2 N3 0.64(4) . ?
N5 N4 1.05(3) 2_665 ?
N5 N4 1.05(3) . ?
N8 N9 1.024(19) . ?
N3 N3 1.28(7) 3_655 ?
N11 N12 0.7(2) . ?
N11 N12 0.7(2) 12_654 ?
N11 N12 0.7(2) 6_665 ?
N11 N10 0.7(2) . ?
N11 N10 0.7(2) 6_665 ?
N11 N10 0.7(2) 12_654 ?
N12 N12 1.2(4) 6_665 ?
N12 N12 1.2(4) 12_654 ?
N13 N15 0.60(18) 6_665 ?
N13 N15 0.60(18) . ?
N13 N15 0.60(18) 12_654 ?
N10 N10 0.8(3) 6_665 ?
N10 N10 0.8(3) 12_654 ?
N15 N15 1.0(3) 6_665 ?
N15 N15 1.0(3) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.4(4) . 46 ?
N1 Co1 N1 107.6(7) 46 48_554 ?
N1 Co1 N1 110.4(4) . 48_554 ?
N1 Co1 N1 107.6(7) . 3_655 ?
N1 Co1 N1 110.4(4) 46 3_655 ?
N1 Co1 N1 110.4(4) 3_655 48_554 ?
C2 N1 Co1 124.6(7) . . ?
C2 N1 C1 105.4(10) . . ?
C1 N1 Co1 129.4(9) . . ?
N1 C2 N1 112.9(13) 14_665 . ?
N1 C2 C3 123.5(6) 14_665 . ?
N1 C2 C3 123.5(6) . . ?
N1 C1 H1 125.9 . . ?
C1 C1 N1 108.1(8) 14_665 . ?
C1 C1 H1 125.9 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.0 3_655 . ?
N4 N5 N4 173(10) 2_665 . ?
N2 N3 N3 0.000(3) . 3_655 ?
N12 N11 N12 116(10) . 12_654 ?
N12 N11 N12 116(10) . 6_665 ?
N12 N11 N12 116(10) 12_654 6_665 ?
N10 N11 N12 60(10) . 12_654 ?
N10 N11 N12 60(10) 12_654 6_665 ?
N10 N11 N12 124(10) 6_665 6_665 ?
N10 N11 N12 60(10) 6_665 12_654 ?
N10 N11 N12 124(10) 12_654 12_654 ?
N10 N11 N12 60(10) . 6_665 ?
N10 N11 N10 78(10) 6_665 12_654 ?
N10 N11 N10 78(10) . 6_665 ?
N10 N11 N10 78(10) . 12_654 ?
N11 N12 N12 32(8) . 12_654 ?
N11 N12 N12 32(8) . 6_665 ?
N12 N12 N12 60.00(3) 12_654 6_665 ?
N15 N13 N15 111(10) 12_654 . ?
N15 N13 N15 111(10) 6_665 12_654 ?
N15 N13 N15 111(10) 6_665 . ?
N11 N10 N10 51(10) . 6_665 ?
N11 N10 N10 51(10) . 12_654 ?
N10 N10 N10 60.00(5) 12_654 6_665 ?
N13 N15 N15 34(10) . 12_654 ?
N13 N15 N15 34(10) . 6_665 ?
N15 N15 N15 60.00(5) 6_665 12_654 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 174.1(6) . . . 14_665 ?
Co1 N1 C2 C3 -4(2) . . . . ?
Co1 N1 C1 C1 -172.8(8) . . . 14_665 ?
C2 N1 C1 C1 -1.1(11) . . . 14_665 ?
C1 N1 C2 N1 1.9(19) . . . 14_665 ?
C1 N1 C2 C3 -176.0(15) . . . . ?
N12 N11 N12 N12 -140(70) 6_665 . . 12_654 ?
N12 N11 N12 N12 140(70) 12_654 . . 6_665 ?
N10 N11 N10 N10 -80(20) 6_665 . . 12_654 ?
N10 N11 N10 N10 80(20) 12_654 . . 6_665 ?
N15 N13 N15 N15 -125(78) 12_654 . . 6_665 ?
N15 N13 N15 N15 125(78) 6_665 . . 12_654 ?

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 11.487
_oxdiff_exptl_absorpt_empirical_full_min 0.622
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p3_w1_70s_0056
_database_code_depnum_ccdc_archive 'CCDC 2299171'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p3_w1_70s_0056 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p3_w1_70s_0056 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.952 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_p3_w1_70s_0056 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0175 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell
;
_vrf_PLAT987_zif67_p3_w1_70s_0056 
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p3_w1_70s_0056 
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in olex2
;
_vrf_PLAT018_zif67_p3_w1_70s_0056 
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell
;
_vrf_PLAT242_zif67_p3_w1_70s_0056 
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of         C2 Check
RESPONSE: The alert is caused by thermal motion of the atoms near C2, and the use of restaints in the surrounding ring to minimise the disorder.
;
_vrf_PLAT260_zif67_p3_w1_70s_0056 
;
PROBLEM: Large Average Ueq of Residue Including       Co1      0.103 Check
RESPONSE: Data are collected at RT, in addition, the mean square atomic displacements parameters are included below. C3 is slightly elongated as would be expected for a terminal methyl C-atom. Atoms in the ring are consrained to have the same thermal motion EADP. Principal mean square atomic displacements U    0.0907   0.0889   0.0889   Co1    0.1141   0.0970   0.0798   N1    0.1141   0.0970   0.0798   C2    0.2201   0.1034   0.0807   C1    0.1141   0.0970   0.0798   C3
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C8 H10 Co N4, 3.833[CH3OH]'
_chemical_formula_sum            'C11.83 H25.33 Co N4 O3.83'
_chemical_formula_weight         343.86
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H20 N4 Co O2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   17.1640(3)
_cell_length_b                   17.1640(3)
_cell_length_c                   17.1640(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5056.6(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1657
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.1920
_cell_measurement_theta_min      1.6850
_shelx_estimated_absorpt_T_max   0.904
_shelx_estimated_absorpt_T_min   0.860
_exptl_absorpt_coefficient_mu    1.036
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.5156
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1236 before and 0.0879 after correction.
The Ratio of minimum to maximum transmission is 0.6922.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             2183
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0524
_diffrn_reflns_Laue_measured_fraction_full 0.952
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            1893
_diffrn_reflns_point_group_measured_fraction_full 0.891
_diffrn_reflns_point_group_measured_fraction_max 0.884
_diffrn_reflns_theta_full        23.199
_diffrn_reflns_theta_max         23.199
_diffrn_reflns_theta_min         1.678
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.952
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0307170000
_diffrn_orient_matrix_UB_12      -0.0271303000
_diffrn_orient_matrix_UB_13      -0.0045011000
_diffrn_orient_matrix_UB_21      0.0111135000
_diffrn_orient_matrix_UB_22      -0.0059939000
_diffrn_orient_matrix_UB_23      -0.0393922000
_diffrn_orient_matrix_UB_31      0.0252280000
_diffrn_orient_matrix_UB_32      -0.0306135000
_diffrn_orient_matrix_UB_33      0.0117727000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.681
_reflns_Friedel_fraction_full    0.814
_reflns_Friedel_fraction_max     0.810
_reflns_number_gt                571
_reflns_number_total             632
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.651
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details 
;
 Flack x determined using 211 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.29(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         632
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0897
_refine_ls_R_factor_gt           0.0845
_refine_ls_restrained_S_all      1.114
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1819P)²+1.0813P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2227
_refine_ls_wR_factor_ref         0.2390
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.35 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.169 with sigma of 0.01
 N1-C2
 1.35 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C3) = Uanis(C2)
5. Rigid body (RIGU) restrains
 C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0895(11) Uani 1 4 d S T P . .
N1 N 0.0286(5) -0.5905(5) -0.3165(4) 0.0970(16) Uani 1 1 d D . . . .
C2 C -0.0102(7) -0.6211(5) -0.3789(5) 0.0970(16) Uani 1 2 d DS T P . .
C1 C -0.0848(10) -0.5898(10) -0.4102(10) 0.135(7) Uani 1 2 d DS T P . .
H1A H -0.076915 -0.529386 -0.426785 0.202 Uiso 0.5 1 calc R U P A -1
H1B H -0.129547 -0.593778 -0.365934 0.202 Uiso 0.5 1 calc R U P A -1
H1C H -0.102123 -0.623351 -0.460765 0.202 Uiso 0.5 1 calc R U P A -1
C3 C 0.0940(5) -0.6359(6) -0.3087(6) 0.0970(16) Uani 1 1 d D . . . .
H3 H 0.138351 -0.628268 -0.264998 0.116 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.989(8) 40_444 ?
Co1 N1 1.989(8) . ?
Co1 N1 1.989(8) 39_544 ?
Co1 N1 1.989(8) 2_545 ?
N1 C2 1.366(8) . ?
N1 C3 1.372(9) . ?
C2 C1 1.489(11) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.35(2) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.0(5) 40_444 39_544 ?
N1 Co1 N1 109.2(2) 39_544 . ?
N1 Co1 N1 109.2(2) 40_444 . ?
N1 Co1 N1 109.2(2) 40_444 2_545 ?
N1 Co1 N1 109.2(2) 39_544 2_545 ?
N1 Co1 N1 110.0(5) 2_545 . ?
C2 N1 Co1 129.0(5) . . ?
C2 N1 C3 104.9(7) . . ?
C3 N1 Co1 126.1(6) . . ?
N1 C2 N1 111.4(9) 20_544 . ?
N1 C2 C1 124.3(4) . . ?
N1 C2 C1 124.3(4) 20_544 . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 H3 125.3 . . ?
C3 C3 N1 109.4(5) 20_544 . ?
C3 C3 H3 125.3 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 179.8(4) . . . 20_544 ?
Co1 N1 C2 C1 0(2) . . . . ?
Co1 N1 C3 C3 -179.7(5) . . . 20_544 ?
C2 N1 C3 C3 -0.1(9) . . . 20_544 ?
C3 N1 C2 N1 0.2(16) . . . 20_544 ?
C3 N1 C2 C1 -179.0(16) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
2 2 2 4.113
0 0 4 4.750
0 3 7 9.072

