# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_Co_MOF1_tpt
_audit_block_doi                 10.5517/cc1kgg3l
_database_code_depnum_ccdc_archive 'CCDC 1443859'
_audit_update_record             
;
2016-03-16 deposited with the CCDC.
2016-03-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         
Co3(O)(C9H6N3O2)3(C18H12N6)(NO3)(H2O)(C2H6O)7(C3H7NO)8
_chemical_formula_sum            'C45 H30 Co3 N15 O7'
_chemical_formula_weight         1069.63

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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           186
_space_group_name_H-M_alt        'P 63 m c'
_space_group_name_Hall           'P 6c -2c'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'x-y, x, z+1/2'
'-y, x-y, z'
'-x, -y, z+1/2'
'-x+y, -x, z'
'y, -x+y, z+1/2'
'-x+y, y, z'
'x, x-y, z'
'-y, -x, z'
'y, x, z+1/2'
'x-y, -y, z+1/2'
'-x, -x+y, z+1/2'

_cell_length_a                   16.679(2)
_cell_length_b                   16.679(2)
_cell_length_c                   19.050(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4589.5(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    113(2)
_cell_measurement_reflns_used    8860
_cell_measurement_theta_min      1.4081
_cell_measurement_theta_max      26.0196

_exptl_crystal_description       block
_exptl_crystal_colour            orange-red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.774
_exptl_crystal_F_000             1084
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_exptl_absorpt_coefficient_mu    0.570
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.8664
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   Higashi,T.(1995).

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      113(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Saturn70 (4x4 bin mode)'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            37425
_diffrn_reflns_av_unetI/netI     0.0707
_diffrn_reflns_av_R_equivalents  0.1148
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.410
_diffrn_reflns_theta_max         24.976
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.974
_reflns_number_total             2862
_reflns_number_gt                2517
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.935
_reflns_Friedel_fraction_max     0.999
_reflns_Friedel_fraction_full    0.974

_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.
;

