# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1405181'
_audit_update_record             
;
2015-06-05 deposited with the CCDC.
2015-07-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        'Holmium-BETB MOF'
_chemical_name_common            TCM-9
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C36 H30 Ho N O11'
_chemical_formula_weight         817.54

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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ho Ho -14.9734 3.7046 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           46
_space_group_name_H-M_alt        'I m a 2'
_space_group_name_Hall           'I 2 -2a'

_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, z'
'-x+1/2, y, z'
'x+1/2, -y, z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-x+1, y+1/2, z+1/2'
'x+1, -y+1/2, z+1/2'

_cell_length_a                   21.403(6)
_cell_length_b                   34.255(9)
_cell_length_c                   8.023(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5882(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    4565
_cell_measurement_theta_min      2.9139
_cell_measurement_theta_max      22.0825

_exptl_crystal_description       needle
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.923
_exptl_crystal_F_000             1632
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    2.820
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4845
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Brucker APEX DUO'
_diffrn_measurement_method       oscillation
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            27706
_diffrn_reflns_av_unetI/netI     0.1093
_diffrn_reflns_av_R_equivalents  0.1263
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.434
_diffrn_reflns_theta_max         70.073
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.988
_reflns_number_total             5370
_reflns_number_gt                3362
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_max     0.988
_reflns_Friedel_fraction_full    0.987

_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       APEX
_computing_cell_refinement       Saint
_computing_data_reduction        APEX
_computing_structure_solution    Shelxs-97
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ortep
_computing_publication_material  ?

_refine_special_details          
;
 Refined as a 2-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)+(0.2000P)²]
 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   0.54(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         5370
_refine_ls_number_parameters     211
_refine_ls_number_restraints     330
_refine_ls_R_factor_all          0.2130
_refine_ls_R_factor_gt           0.1469
_refine_ls_wR_factor_ref         0.4213
_refine_ls_wR_factor_gt          0.3668
_refine_ls_goodness_of_fit_ref   1.507
_refine_ls_restrained_S_all      1.658
_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
C1 C 0.7500 0.1786(11) 0.519(7) 0.054(9) Uani 1 2 d S TU P . .
C2 C 0.7500 0.1368(6) 0.505(5) 0.064(10) Uani 1 2 d DGS TU P . .
C3 C 0.7500(10) 0.1159(9) 0.654(4) 0.114(15) Uani 1 2 d DG TU P . .
H3 H 0.7500 0.1293 0.7574 0.137 Uiso 1 2 calc R U P . .
C4 C 0.7500(10) 0.0753(9) 0.651(4) 0.116(16) Uani 1 2 d DG TU P . .
H4 H 0.7500 0.0610 0.7523 0.140 Uiso 1 2 calc R U P . .
C5 C 0.7500(3) 0.0556(6) 0.499(4) 0.112(14) Uani 1 2 d DG TU P . .
C6 C 0.7500(9) 0.0765(7) 0.351(4) 0.087(12) Uani 1 2 d DG TU P . .
H6 H 0.7500 0.0631 0.2472 0.104 Uiso 1 2 calc R U P . .
C7 C 0.7500(9) 0.1171(7) 0.354(4) 0.055(9) Uani 1 2 d DG TU P . .
H7 H 0.7500 0.1314 0.2523 0.066 Uiso 1 2 calc R U P . .
C8 C 0.7500 0.013(2) 0.49243(2) 0.131(17) Uani 1 2 d DS TU P . .
C9 C 0.7500 -0.0233(19) 0.487(4) 0.114(16) Uani 1 2 d DS TU P . .
C10 C 0.7500 -0.0648(16) 0.475(10) 0.113(17) Uani 1 2 d DS TU P . .
C11 C 0.8075(17) -0.0838(10) 0.462(8) 0.137(18) Uani 1 1 d D U . . .
H11 H 0.8453 -0.0695 0.4729 0.164 Uiso 1 1 calc R U . . .
C12 C 0.8091(13) -0.1241(9) 0.433(6) 0.102(13) Uani 1 1 d D U . . .
C13 C 0.7500 -0.1420(14) 0.432(8) 0.093(17) Uani 1 2 d DS TU P . .
H13 H 0.7500 -0.1697 0.4304 0.112 Uiso 1 2 calc R U P . .
C14 C 0.8613(13) -0.1451(8) 0.451(7) 0.15(2) Uani 1 1 d D U . . .
C15 C 0.9094(14) -0.1638(8) 0.478(7) 0.20(3) Uani 1 1 d D U . . .
C16 C 0.9612(18) -0.1842(8) 0.505(6) 0.23(2) Uani 1 1 d DG U . . .
C17 C 0.989(2) -0.2049(12) 0.375(6) 0.24(2) Uani 1 1 d DG U . . .
H17 H 0.9706 -0.2045 0.2674 0.283 Uiso 1 1 calc R U . . .
C18 C 1.043(2) -0.2262(12) 0.404(8) 0.23(2) Uani 1 1 d G U . . .
H18 H 1.0619 -0.2403 0.3152 0.271 Uiso 1 1 calc R U . . .
C19 C 1.0698(19) -0.2267(11) 0.562(8) 0.21(2) Uani 1 1 d DG U . . .
C20 C 1.042(2) -0.2060(15) 0.691(7) 0.24(2) Uani 1 1 d G U . . .
H20 H 1.0604 -0.2064 0.7991 0.284 Uiso 1 1 calc R U . . .
C21 C 0.988(2) -0.1847(14) 0.663(6) 0.27(2) Uani 1 1 d DG U . . .
H21 H 0.9691 -0.1706 0.7514 0.319 Uiso 1 1 calc R U . . .
O1 O 0.7500 0.1963(8) 0.666(6) 0.072(8) Uani 1 2 d S TU P . .
O2 O 0.7500 0.1971(8) 0.382(11) 0.081(7) Uani 1 2 d S TU P . .
O5 O 0.8223(11) 0.1839(6) 0.997(5) 0.087(7) Uani 1 1 d . U . . .
Ho1 Ho 0.7500 0.23370(4) 0.883(4) 0.0355(7) Uani 1 2 d S TU P . .
O6 O 0.891(3) 0.1431(18) 1.196(11) 0.28(3) Uiso 1 1 d . . . . .
O3 O 1.1503(10) -0.2478(7) 0.773(5) 0.071(6) Uani 1 1 d D U . . .
O4 O 1.188(2) -0.2346(16) 0.528(8) 0.25(3) Uani 1 1 d D U . . .
O7 O 0.7500 -0.244(3) 0.441(15) 0.26(4) Uiso 1 2 d DS . P . .
N1 N 0.681(4) -0.286(3) 0.494(19) 0.23(6) Uiso 0.5 1 d D . P . .
C23 C 0.696(4) -0.254(4) 0.396(19) 0.21(6) Uiso 0.5 1 d D . P . .
C24 C 0.613(4) -0.296(3) 0.507(13) 0.11(3) Uiso 0.5 1 d D . P . .
C25 C 0.734(6) -0.311(5) 0.56(3) 0.39(14) Uiso 0.5 1 d D . P . .
C22 C 1.130(3) -0.2382(10) 0.644(12) 0.168(19) Uiso 1 1 d D 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
C1 O2 1.27(8) . ?
C1 O1 1.32(5) . ?
C1 C2 1.44(4) . ?
C2 C3 1.3900 . ?
C2 C7 1.3900 . ?
C3 C4 1.3900 . ?
C4 C5 1.3900 . ?
C5 C6 1.3900 . ?
C5 C8 1.47(7) . ?
C6 C7 1.3900 . ?
C8 C9 1.24(3) . ?
C9 C10 1.43(8) . ?
C10 C11 1.396(18) 3_655 ?
C10 C11 1.396(18) . ?
C11 C12 1.401(18) . ?
C12 C14 1.34(3) . ?
C12 C13 1.406(18) . ?
C13 C12 1.406(18) 3_655 ?
C14 C15 1.23(3) . ?
C15 C16 1.33(3) . ?
C16 C17 1.3900 . ?
C16 C21 1.3900 . ?
C17 C18 1.3900 . ?
C18 C19 1.3900 . ?
C19 C20 1.3900 . ?
C19 C22 1.49(3) . ?
C20 C21 1.3900 . ?
O1 Ho1 2.16(3) . ?
O2 Ho1 2.37(3) 6_654 ?
O5 Ho1 2.48(3) . ?
Ho1 O4 2.08(5) 7_655 ?
Ho1 O4 2.08(5) 5_455 ?
Ho1 O3 2.36(2) 4_455 ?
Ho1 O3 2.36(2) 2_755 ?
Ho1 O2 2.37(3) 6_655 ?
Ho1 O5 2.48(3) 3_655 ?
O3 C22 1.17(7) . ?
O3 Ho1 2.36(2) 2_755 ?
O4 C22 1.56(9) . ?
O4 Ho1 2.08(5) 5_544 ?
O7 C23 1.26(3) 3_655 ?
O7 C23 1.26(3) . ?
N1 C23 1.40(3) . ?
N1 C24 1.49(3) . ?
N1 C25 1.51(3) . ?
C25 C25 0.7(2) 3_655 ?