_platon_squeeze_details          
;
TITL zif67_p3_w1_70s_0056_a.res in I-43m
CELL   17.1640   17.1640   17.1640     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2589
# Electrons Found in S.A.V. =       836
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.255 0.755 0.245 !       2.04 eA-3
C102 0.267 0.299 0.270 !       1.71 eA-3
C103 0.239 1.000 0.000 !       1.64 eA-3
C104 0.217 0.030 0.222 !       1.51 eA-3
C105 0.015 0.017 0.187 !       1.21 eA-3
C106 0.500 0.504 0.219 !       1.19 eA-3
C107 0.532 0.237 0.463 !       1.19 eA-3
C108 0.365 0.630 0.363 !       1.17 eA-3
C109 0.018 0.811 0.188 !       1.07 eA-3
Q110 0.837 0.404 0.404 !       1.00 eA-3
Q111 0.702 0.075 0.075 !       0.96 eA-3
Q112 0.045 0.686 0.047 !       0.96 eA-3
C113 0.073 0.200 0.200 !       0.95 eA-3
Q114 0.881 0.868 0.318 !       0.92 eA-3
C115 0.424 0.424 0.424 !       0.90 eA-3
C116 0.399 0.399 0.399 !       0.89 eA-3
C117 0.558 0.544 0.300 !       0.86 eA-3
C118 0.338 0.338 0.338 !       0.84 eA-3
C119 0.063 0.059 0.313 !       0.84 eA-3
C120 0.068 0.064 0.146 !       0.81 eA-3
C121 0.880 0.876 0.021 !       0.81 eA-3
Q122 0.286 0.222 0.222 !       0.80 eA-3
C123 0.561 0.646 0.355 !       0.79 eA-3
C124 0.151 0.042 0.156 !       0.79 eA-3
C125 0.311 0.359 0.359 !       0.78 eA-3
C126 0.811 0.859 0.859 !       0.78 eA-3
Q127 0.683 0.344 0.220 !       0.77 eA-3
C128 0.049 0.862 0.045 !       0.77 eA-3
Q129 0.057 0.354 0.066 !       0.75 eA-3
C130 0.234 0.189 0.189 !       0.73 eA-3
C131 0.169 0.169 0.169 !       0.72 eA-3
Q132 0.335 0.112 0.049 !       0.72 eA-3
C133 0.879 0.083 0.215 !       0.70 eA-3
C134 0.908 0.911 0.267 !       0.70 eA-3
C135 0.846 0.998 0.155 !       0.69 eA-3
Q136 0.314 0.834 0.166 !       0.69 eA-3
C137 0.953 0.047 0.047 !       0.68 eA-3
C138 0.265 0.152 0.049 !       0.66 eA-3
C139 0.232 0.111 0.005 !       0.64 eA-3
C140 0.566 0.521 0.479 !       0.60 eA-3
C141 0.317 0.531 0.396 !       0.59 eA-3
Q142 0.541 0.205 0.205 !       0.59 eA-3
Q143 0.732 0.361 0.249 !       0.58 eA-3
C144 0.672 0.407 0.407 !       0.58 eA-3
Q145 0.359 0.565 0.212 !       0.56 eA-3
C146 0.404 0.581 0.460 !       0.51 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 838 electrons were 
found in a volume of 2570Å³ in 1 void per unit cell. 
This is consistent with the presence of 
46[CH3OH] per Unit Cell 
which account for 828 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.012 -0.006 -0.004 2570 838 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.976
_oxdiff_exptl_absorpt_empirical_full_min 0.614
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_w2_70s_0051
_database_code_depnum_ccdc_archive 'CCDC 2299175'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_w2_70s_0051   
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_w2_70s_0051   
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.937 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_w2_70s_0051   
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_w2_70s_0051   
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in olex2
;
_vrf_PLAT018_zif67_w2_70s_0051   
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT260_zif67_w2_70s_0051   
;
PROBLEM: Large Average Ueq of Residue Including       Co1      0.101 Check
RESPONSE: Data are collected at RT, in addition, the mean square atomic displacements parameters are included below. C3 is slightly elongated as would be expected for a terminal methyl C-atom. Atoms in the ring are consrained to have the same thermal motion EADP. Principal mean square atomic displacements U    0.0940   0.0940   0.0922   Co1    0.1144   0.0960   0.0800   N1    0.1144   0.0960   0.0800   C2    0.1799   0.0905   0.0884   C1    0.1144   0.0960   0.0800   C3
;
_vrf_PLAT341_zif67_w2_70s_0051   
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.013 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ZIF-67
_chemical_formula_moiety         'C8 H10 Co N4, 1.5[C2H5OH]'
_chemical_formula_sum            'C11 H19 Co N4 O1.50'
_chemical_formula_weight         290.23
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C10 H20 Co N4 O2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   17.1155(2)
_cell_length_b                   17.1155(2)
_cell_length_c                   17.1155(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5013.82(18)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    983
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      18.6070
_cell_measurement_theta_min      1.6850
_shelx_estimated_absorpt_T_max   0.905
_shelx_estimated_absorpt_T_min   0.862
_exptl_absorpt_coefficient_mu    1.023
_exptl_absorpt_correction_T_max  0.7443
_exptl_absorpt_correction_T_min  0.4357
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1140 before and 0.0939 after correction.
The Ratio of minimum to maximum transmission is 0.5854.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.153
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0532
_diffrn_reflns_Laue_measured_fraction_full 0.937
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            1212
_diffrn_reflns_point_group_measured_fraction_full 0.897
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        18.600
_diffrn_reflns_theta_max         18.600
_diffrn_reflns_theta_min         1.683
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.937
_diffrn_measured_fraction_theta_max 0.933
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0270075000
_diffrn_orient_matrix_UB_12      -0.0053143000
_diffrn_orient_matrix_UB_13      -0.0309013000
_diffrn_orient_matrix_UB_21      0.0048838000
_diffrn_orient_matrix_UB_22      -0.0410839000
_diffrn_orient_matrix_UB_23      0.0028426000
_diffrn_orient_matrix_UB_31      -0.0310869000
_diffrn_orient_matrix_UB_32      -0.0018131000
_diffrn_orient_matrix_UB_33      0.0274033000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.683
_reflns_Friedel_fraction_full    0.844
_reflns_Friedel_fraction_max     0.845
_reflns_number_gt                329
_reflns_number_total             350
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.091
_refine_diff_density_min         -0.128
_refine_diff_density_rms         0.023
_refine_ls_abs_structure_details 
;
 Flack x determined using 124 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.16(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         350
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0317
_refine_ls_R_factor_gt           0.0301
_refine_ls_restrained_S_all      1.137
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0313P)²+1.2167P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0809
_refine_ls_wR_factor_ref         0.0816
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(N1) = Uanis(C2)
4. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0938(8) Uani 1 4 d S T P . .
N1 N 0.0321(3) -0.5899(4) -0.3168(3) 0.0970(15) Uani 1 1 d . . . . .
C2 C -0.0081(8) -0.6227(3) -0.3773(3) 0.0970(15) Uani 1 2 d S T P . .
C1 C -0.0854(6) -0.5938(6) -0.4062(6) 0.118(4) Uani 1 2 d S T P . .
H1A H -0.126697 -0.592517 -0.358283 0.177 Uiso 0.5 1 calc R U P A -1
H1B H -0.106780 -0.632490 -0.451477 0.177 Uiso 0.5 1 calc R U P A -1
H1C H -0.078592 -0.535464 -0.429771 0.177 Uiso 0.5 1 calc R U P A -1
C3 C 0.1002(4) -0.6304(4) -0.3124(4) 0.0970(15) Uani 1 1 d . . . . .
H3 H 0.146516 -0.619815 -0.271217 0.116 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.994(5) . ?
Co1 N1 1.994(5) 39_544 ?
Co1 N1 1.994(5) 2_545 ?
Co1 N1 1.994(5) 40_444 ?
N1 C2 1.365(8) . ?
N1 C3 1.357(7) . ?
C2 C1 1.496(14) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.384(13) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 109.19(16) . 40_444 ?
N1 Co1 N1 109.20(16) 40_444 2_545 ?
N1 Co1 N1 110.0(3) . 2_545 ?
N1 Co1 N1 109.20(16) . 39_544 ?
N1 Co1 N1 110.0(3) 40_444 39_544 ?
N1 Co1 N1 109.20(16) 39_544 2_545 ?
C2 N1 Co1 127.8(5) . . ?
C3 N1 Co1 126.8(4) . . ?
C3 N1 C2 105.4(7) . . ?
N1 C2 N1 111.7(9) 20_544 . ?
N1 C2 C1 124.1(5) . . ?
N1 C2 C1 124.1(5) 20_544 . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 C3 108.8(4) . 20_544 ?
N1 C3 H3 125.6 . . ?
C3 C3 H3 125.6 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 179.6(3) . . . 20_544 ?
Co1 N1 C2 C1 2.0(14) . . . . ?
Co1 N1 C3 C3 -179.3(4) . . . 20_544 ?
C2 N1 C3 C3 -0.5(6) . . . 20_544 ?
C3 N1 C2 N1 0.9(11) . . . 20_544 ?
C3 N1 C2 C1 -176.7(10) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 0 2 2.380
0 3 7 9.098