_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
 Refined as a 4-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0912P)²+3.0088P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   ?
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2862
_refine_ls_number_parameters     124
_refine_ls_number_restraints     38
_refine_ls_R_factor_all          0.0734
_refine_ls_R_factor_gt           0.0641
_refine_ls_wR_factor_ref         0.1691
_refine_ls_wR_factor_gt          0.1621
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.101
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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 0.47093(7) 0.73546(3) 0.79685(11) 0.0184(3) Uani 1 2 d S T P . .
O2 O 0.4837(4) 0.6517(4) 0.7214(3) 0.0307(13) Uani 1 1 d . . . . .
O1 O 0.3333 0.6667 0.7766(5) 0.017(2) Uani 1 6 d S T P . .
N3 N 0.6155(5) 0.8077(2) 0.8051(6) 0.0309(19) Uani 1 2 d S T P . .
N1 N 0.4490(4) 0.6347(4) 0.8757(3) 0.0276(15) Uani 1 1 d . . . . .
C2 C 0.4293(4) 0.5707(4) 0.6995(5) 0.031(2) Uani 1 2 d S T P . .
N4 N 0.9522(3) 0.9043(5) 0.8143(5) 0.028(2) Uani 1 2 d S T P . .
N2 N 0.5537(3) 0.4463(3) 0.4664(4) 0.0276(16) Uani 1 2 d S TU P . .
C5 C 0.8079(6) 0.9040(3) 0.8123(5) 0.025(2) Uani 1 2 d S T P . .
C3 C 0.5046(5) 0.3669(5) 0.4312(4) 0.0259(16) Uani 1 1 d . . . . .
H3 H 0.4448 0.3186 0.4443 0.031 Uiso 1 1 calc R U . . .
C1 C 0.4648(5) 0.5352(5) 0.6411(7) 0.0460(16) Uani 1 2 d DS TU P . .
C6 C 0.6626(4) 0.7615(4) 0.8090(4) 0.0280(16) Uani 1 1 d . . . . .
H6 H 0.6291 0.6958 0.8107 0.034 Uiso 1 1 calc R U . . .
C4 C 0.7577(4) 0.8068(5) 0.8103(6) 0.040(2) Uani 1 1 d . . . . .
H4 H 0.7893 0.7726 0.8099 0.048 Uiso 1 1 calc R U . . .
C10 C 0.9111(7) 0.9555(3) 0.8131(7) 0.037(3) Uani 1 2 d S T P . .
C11 C 0.5252(4) 0.4748(4) 0.5296(7) 0.0452(19) Uani 1 2 d S TU P . .
C7 C 0.4392(6) 0.4198(6) 0.5553(5) 0.0470(18) Uani 1 1 d . U . . .
H7 H 0.3989 0.3611 0.5349 0.056 Uiso 1 1 calc R U . . .
C8 C 0.4115(7) 0.4518(6) 0.6126(5) 0.0498(16) Uani 1 1 d D U . . .
H8 H 0.3521 0.4126 0.6324 0.060 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 O1 2.025(2) . ?
Co1 O2 2.088(5) 8_565 ?
Co1 O2 2.088(5) . ?
Co1 N3 2.094(7) . ?
Co1 N1 2.145(6) . ?
Co1 N1 2.145(6) 8_565 ?
O2 C2 1.264(7) . ?
O1 Co1 2.025(2) 3_665 ?
O1 Co1 2.025(2) 5_565 ?
N3 C6 1.351(7) . ?
N3 C6 1.351(7) 8_565 ?
N1 C3 1.318(9) 4_665 ?
N1 N1 1.395(12) 9_665 ?
C2 O2 1.264(7) 9_665 ?
C2 C1 1.513(17) . ?
N4 C10 1.336(6) . ?
N4 C10 1.336(6) 3_765 ?
N2 C3 1.337(8) . ?
N2 C3 1.337(8) 9_665 ?
N2 C11 1.460(14) . ?
C5 C4 1.404(8) 8_565 ?
C5 C4 1.404(8) . ?
C5 C10 1.490(13) . ?
C3 N1 1.318(9) 4_664 ?
C3 H3 0.9500 . ?
C1 C8 1.335(10) . ?
C1 C8 1.335(10) 9_665 ?
C6 C4 1.375(9) . ?
C6 H6 0.9500 . ?
C4 H4 0.9500 . ?
C10 N4 1.336(6) 5_675 ?
C11 C7 1.350(10) . ?
C11 C7 1.350(10) 9_665 ?
C7 C8 1.392(13) . ?
C7 H7 0.9500 . ?
C8 H8 0.9500 . ?

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
O1 Co1 O2 87.5(2) . 8_565 ?
O1 Co1 O2 87.5(2) . . ?
O2 Co1 O2 92.1(3) 8_565 . ?
O1 Co1 N3 173.4(4) . . ?
O2 Co1 N3 87.9(3) 8_565 . ?
O2 Co1 N3 87.9(3) . . ?
O1 Co1 N1 89.3(3) . . ?
O2 Co1 N1 176.3(2) 8_565 . ?
O2 Co1 N1 89.5(2) . . ?
N3 Co1 N1 95.4(3) . . ?
O1 Co1 N1 89.3(3) . 8_565 ?
O2 Co1 N1 89.5(2) 8_565 8_565 ?
O2 Co1 N1 176.3(3) . 8_565 ?
N3 Co1 N1 95.4(3) . 8_565 ?
N1 Co1 N1 88.6(4) . 8_565 ?
C2 O2 Co1 133.2(6) . . ?
Co1 O1 Co1 116.46(17) . 3_665 ?
Co1 O1 Co1 116.46(17) . 5_565 ?
Co1 O1 Co1 116.46(17) 3_665 5_565 ?
C6 N3 C6 119.1(7) . 8_565 ?
C6 N3 Co1 120.4(4) . . ?
C6 N3 Co1 120.4(4) 8_565 . ?
C3 N1 N1 106.5(4) 4_665 9_665 ?
C3 N1 Co1 134.9(5) 4_665 . ?
N1 N1 Co1 118.51(17) 9_665 . ?
O2 C2 O2 126.6(10) . 9_665 ?
O2 C2 C1 116.7(5) . . ?
O2 C2 C1 116.7(5) 9_665 . ?
C10 N4 C10 112.8(9) . 3_765 ?
C3 N2 C3 106.5(8) . 9_665 ?
C3 N2 C11 126.7(4) . . ?
C3 N2 C11 126.7(4) 9_665 . ?
C4 C5 C4 117.7(8) 8_565 . ?
C4 C5 C10 121.1(4) 8_565 . ?
C4 C5 C10 121.1(4) . . ?
N1 C3 N2 110.3(6) 4_664 . ?
N1 C3 H3 124.9 4_664 . ?
N2 C3 H3 124.9 . . ?
C8 C1 C8 117.3(13) . 9_665 ?
C8 C1 C2 121.3(6) . . ?
C8 C1 C2 121.3(6) 9_665 . ?
N3 C6 C4 121.9(6) . . ?
N3 C6 H6 119.1 . . ?
C4 C6 H6 119.1 . . ?
C6 C4 C5 119.6(6) . . ?
C6 C4 H4 120.2 . . ?
C5 C4 H4 120.2 . . ?
N4 C10 N4 127.2(9) . 5_675 ?
N4 C10 C5 116.4(5) . . ?
N4 C10 C5 116.4(5) 5_675 . ?
C7 C11 C7 121.2(12) . 9_665 ?
C7 C11 N2 119.1(6) . . ?
C7 C11 N2 119.1(6) 9_665 . ?
C11 C7 C8 117.8(9) . . ?
C11 C7 H7 121.1 . . ?
C8 C7 H7 121.1 . . ?
C1 C8 C7 122.8(10) . . ?
C1 C8 H8 118.6 . . ?
C7 C8 H8 118.6 . . ?