_platon_squeeze_details          
;
TITL zif67_w2_70s_0051_a.res in I-43m
CELL   17.1155   17.1155   17.1155     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2531
# Electrons Found in S.A.V. =       456
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.357 0.638 0.362 !       1.04 eA-3
C102 0.622 0.371 0.488 !       0.66 eA-3
C103 0.122 0.871 0.988 !       0.66 eA-3
C104 0.122 0.988 0.871 !       0.66 eA-3
C105 0.685 0.690 0.482 !       0.65 eA-3
C106 0.403 0.408 0.543 !       0.61 eA-3
C107 0.575 0.583 0.340 !       0.61 eA-3
C108 0.080 0.080 0.080 !       0.61 eA-3
C109 0.334 0.334 0.334 !       0.56 eA-3
C110 0.467 0.467 0.467 !       0.54 eA-3
C111 0.640 0.702 0.437 !       0.51 eA-3
C112 0.197 0.072 0.204 !       0.50 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 458 electrons were 
found in a volume of 2507Å³ in 1 void per unit cell. 
This is consistent with the presence of 
18[C2H5OH] per Unit Cell 
which account for 468 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.013 -0.006 -0.004 2507 458 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.715
_oxdiff_exptl_absorpt_empirical_full_min 0.336
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p5_w1_70s_0058
_database_code_depnum_ccdc_archive 'CCDC 2299173'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p5_w1_70s_0058 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p5_w1_70s_0058 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.958 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_p5_w1_70s_0058 
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p5_w1_70s_0058 
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in olex2
;
_vrf_PLAT018_zif67_p5_w1_70s_0058 
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_p5_w1_70s_0058 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0075 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ZIF-67
_chemical_formula_moiety         'C8 H10 Co N4, 4.5[CH3OH]'
_chemical_formula_sum            'C12.50 H28 Co N4 O4.50'
_chemical_formula_weight         365.32
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H20 Co N4 O4'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   16.9823(4)
_cell_length_b                   16.9823(4)
_cell_length_c                   16.9823(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4897.7(4)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1106
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.1970
_cell_measurement_theta_min      2.3830
_shelx_estimated_absorpt_T_max   0.900
_shelx_estimated_absorpt_T_min   0.855
_exptl_absorpt_coefficient_mu    1.077
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.5245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0917 before and 0.0676 after correction.
The Ratio of minimum to maximum transmission is 0.7041.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             2328
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.958
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            2317
_diffrn_reflns_point_group_measured_fraction_full 0.920
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        23.186
_diffrn_reflns_theta_max         23.186
_diffrn_reflns_theta_min         1.696
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.951
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0049956000
_diffrn_orient_matrix_UB_12      -0.0311397000
_diffrn_orient_matrix_UB_13      -0.0272343000
_diffrn_orient_matrix_UB_21      -0.0398394000
_diffrn_orient_matrix_UB_22      0.0113736000
_diffrn_orient_matrix_UB_23      -0.0056573000
_diffrn_orient_matrix_UB_31      0.0116657000
_diffrn_orient_matrix_UB_32      0.0253913000
_diffrn_orient_matrix_UB_33      -0.0311095000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.724
_reflns_Friedel_fraction_full    0.871
_reflns_Friedel_fraction_max     0.869
_reflns_number_gt                623
_reflns_number_total             631
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details 
;
 Flack x determined using 258 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.137
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         631
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0363
_refine_ls_restrained_S_all      1.148
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0701P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1003
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.35 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.169 with sigma of 0.01
 N1-C2
 1.35 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(N1) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0343(4) Uani 1 4 d S T P . .
N1 N 0.03492(19) -0.5883(2) -0.3187(2) 0.0390(7) Uani 1 1 d D . . . .
C2 C -0.0086(3) -0.6352(2) -0.3648(2) 0.0390(7) Uani 1 2 d DS T P . .
C1 C -0.0969(4) -0.6338(3) -0.3662(3) 0.0493(18) Uani 1 2 d DS T P . .
H1A H -0.118108 -0.589646 -0.325357 0.074 Uiso 0.5 1 calc R U P A -1
H1B H -0.119334 -0.691048 -0.349105 0.074 Uiso 0.5 1 calc R U P A -1
H1C H -0.117010 -0.619802 -0.425043 0.074 Uiso 0.5 1 calc R U P A -1
C3 C 0.1118(2) -0.6042(3) -0.3397(3) 0.0390(7) Uani 1 1 d D . . . .
H3 H 0.163296 -0.576420 -0.315271 0.047 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.990(4) . ?
Co1 N1 1.990(4) 2_545 ?
Co1 N1 1.990(4) 40_444 ?
Co1 N1 1.990(4) 39_544 ?
N1 C2 1.339(4) . ?
N1 C3 1.380(6) . ?
C2 C1 1.500(8) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.346(11) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.12(11) . 40_444 ?
N1 Co1 N1 110.12(11) 40_444 2_545 ?
N1 Co1 N1 108.2(2) . 2_545 ?
N1 Co1 N1 110.12(11) . 39_544 ?
N1 Co1 N1 108.2(2) 40_444 39_544 ?
N1 Co1 N1 110.12(11) 39_544 2_545 ?
C2 N1 Co1 128.8(3) . . ?
C2 N1 C3 104.7(4) . . ?
C3 N1 Co1 125.5(3) . . ?
N1 C2 N1 113.0(5) 20_544 . ?
N1 C2 C1 123.5(3) . . ?
N1 C2 C1 123.5(3) 20_544 . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 H3 125.6 . . ?
C3 C3 N1 108.7(3) 20_544 . ?
C3 C3 H3 125.6 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 170.97(18) . . . 20_544 ?
Co1 N1 C2 C1 -6.5(7) . . . . ?
Co1 N1 C3 C3 -170.7(2) . . . 20_544 ?
C2 N1 C3 C3 -1.0(3) . . . 20_544 ?
C3 N1 C2 N1 1.7(6) . . . 20_544 ?
C3 N1 C2 C1 -175.7(5) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
2 2 2 4.157
0 0 4 4.801
0 3 7 9.170

_platon_squeeze_details          
;
TITL zif67_p5_w1_70s_0058_a.res in I-43m
CELL   16.9823   16.9823   16.9823     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2527
# Electrons Found in S.A.V. =       966
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 0.500 0.500 0.000 !       6.08 eA-3
C102 0.724 0.542 0.283 !       4.19 eA-3
C103 1.000 0.438 0.000 !       3.96 eA-3
C104 0.733 0.267 0.267 !       3.50 eA-3
C105 0.527 0.286 0.286 !       3.12 eA-3
C106 0.500 0.509 0.219 !       2.98 eA-3
C107 0.580 0.420 0.420 !       2.37 eA-3
C108 0.127 0.865 0.170 !       1.98 eA-3
Q109 0.328 0.784 0.216 !       1.04 eA-3
C110 0.427 0.427 0.427 !       0.99 eA-3
C111 0.190 0.815 0.185 !       0.73 eA-3
C112 0.038 0.038 0.038 !       0.71 eA-3
Q113 0.910 0.201 0.299 !       0.68 eA-3
C114 0.020 0.992 0.059 !       0.65 eA-3
Q115 0.644 0.363-0.004 !       0.60 eA-3
Q116 0.750 0.998 0.475 !       0.56 eA-3
Q117 0.250 0.498 0.975 !       0.56 eA-3
Q118 0.250 0.970 0.537 !       0.56 eA-3
C119 0.120 0.134 0.198 !       0.52 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 974 electrons were 
found in a volume of 2489Å³ in 1 void per unit cell. 
This is consistent with the presence of 
54[CH3OH] per Unit Cell 
which account for 900 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.025 -0.015 -0.006 2489 974 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.829
_oxdiff_exptl_absorpt_empirical_full_min 0.721
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p4_w1_70s_0057
_database_code_depnum_ccdc_archive 'CCDC 2299172'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p4_w1_70s_0057 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_p4_w1_70s_0057 
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p4_w1_70s_0057 
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in Olex2
;
_vrf_PLAT018_zif67_p4_w1_70s_0057 
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p4_w1_70s_0057 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.962 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_p4_w1_70s_0057 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.015 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C8 H10 Co N4, 5.417[CH3OH]'
_chemical_formula_sum            'C13.42 H31.67 Co N4 O5.42'
_chemical_formula_weight         394.79
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H25 Co N4 O4'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   17.1651(3)
_cell_length_b                   17.1651(3)
_cell_length_c                   17.1651(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5057.5(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1616
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.2000
_cell_measurement_theta_min      2.3570
_shelx_estimated_absorpt_T_max   0.902
_shelx_estimated_absorpt_T_min   0.858
_exptl_absorpt_coefficient_mu    1.053
_exptl_absorpt_correction_T_max  0.7441
_exptl_absorpt_correction_T_min  0.5642
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1055 before and 0.0819 after correction.
The Ratio of minimum to maximum transmission is 0.7582.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.555
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             2527
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0516
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            2236
_diffrn_reflns_point_group_measured_fraction_full 0.884
_diffrn_reflns_point_group_measured_fraction_max 0.877
_diffrn_reflns_theta_full        23.197
_diffrn_reflns_theta_max         23.197
_diffrn_reflns_theta_min         1.678
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0263789000
_diffrn_orient_matrix_UB_12      -0.0048160000
_diffrn_orient_matrix_UB_13      -0.0313199000
_diffrn_orient_matrix_UB_21      -0.0057060000
_diffrn_orient_matrix_UB_22      -0.0394790000
_diffrn_orient_matrix_UB_23      0.0109308000
_diffrn_orient_matrix_UB_31      -0.0313134000
_diffrn_orient_matrix_UB_32      0.0113287000
_diffrn_orient_matrix_UB_33      0.0245592000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.650
_reflns_Friedel_fraction_full    0.785
_reflns_Friedel_fraction_max     0.782
_reflns_number_gt                581
_reflns_number_total             627
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.358
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details 
;
 Flack x determined using 220 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.22(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         627
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0634
_refine_ls_restrained_S_all      1.148
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1067P)²+8.5343P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1727
_refine_ls_wR_factor_ref         0.1801
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.35 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.169 with sigma of 0.01
 N1-C2
 1.35 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(N1) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0633(9) Uani 1 4 d S T P . .
N1 N 0.0322(4) -0.5889(4) -0.3183(4) 0.0697(15) Uani 1 1 d D . . . .
C2 C -0.0123(5) -0.6366(4) -0.3634(4) 0.0697(15) Uani 1 2 d DS T P . .
C1 C -0.0992(7) -0.6345(8) -0.3655(8) 0.092(5) Uani 1 2 d DS T P . .
H1A H -0.122033 -0.690991 -0.349043 0.138 Uiso 0.5 1 calc R U P A -1
H1B H -0.118477 -0.620217 -0.423853 0.138 Uiso 0.5 1 calc R U P A -1
H1C H -0.120170 -0.590780 -0.325117 0.138 Uiso 0.5 1 calc R U P A -1
C3 C 0.1077(4) -0.6063(6) -0.3397(6) 0.0697(15) Uani 1 1 d D . . . .
H3 H 0.159067 -0.579476 -0.315552 0.084 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 2.002(7) 40_444 ?
Co1 N1 2.002(7) . ?
Co1 N1 2.002(7) 39_544 ?
Co1 N1 2.002(7) 2_545 ?
N1 C2 1.362(8) . ?
N1 C3 1.380(9) . ?
C2 C1 1.492(11) . ?
C1 H1A 1.0831 . ?
C1 H1B 1.0831 . ?
C1 H1C 1.0831 . ?
C3 C3 1.31(2) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 108.3(4) 40_444 39_544 ?
N1 Co1 N1 110.1(2) 39_544 . ?
N1 Co1 N1 110.0(2) 40_444 . ?
N1 Co1 N1 110.0(2) 40_444 2_545 ?
N1 Co1 N1 110.0(2) 39_544 2_545 ?
N1 Co1 N1 108.3(4) 2_545 . ?
C2 N1 Co1 129.5(5) . . ?
C2 N1 C3 104.2(7) . . ?
C3 N1 Co1 125.5(6) . . ?
N1 C2 N1 111.6(8) 20_544 . ?
N1 C2 C1 124.1(4) . . ?
N1 C2 C1 124.1(4) 20_544 . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 H3 125.0 . . ?
C3 C3 N1 110.0(5) 20_544 . ?
C3 C3 H3 125.0 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 169.8(3) . . . 20_544 ?
Co1 N1 C2 C1 -4.9(16) . . . . ?
Co1 N1 C3 C3 -170.5(4) . . . 20_544 ?
C2 N1 C3 C3 0.2(7) . . . 20_544 ?
C3 N1 C2 N1 -0.3(12) . . . 20_544 ?
C3 N1 C2 C1 -175.0(10) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 0 4 4.750
0 3 7 9.072