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 O2 C2 O2 -1.8(16) . . . 9_665 ?
Co1 O2 C2 C1 178.1(7) . . . . ?
C3 N2 C3 N1 0.2(12) 9_665 . . 4_664 ?
C11 N2 C3 N1 178.5(10) . . . 4_664 ?
O2 C2 C1 C8 -177.6(10) . . . . ?
O2 C2 C1 C8 2.3(17) 9_665 . . . ?
O2 C2 C1 C8 -2.3(17) . . . 9_665 ?
O2 C2 C1 C8 177.6(10) 9_665 . . 9_665 ?
C6 N3 C6 C4 -5.9(18) 8_565 . . . ?
Co1 N3 C6 C4 176.1(8) . . . . ?
N3 C6 C4 C5 4.1(15) . . . . ?
C4 C5 C4 C6 -2.2(18) 8_565 . . . ?
C10 C5 C4 C6 -179.4(10) . . . . ?
C10 N4 C10 N4 -3(2) 3_765 . . 5_675 ?
C10 N4 C10 C5 178.3(6) 3_765 . . . ?
C4 C5 C10 N4 -179.4(10) 8_565 . . . ?
C4 C5 C10 N4 -2.2(15) . . . . ?
C4 C5 C10 N4 2.2(15) 8_565 . . 5_675 ?
C4 C5 C10 N4 179.4(10) . . . 5_675 ?
C3 N2 C11 C7 -3.5(18) . . . . ?
C3 N2 C11 C7 174.5(10) 9_665 . . . ?
C3 N2 C11 C7 -174.5(10) . . . 9_665 ?
C3 N2 C11 C7 3.5(18) 9_665 . . 9_665 ?
C7 C11 C7 C8 -4.7(19) 9_665 . . . ?
N2 C11 C7 C8 -175.5(10) . . . . ?
C8 C1 C8 C7 -1(2) 9_665 . . . ?
C2 C1 C8 C7 174.9(10) . . . . ?
C11 C7 C8 C1 2.6(16) . . . . ?

_refine_diff_density_max         0.868
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.072
# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
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 -0.018 -0.012 0.136 2985 1102 ' '
_platon_squeeze_details          
;
In the final refinement, the contributions of disordered 
counter ions and solvent to the structure factors in 
Co-MOF1-tpt were removed with the SQUEEZE program 
and the crystal structure was then further refined with new 
hkl file generated by the SQUEEZE calculation. Based on
the SQUEEZE calculation results, IR, TG analysis,one NO3-,
one water moleculer, seven EtOH and eight DMF moleculers 
were added directly to the final molecular formula.
;
_shelxl_version_number           2014-3