_platon_squeeze_details          
;
TITL zif67_p4_w1_70s_0057_a.res in I-43m
CELL   17.1651   17.1651   17.1651     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2667
# Electrons Found in S.A.V. =      1164
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 1.000 1.003 0.469 !       3.29 eA-3
C102 0.219 0.219 0.219 !       2.85 eA-3
C103 0.724 0.725 0.459 !       2.79 eA-3
C104 0.029 0.220 0.220 !       2.63 eA-3
C105 0.501 0.491 0.266 !       1.88 eA-3
C106 0.378 0.378 0.378 !       1.84 eA-3
C107 0.278 1.000 0.000 !       1.72 eA-3
C108 0.921 0.078 0.079 !       1.71 eA-3
C109 0.032 0.080 0.080 !       1.54 eA-3
C110 0.094 0.094 0.094 !       1.47 eA-3
C111 0.329 0.673 0.327 !       1.37 eA-3
C112 0.274 0.951 0.048 !       1.23 eA-3
C113 0.259 0.064 0.039 !       1.19 eA-3
C114 0.537 0.548 0.406 !       1.14 eA-3
Q115 0.408 0.408 0.204 !       1.08 eA-3
C116 0.878 0.871 0.128 !       1.06 eA-3
C117 0.206 0.199 0.144 !       1.06 eA-3
Q118 0.060 0.705 0.120 !       1.04 eA-3
Q119 0.560 0.205 0.620 !       1.04 eA-3
Q120 0.127 0.299 0.942 !       1.02 eA-3
C121 0.538 0.541 0.467 !       1.00 eA-3
C122 0.030 0.030 0.030 !       0.99 eA-3
Q123 0.171 0.301 0.941 !       0.97 eA-3
Q124 0.736 0.735 0.002 !       0.94 eA-3
C125 0.278 0.545 0.455 !       0.93 eA-3
C126 0.579 0.582 0.360 !       0.93 eA-3
Q127 0.562 0.172 0.435 !       0.91 eA-3
C128 0.683 0.692 0.308 !       0.91 eA-3
C129 0.333 0.364 0.380 !       0.91 eA-3
C130 0.364 0.380 0.333 !       0.91 eA-3
C131 0.094 0.091 0.156 !       0.90 eA-3
C132 0.184 0.740 0.249 !       0.89 eA-3
C133 0.846 0.843 0.003 !       0.88 eA-3
Q134 0.247 0.084 0.185 !       0.87 eA-3
Q135 0.651 0.032 0.032 !       0.87 eA-3
C136 0.152 0.862 0.054 !       0.85 eA-3
Q137 0.031 0.455 0.455 !       0.84 eA-3
C138 0.294 0.452 0.453 !       0.81 eA-3
Q139 0.783 0.658 0.373 !       0.81 eA-3
Q140 0.195 0.451 0.280 !       0.80 eA-3
C141 0.862 0.095 0.190 !       0.78 eA-3
Q142 0.188 0.704 0.188 !       0.78 eA-3
Q143 0.860 0.730 0.270 !       0.75 eA-3
Q144 0.360 0.230 0.770 !       0.75 eA-3
C145 0.465 0.366 0.417 !       0.74 eA-3
C146 0.754 0.079 0.079 !       0.74 eA-3
Q147 0.756 0.375 0.482 !       0.73 eA-3
C148 0.656 0.346 0.437 !       0.72 eA-3
Q149 0.222 0.703 0.108 !       0.72 eA-3
Q150 0.296 0.704 0.048 !       0.67 eA-3
Q151 0.341 0.211 0.789 !       0.62 eA-3
C152 1.000 0.875 0.008 !       0.56 eA-3
Q153 0.307 0.689 0.193 !       0.56 eA-3
Q154 0.252 0.096 0.139 !       0.54 eA-3
Q155 0.223 0.637 0.301 !       0.53 eA-3
Q156 0.338 0.078 0.024 !       0.52 eA-3
C157 0.473 0.494 0.307 !       0.51 eA-3
C158 0.499 0.671 0.509 !       0.50 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 1168 electrons were 
found in a volume of 2626Å³ in 1 void per unit cell. 
This is consistent with the presence of 
65[CH3OH] per Unit Cell 
which account for 1080 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.026 -0.017 -0.007 2626 1168 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.575
_oxdiff_exptl_absorpt_empirical_full_min 0.616
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_p6_w1_70s_0063
_database_code_depnum_ccdc_archive 'CCDC 2299174'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_p6_w1_70s_0063 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT987_zif67_p6_w1_70s_0063 
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_CRYSC01_zif67_p6_w1_70s_0063 
;
PROBLEM: The word below has not been recognised as a standard
RESPONSE: "bluish" is a standard colour variation descriptor in Olex2
;
_vrf_PLAT018_zif67_p6_w1_70s_0063 
;
PROBLEM: _diffrn_measured_fraction_theta_max .NE. *_full           ! Check
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT029_zif67_p6_w1_70s_0063 
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.963 Why?
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT341_zif67_p6_w1_70s_0063 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0075 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_audit_creation_date             2023-10-02
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C8 H10 Co N4, 4.833[CH3OH]'
_chemical_formula_sum            'C12.83 H29.33 Co N4 O4.83'
_chemical_formula_weight         375.90
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
_chemical_absolute_configuration ad
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            'bluish violet'
_diffrn_ambient_temperature      293(2)
_chemical_oxdiff_formula         'C12 H25 Co N4 O4'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

_cell_length_a                   16.8677(5)
_cell_length_b                   16.8677(5)
_cell_length_c                   16.8677(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4799.2(4)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    952
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.2230
_cell_measurement_theta_min      2.4140
_shelx_estimated_absorpt_T_max   0.898
_shelx_estimated_absorpt_T_min   0.852
_exptl_absorpt_coefficient_mu    1.103
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0674 before and 0.0508 after correction.
The Ratio of minimum to maximum transmission is 0.8389.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             2399
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.963
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            2322
_diffrn_reflns_point_group_measured_fraction_full 0.920
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        23.213
_diffrn_reflns_theta_max         23.213
_diffrn_reflns_theta_min         1.707
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 13.3333
_diffrn_measured_fraction_theta_full 0.963
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    -31.60  35.00   0.10    0.10   0.00   0.00   0.00    --   666
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'dectris-CrysAlisPro-abstract goniometer imported dectris images'
_diffrn_measurement_method       'φ scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0277149000
_diffrn_orient_matrix_UB_12      -0.0049529000
_diffrn_orient_matrix_UB_13      -0.0311297000
_diffrn_orient_matrix_UB_21      -0.0060577000
_diffrn_orient_matrix_UB_22      -0.0399511000
_diffrn_orient_matrix_UB_23      0.0117705000
_diffrn_orient_matrix_UB_31      -0.0310589000
_diffrn_orient_matrix_UB_32      0.0122620000
_diffrn_orient_matrix_UB_33      0.0256438000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   Synchrotron
_diffrn_source_type              'AS beamline MX1'
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    0.866
_reflns_Friedel_fraction_max     0.866
_reflns_number_gt                616
_reflns_number_total             623
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.223
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details 
;
 Flack x determined using 250 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.127(19)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     23
_refine_ls_number_reflns         623
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0278
_refine_ls_restrained_S_all      1.125
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0378P)²+3.8957P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0782
_refine_ls_wR_factor_ref         0.0783
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-N1
 1.35 with sigma of 0.01
 C2-C1
 1.48 with sigma of 0.01
 C3-C2
 2.169 with sigma of 0.01
 N1-C2
 1.35 with sigma of 0.01
3. Restrained planarity
 C3, N1, C2, C1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(N1) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H1C(0.5)
7.a Me refined with riding coordinates:
 C1(H1A,H1B,H1C)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 -0.500000 -0.250000 0.0366(4) Uani 1 4 d S T P . .
N1 N 0.03662(18) -0.5875(2) -0.3188(2) 0.0396(7) Uani 1 1 d D . . . .
C2 C -0.0076(3) -0.6352(2) -0.3648(2) 0.0396(7) Uani 1 2 d DS T P . .
C1 C -0.0967(4) -0.6345(3) -0.3655(3) 0.0476(17) Uani 1 2 d DS T P . .
H1A H -0.118113 -0.678237 -0.407340 0.071 Uiso 0.5 1 calc R U P A -1
H1B H -0.118695 -0.648445 -0.306817 0.071 Uiso 0.5 1 calc R U P A -1
H1C H -0.117476 -0.576287 -0.382874 0.071 Uiso 0.5 1 calc R U P A -1
C3 C 0.1143(2) -0.6024(3) -0.3391(3) 0.0396(7) Uani 1 1 d D . . . .
H3 H 0.165830 -0.574023 -0.314321 0.047 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.977(3) 40_444 ?
Co1 N1 1.977(3) . ?
Co1 N1 1.977(3) 39_544 ?
Co1 N1 1.977(3) 2_545 ?
N1 C2 1.344(4) . ?
N1 C3 1.378(5) . ?
C2 C1 1.503(8) . ?
C1 H1A 1.0830 . ?
C1 H1B 1.0830 . ?
C1 H1C 1.0830 . ?
C3 C3 1.394(10) 20_544 ?
C3 H3 1.0770 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 108.11(19) 40_444 39_544 ?
N1 Co1 N1 110.16(9) 39_544 . ?
N1 Co1 N1 110.16(9) 40_444 . ?
N1 Co1 N1 110.16(9) 40_444 2_545 ?
N1 Co1 N1 110.16(9) 39_544 2_545 ?
N1 Co1 N1 108.11(19) 2_545 . ?
C2 N1 Co1 127.8(3) . . ?
C2 N1 C3 106.0(4) . . ?
C3 N1 Co1 125.4(3) . . ?
N1 C2 N1 112.5(5) . 20_544 ?
N1 C2 C1 123.7(2) 20_544 . ?
N1 C2 C1 123.7(2) . . ?
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1B 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N1 C3 C3 107.8(2) . 20_544 ?
N1 C3 H3 126.1 . . ?
C3 C3 H3 126.1 20_544 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 171.15(16) . . . 20_544 ?
Co1 N1 C2 C1 -6.1(7) . . . . ?
Co1 N1 C3 C3 -170.94(18) . . . 20_544 ?
C2 N1 C3 C3 -0.7(3) . . . 20_544 ?
C3 N1 C2 N1 1.2(5) . . . 20_544 ?
C3 N1 C2 C1 -176.1(4) . . . . ?

loop_
_platon_missing_refln_index_h
_platon_missing_refln_index_k
_platon_missing_refln_index_l
_platon_missing_refln_theta
0 0 4 4.834
1 2 5 6.626

_platon_squeeze_details          
;
TITL zif67_p6_w1_70s_0063_a.res in I-43m
CELL   16.8677   16.8677   16.8677     90.00     90.00     90.00
SPGR I-43m
# Solvent Accessible Volume =      2427
# Electrons Found in S.A.V. =      1034
# Note: Atoms in Void are Labelled as Cxxx and Qxxx for all Others
C101 1.000 0.500 0.000 !       5.77 eA-3
C102 1.000 0.438-0.001 !       4.21 eA-3
C103 0.227 0.785 0.039 !       4.16 eA-3
C104 0.733 0.267 0.267 !       4.06 eA-3
C105 1.000 0.719 0.008 !       2.88 eA-3
C106 0.515 0.287 0.287 !       2.53 eA-3
C107 0.422 0.422 0.422 !       2.45 eA-3
C108 0.610 0.390 0.389 !       1.65 eA-3
C109 0.389 0.392 0.608 !       1.63 eA-3
C110 0.127 0.877 0.124 !       1.59 eA-3
C111 0.582 0.418 0.417 !       1.50 eA-3
C112 0.627 0.705 0.624 !       1.37 eA-3
C113 0.127 0.205 0.124 !       1.37 eA-3
C114 0.173 0.157 0.175 !       1.28 eA-3
C115 0.673 0.657 0.675 !       1.28 eA-3
C116 0.401 0.667 0.399 !       1.25 eA-3
C117 0.398 0.408 0.648 !       1.25 eA-3
C118 0.641 0.647 0.687 !       1.22 eA-3
C119 0.277 0.276 0.277 !       1.05 eA-3
C120 0.159 0.111 0.152 !       1.04 eA-3
C121 0.966 0.037 0.037 !       0.88 eA-3
C122 1.000 0.844-0.004 !       0.86 eA-3
C123 0.016 0.060 0.060 !       0.71 eA-3
C124 0.033 0.096 0.029 !       0.58 eA-3
Q125 0.249 0.249 0.139 !       0.57 eA-3
;
_platon_squeeze_special_details  
;
A solvent mask was calculated and 1037 electrons were 
found in a volume of 2401Å³ in 1 void per unit cell. 
This is consistent with the presence of 
58[CH3OH] per Unit Cell 
which account for 1044 electrons 
per unit cell.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.025 -0.016 -0.007 2401 1037 ' '

_platon_squeeze_void_probe_radius 1.20

loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00000000
omega rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.00000000 -0.76604444 0.00000000 0.64278761
phi rotation goniometer -1 kappa . 0.00000000 0.00000000 1.00000000
theta rotation goniometer -1 . 0.00000000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.081
_oxdiff_exptl_absorpt_empirical_full_min 0.739
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif_67_2
_database_code_depnum_ccdc_archive 'CCDC 2299176'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
_audit_creation_date             2023-10-03
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ZIF-67
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 1.833[C2H5OH]'
_chemical_formula_sum            'C11.67 H21 Co N4 O1.83'
_chemical_formula_weight         305.57
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF-67 test 2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co -2.3653 3.6143 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.9230(5)
_cell_length_b                   16.9230(5)
_cell_length_c                   16.9230(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4846.5(4)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    1379
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      71.4330
_cell_measurement_theta_min      3.6440
_shelx_estimated_absorpt_T_max   0.520
_shelx_estimated_absorpt_T_min   0.388
_exptl_absorpt_coefficient_mu    8.347
_exptl_absorpt_correction_T_max  0.711
_exptl_absorpt_correction_T_min  0.475
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1928
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
8 -2 7 0.0709
-8 2 -7 0.0705
5 -8 6 0.0441
-5 8 -6 0.0442
0 -7 -9 0.0586
0 7 9 0.0575
9 5 2 0.0643
-9 -5 -2 0.0640
-9 -2 6 0.0482
9 2 -6 0.0476

_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
8.4766 -2.4335 6.5453 0.5277 0.1259 -0.8400
-8.4766 2.4335 -6.5453 -0.5277 -0.1259 0.8400
4.8586 -7.8585 5.9334 -0.0384 0.0317 -0.9988
-4.8586 7.8585 -5.9334 0.0384 -0.0317 0.9988
-0.4730 -6.7549 -8.6671 -0.7589 0.6489 0.0555
0.4730 6.7549 8.6671 0.7589 -0.6489 -0.0555
9.3346 5.2878 2.3950 0.9282 0.3280 -0.1755
-9.3346 -5.2878 -2.3950 -0.9282 -0.3280 0.1755
-8.6897 -2.0241 6.3829 -0.3809 -0.9180 -0.1100
8.6897 2.0241 -6.3829 0.3809 0.9180 0.1100

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            4186
_diffrn_reflns_point_group_measured_fraction_full 0.944
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.582
_diffrn_reflns_theta_min         3.694
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -28.00  22.00   0.50    1.81    --   45.98 -13.00 -62.00  100
  2  ω     79.00 175.00   0.50   26.93    --  102.69  87.00 106.00  192
  3  ω     74.00 119.00   0.50    1.81    --   45.98 125.00-180.00   90
  4  ω     30.00  69.00   0.50   26.93    --  102.69 -61.00  30.00   78
  5  ω     25.00  60.00   0.50    1.81    --   45.98  74.00   2.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0541423000
_diffrn_orient_matrix_UB_12      0.0643617000
_diffrn_orient_matrix_UB_13      0.0344414000
_diffrn_orient_matrix_UB_21      0.0610527000
_diffrn_orient_matrix_UB_22      -0.0159498000
_diffrn_orient_matrix_UB_23      -0.0657676000
_diffrn_orient_matrix_UB_31      -0.0405417000
_diffrn_orient_matrix_UB_32      0.0622410000
_diffrn_orient_matrix_UB_33      -0.0526951000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.673
_reflns_Friedel_fraction_full    0.879
_reflns_Friedel_fraction_max     0.812
_reflns_number_gt                741
_reflns_number_total             880
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details 
;
 Flack x determined using 243 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.020(11)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     24
_refine_ls_number_reflns         880
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0584
_refine_ls_restrained_S_all      1.096
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1285P)²+0.6552P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1773
_refine_ls_wR_factor_ref         0.1899
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C1, N1, C2, C3
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(N1) = Uanis(C2)
4. Rigid body (RIGU) restrains
 C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1)
6.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.000000 0.250000 0.500000 0.0646(7) Uani 1 4 d S T P . .
N1 N 0.0348(3) 0.3178(3) 0.5891(4) 0.0708(10) Uani 1 1 d . . . . .
C2 C -0.0041(8) 0.3766(3) 0.6234(3) 0.0708(10) Uani 1 2 d S T P . .
C1 C 0.1073(4) 0.3159(4) 0.6280(4) 0.0708(10) Uani 1 1 d . . . . .
H1 H 0.155253 0.276128 0.615280 0.085 Uiso 1 1 calc R U . . .
C3 C -0.0856(6) 0.4019(5) 0.5981(5) 0.079(3) Uani 1 2 d S T P . .
H3A H -0.084429 0.419378 0.536575 0.118 Uiso 0.5 1 calc R U P A -1
H3B H -0.104719 0.451322 0.634002 0.118 Uiso 0.5 1 calc R U P A -1
H3C H -0.126371 0.353083 0.605640 0.118 Uiso 0.5 1 calc R U P A -1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.985(6) 48 ?
Co1 N1 1.985(6) . ?
Co1 N1 1.985(6) 3_556 ?
Co1 N1 1.985(6) 46_455 ?
N1 C2 1.326(8) . ?
N1 C1 1.393(9) . ?
C2 C3 1.506(15) . ?
C1 C1 1.341(14) 20_566 ?
C1 H1 1.0770 . ?
C3 H3A 1.0831 . ?
C3 H3B 1.0831 . ?
C3 H3C 1.0831 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 109.55(17) 48 3_556 ?
N1 Co1 N1 109.3(3) 3_556 . ?
N1 Co1 N1 109.55(17) 48 . ?
N1 Co1 N1 109.3(3) 48 46_455 ?
N1 Co1 N1 109.55(17) 3_556 46_455 ?
N1 Co1 N1 109.55(17) 46_455 . ?
C2 N1 Co1 128.2(6) . . ?
C2 N1 C1 104.4(7) . . ?
C1 N1 Co1 127.4(5) . . ?
N1 C2 N1 114.1(10) . 20_566 ?
N1 C2 C3 122.9(5) 20_566 . ?
N1 C2 C3 122.9(5) . . ?
N1 C1 H1 125.7 . . ?
C1 C1 N1 108.5(4) 20_566 . ?
C1 C1 H1 125.7 20_566 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 179.7(3) . . . 20_566 ?
Co1 N1 C2 C3 0.2(13) . . . . ?
Co1 N1 C1 C1 179.3(4) . . . 20_566 ?
C2 N1 C1 C1 1.3(6) . . . 20_566 ?
C1 N1 C2 N1 -2.3(11) . . . 20_566 ?
C1 N1 C2 C3 178.2(9) . . . . ?

_smtbx_masks_special_details     
;
A solvent mask was calculated and 577 electrons were 
found in a volume of 2453Å³ in 1 void per unit cell. 
This is consistent with the presence of 22[C2H5OH] per Unit Cell 
which account for 572 electrons 
per unit cell.
;
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.503 -0.384 -0.283 2452.7 576.7 '22 C2H5OH'

_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_platon_squeeze_special_details  ?
_platon_squeeze_void_probe_radius 1.20

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.328
_oxdiff_exptl_absorpt_empirical_full_min 0.745
# start Validation Reply Form
_vrf_PLAT341_zif_67_2            
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............      0.013 Ang.  
RESPONSE: ZIF-67 has large pore volume with significant 
disordered solvent, which reduces resolution 
and thus precision.
;
_vrf_PLAT911_zif_67_2            
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report
RESPONSE: These two reflections were omitted due to high error. 
0 4 0 in particular, is a problem reflection in ZIF-67.
;
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zif67_ln2_2900
_database_code_depnum_ccdc_archive 'CCDC 2299166'
loop_
_audit_author_name
_audit_author_address
'Stephen Moggach'
;The University of Western Australia
Australia
;
_audit_update_record             
;
2023-10-04 deposited with the CCDC.	2023-11-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_zif67_ln2_2900      
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: This is caused by shading by the diamond anvil cell.
;
_vrf_PLAT090_zif67_ln2_2900      
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       4.39 Note
RESPONSE: The sample is shaded by the diamond anvil cell preventing collection of reflections from multiple angles. This is common in high pressure experiments
;
_vrf_PLAT341_zif67_ln2_2900      
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.02 Ang.
RESPONSE: ZIF-67 has large pore volume which reduces resolution, and is further shaded by the diamond anvil cell.
;
_vrf_PLAT430_zif67_ln2_2900      
;
PROBLEM: Short Inter D...A Contact  N4       ..N10      .       2.82 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2900_2    
;
PROBLEM: Short Inter D...A Contact  N8       ..N6       .       2.81 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2900_3    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2900_4    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT430_zif67_ln2_2900_5    
;
PROBLEM: Short Inter D...A Contact  N13      ..N12      .       2.80 Ang.
RESPONSE: This is not a H bonding, and is just N disorder.
;
_vrf_PLAT987_zif67_ln2_2900      
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check
RESPONSE: Due to the use of Mo radiation and shading from diamond anvil, accurate refinement of flack is not possible/flack is meaningless. No Twin is believed to be present.
;
_vrf_PLAT042_zif67_ln2_2900      
;
PROBLEM: Calc. and Reported MoietyFormula Strings  Differ     Please Check
RESPONSE: Occupancy of N in pores are in different, disordered positions and do not add to integers,causing this particular error
;
_vrf_PLAT202_zif67_ln2_2900      
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          6 Check
RESPONSE: N atoms are too disordered to model with thermal parameters, it is more appropriate to model them isotropically.
;
_vrf_PLAT723_zif67_ln2_2900      
;
PROBLEM: Torsion Calc     -119.00, Rep    -117(63) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_vrf_PLAT723_zif67_ln2_2900_2    
;
PROBLEM: Torsion Calc      119.00, Rep     117(63) Dev...       2.00 Sigma
RESPONSE: Not a real torsion angle, N solvent atoms are extremely disordered.
;
_audit_creation_date             2023-10-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C8 H10 Co N4, 18.667(N0.5)'
_chemical_formula_sum            'C8 H10 Co N13.33'
_chemical_formula_weight         351.89
_chemical_absolute_configuration ad
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Co C8 H10 N4'
_chemical_oxdiff_usercomment     'ZIF67 @ 2.9 GPa in LN2'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_H-M_alt        'I -4 3 m'
_space_group_name_Hall           'I -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'z+1/2, x+1/2, y+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'y+1/2, x+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, z+1/2, y+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, -z+1/2, y+1/2'
'x+1/2, -z+1/2, -y+1/2'
'z+1/2, y+1/2, x+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, y+1/2, -x+1/2'
'-z+1/2, -y+1/2, x+1/2'

_cell_length_a                   16.5684(3)
_cell_length_b                   16.5684(3)
_cell_length_c                   16.5684(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4548.2(2)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    7907
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.7480
_cell_measurement_theta_min      3.4610
_shelx_estimated_absorpt_T_max   0.903
_shelx_estimated_absorpt_T_min   0.855
_exptl_absorpt_coefficient_mu    1.153
_exptl_absorpt_correction_T_max  0.7309
_exptl_absorpt_correction_T_min  0.6756
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0861 before and 0.0728 after correction.
The Ratio of minimum to maximum transmission is 0.9243.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear bluish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2140
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16850
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        18.983
_diffrn_reflns_theta_max         18.983
_diffrn_reflns_theta_min         3.478
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -84.00 -30.00   0.50   33.13    --   13.12 -29.00 -95.00  108
  2  ω     62.00  96.00   0.50   33.13    --   13.12  29.00  65.00   68
  3  ω    -99.00 -30.00   0.50   33.13    --  -13.27 -29.00 -95.00  138
  4  ω    -16.00  43.00   0.50   33.13    --   13.12 -38.00-180.00  118
  5  ω    -41.00  22.00   0.50   33.13    --   13.12  53.00 162.00  126
  6  ω    -41.00  22.00   0.50   33.13    --   13.12  53.00 -17.00  126
  7  ω    -22.00  57.00   0.50   33.13    --   13.12 -53.00  17.00  158
  8  ω      5.00  84.00   0.50   33.13    --   13.12-114.00  45.00  158
  9  ω    -59.00  -5.00   0.50   33.13    --   13.12 114.00 135.00  108
 10  ω    -10.00  68.00   0.50   33.13    --   13.12 -82.00-151.00  156
 11  ω    -94.00 -68.00   0.50   33.13    --   13.12 178.00 -90.00   52
 12  ω    -26.00  53.00   0.50   33.13    --  -13.27 -40.00-167.00  158
 13  ω    -53.00  26.00   0.50   33.13    --  -13.27  40.00 -12.00  158
 14  ω    -63.00   4.00   0.50   33.13    --  -13.27  57.00-180.00  134
 15  ω     -3.00  50.00   0.50   33.13    --  -13.27 -97.00  35.00  106
 16  ω     54.00  96.00   0.50   33.13    --   13.12-178.00 -90.00   84
 17  ω    -36.00 -16.00   0.50   33.13    --   13.12  38.00   0.00   40
 18  ω     68.00  96.00   0.50   33.13    --   13.12-178.00  90.00   56
 19  ω    -27.00  -3.00   0.50   33.13    --  -13.27  19.00-150.00   48
 20  ω    -43.00 -18.00   0.50   33.13    --  -13.27  38.00-180.00   50
 21  ω    -68.00  10.00   0.50   33.13    --  -13.27  82.00 -29.00  156
 22  ω    -32.00  47.00   0.50   33.13    --  -13.27 -26.00   8.00  158
 23  ω    -38.00  -9.00   0.50   33.13    --  -13.27  77.00 150.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0392875000
_diffrn_orient_matrix_UB_12      -0.0074377000
_diffrn_orient_matrix_UB_13      -0.0152804000
_diffrn_orient_matrix_UB_21      0.0063490000
_diffrn_orient_matrix_UB_22      -0.0421331000
_diffrn_orient_matrix_UB_23      0.0041757000
_diffrn_orient_matrix_UB_31      -0.0157705000
_diffrn_orient_matrix_UB_32      0.0015640000
_diffrn_orient_matrix_UB_33      0.0397717000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                346
_reflns_number_total             373
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.747
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details 
;
 Flack x determined using 143 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.088(18)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     49
_refine_ls_number_reflns         373
_refine_ls_number_restraints     11
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0796
_refine_ls_restrained_S_all      1.172
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1708P)²+9.6005P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2069
_refine_ls_wR_factor_ref         0.2121
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3-C2
 1.55 with sigma of 0.01
 N1-C2
 1.337 with sigma of 0.01
 C1-N1
 1.387 with sigma of 0.01
 C1-C2
 2.175 with sigma of 0.01
 N9-N8
 1.08 with sigma of 0.02
 N4-N5
 1.08 with sigma of 0.02
 N8-N9
 1.09 with sigma of 0.02
3. Restrained planarity
 C1, C2, N1, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(C2) = Uanis(N1)
Uiso(N15) = Uiso(N13)
Uiso(N4) = Uiso(N5)
Uiso(N3) = Uiso(N2)
Uiso(N6) = Uiso(N7)
Uiso(N9) = Uiso(N8)
5. Rigid body (RIGU) restrains
 C3, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: H3A(0.5) H3B(0.5) H3C(0.5) N2(0.083333) N3(0.166667) N6(0.05555)
 N4(0.25) N11(0.083333) N12(0.083333) N7(0.11112) N13(0.083333) N10(0.083333)
 N15(0.08335)
7.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.500000 0.250000 0.000000 0.041(2) Uani 1 4 d S T P . .
N1 N 0.5851(7) 0.3201(7) 0.0426(7) 0.039(3) Uani 1 1 d D . . . .
C2 C 0.6321(7) 0.3679(7) -0.0022(9) 0.039(3) Uani 1 2 d DS T P . .
C1 C 0.6025(10) 0.3391(11) 0.1217(7) 0.039(3) Uani 1 1 d D . . . .
H1 H 0.575005 0.312663 0.174301 0.047 Uiso 1 1 calc R U . . .
C3 C 0.6290(11) 0.3710(11) -0.0953(11) 0.047(7) Uani 1 2 d DS T P . .
H3A H 0.585750 0.327125 -0.117117 0.071 Uiso 0.5 1 calc R U P A -1
H3B H 0.610809 0.430847 -0.114421 0.071 Uiso 0.5 1 calc R U P A -1
H3C H 0.688080 0.357390 -0.119587 0.071 Uiso 0.5 1 calc R U P A -1
N2 N 0.500000 0.500000 0.000000 0.066(10) Uiso 0.6666 8 d S . P . .
N5 N 0.500000 0.500000 -0.232(3) 0.120(14) Uiso 1 4 d DS . P . .
N8 N 0.7848(15) 0.2152(15) 0.078(2) 0.126(9) Uiso 1 2 d DS . P B 1
N3 N 0.500000 0.500000 -0.039(2) 0.066(10) Uiso 0.6667 4 d S . P . .
N9 N 0.7624(15) 0.2376(15) 0.025(2) 0.126(9) Uiso 1 2 d DS . P B 1
N6 N 0.743(5) 0.257(5) -0.257(5) 0.064(14) Uiso 0.3333 6 d S . P . .
N4 N 0.5446(12) 0.4554(12) -0.228(4) 0.120(14) Uiso 0.5 2 d DS . P . .
N11 N 0.565(6) 0.435(6) -0.435(6) 0.08(4) Uiso 0.5 6 d S . P . .
N12 N 0.589(9) 0.411(9) -0.465(12) 0.09(8) Uiso 0.1667 2 d S . P . 1
N7 N 0.765(2) 0.235(2) -0.235(2) 0.064(14) Uiso 0.6667 6 d S . P . .
N13 N 0.875(5) 0.125(5) -0.125(5) 0.07(3) Uiso 0.5 6 d S . P . .
N10 N 0.576(5) 0.424(5) -0.392(9) 0.04(6) Uiso 0.1667 2 d S . P . 2
N15 N 0.839(10) 0.118(7) -0.118(7) 0.07(3) Uiso 0.1667 2 d S . P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 1.958(11) . ?
Co1 N1 1.958(11) 3_655 ?
Co1 N1 1.958(11) 46 ?
Co1 N1 1.958(11) 48_554 ?
N1 C2 1.336(11) . ?
N1 C1 1.379(12) . ?
C2 C3 1.543(14) . ?
C1 C1 1.37(4) 14_665 ?
C1 H1 1.0770 . ?
C3 H3A 1.0830 . ?
C3 H3B 1.0830 . ?
C3 H3C 1.0830 . ?
N2 N3 0.64(4) . ?
N2 N3 0.64(4) 3_655 ?
N5 N4 1.05(3) . ?
N5 N4 1.05(3) 2_665 ?
N8 N9 1.02(2) . ?
N3 N3 1.29(7) 3_655 ?
N6 N7 0.63(13) . ?
N11 N12 0.7(2) . ?
N11 N12 0.7(2) 12_654 ?
N11 N12 0.7(2) 6_665 ?
N11 N10 0.76(17) 6_665 ?
N11 N10 0.76(17) . ?
N11 N10 0.76(17) 12_654 ?
N12 N12 1.3(4) 6_665 ?
N12 N12 1.3(4) 12_654 ?
N13 N15 0.61(17) 6_665 ?
N13 N15 0.61(17) . ?
N13 N15 0.61(17) 12_654 ?
N10 N10 0.7(2) 6_665 ?
N10 N10 0.7(2) 12_654 ?
N15 N15 1.0(3) 6_665 ?
N15 N15 1.0(3) 12_654 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Co1 N1 110.6(4) . 46 ?
N1 Co1 N1 107.2(7) 46 48_554 ?
N1 Co1 N1 110.6(4) . 48_554 ?
N1 Co1 N1 107.2(7) . 3_655 ?
N1 Co1 N1 110.6(4) 46 3_655 ?
N1 Co1 N1 110.6(4) 3_655 48_554 ?
C2 N1 Co1 124.9(7) . . ?
C2 N1 C1 105.7(11) . . ?
C1 N1 Co1 129.0(10) . . ?
N1 C2 N1 112.5(13) 14_665 . ?
N1 C2 C3 123.7(7) 14_665 . ?
N1 C2 C3 123.7(7) . . ?
N1 C1 H1 126.0 . . ?
C1 C1 N1 108.1(9) 14_665 . ?
C1 C1 H1 126.0 14_665 . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 N2 N3 180.0 . 3_655 ?
N4 N5 N4 173(10) . 2_665 ?
N2 N3 N3 0.000(3) . 3_655 ?
N12 N11 N12 115(10) . 12_654 ?
N12 N11 N12 115(10) . 6_665 ?
N12 N11 N12 115(10) 12_654 6_665 ?
N12 N11 N10 111(10) 12_654 12_654 ?
N12 N11 N10 62(10) . 12_654 ?
N12 N11 N10 62(10) 12_654 6_665 ?
N12 N11 N10 62(10) 6_665 12_654 ?
N12 N11 N10 62(10) . 6_665 ?
N12 N11 N10 111(10) 6_665 6_665 ?
N10 N11 N10 58(10) 6_665 12_654 ?
N10 N11 N10 58(10) 6_665 . ?
N10 N11 N10 58(10) 12_654 . ?
N11 N12 N12 33(9) . 12_654 ?
N11 N12 N12 33(9) . 6_665 ?
N12 N12 N12 60.00(3) 12_654 6_665 ?
N15 N13 N15 108(10) 6_665 12_654 ?
N15 N13 N15 108(10) 6_665 . ?
N15 N13 N15 108(10) 12_654 . ?
N10 N10 N11 61(9) 12_654 . ?
N10 N10 N11 61(9) 6_665 . ?
N10 N10 N10 60.00(5) 12_654 6_665 ?
N13 N15 N15 36(10) . 12_654 ?
N13 N15 N15 36(10) . 6_665 ?
N15 N15 N15 60.00(4) 6_665 12_654 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Co1 N1 C2 N1 174.0(6) . . . 14_665 ?
Co1 N1 C2 C3 -3(2) . . . . ?
Co1 N1 C1 C1 -173.0(8) . . . 14_665 ?
C2 N1 C1 C1 -0.8(11) . . . 14_665 ?
C1 N1 C2 N1 1.4(19) . . . 14_665 ?
C1 N1 C2 C3 -176.0(15) . . . . ?
N12 N11 N12 N12 -136(69) 6_665 . . 12_654 ?
N12 N11 N12 N12 136(69) 12_654 . . 6_665 ?
N10 N11 N10 N10 -70(7) 6_665 . . 12_654 ?
N10 N11 N10 N10 70(7) 12_654 . . 6_665 ?
N15 N13 N15 N15 -117(63) 12_654 . . 6_665 ?
N15 N13 N15 N15 117(63) 6_665 . . 12_654 ?


loop_
_axis.id
_axis.type
_axis.equipment
_axis.parity
_axis.depends_on
_axis.zero
_axis.vector[1]
_axis.vector[2]
_axis.vector[3]
source . source . . . 1.00000000 0.00000000 0.00003403
omega rotation goniometer -1 . 0.12240000 0.00000000 0.00000000 1.00000000
kappa rotation goniometer -1 omega 0.28425000 -0.76560404 0.00000000 0.64331210
phi rotation goniometer -1 kappa . -0.00006266 0.00000000 1.00000000
theta rotation goniometer -1 . 0.19892000 0.00000000 0.00000000 1.00000000
matrixX general general . phi . 1.00000000 0.00000000 0.00000000
matrixY general general . phi . 0.00000000 1.00000000 0.00000000
matrixZ general general . phi . 0.00000000 0.00000000 1.00000000
dacX translation general . phi . 0.00000000 1.00000000 0.00000000
dacY translation general . phi . -1.00000000 0.00000000 0.00000000
dacZ translation general . phi . 0.00000000 0.00000000 1.00000000

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 15.828
_oxdiff_exptl_absorpt_empirical_full_min 0.726