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
O2 C1 O1 123(4) . . ?
O2 C1 C2 115(4) . . ?
O1 C1 C2 122(3) . . ?
C3 C2 C7 120.0 . . ?
C3 C2 C1 117(2) . . ?
C7 C2 C1 123(2) . . ?
C2 C3 C4 120.0 . . ?
C5 C4 C3 120.0 . . ?
C4 C5 C6 120.0 . . ?
C4 C5 C8 121.2(18) . . ?
C6 C5 C8 118.8(18) . . ?
C5 C6 C7 120.0 . . ?
C6 C7 C2 120.0 . . ?
C9 C8 C5 180.0(2) . . ?
C8 C9 C10 178(4) . . ?
C11 C10 C11 124(6) 3_655 . ?
C11 C10 C9 118(3) 3_655 . ?
C11 C10 C9 118(3) . . ?
C10 C11 C12 120(5) . . ?
C14 C12 C11 122(2) . . ?
C14 C12 C13 121(2) . . ?
C11 C12 C13 114(4) . . ?
C12 C13 C12 128(5) 3_655 . ?
C15 C14 C12 176(4) . . ?
C14 C15 C16 179(3) . . ?
C15 C16 C17 119.9(11) . . ?
C15 C16 C21 120.1(11) . . ?
C17 C16 C21 120.0 . . ?
C18 C17 C16 120.0 . . ?
C17 C18 C19 120.0 . . ?
C20 C19 C18 120.0 . . ?
C20 C19 C22 100(4) . . ?
C18 C19 C22 139(4) . . ?
C19 C20 C21 120.0 . . ?
C20 C21 C16 120.0 . . ?
C1 O1 Ho1 171(3) . . ?
C1 O2 Ho1 120(4) . 6_654 ?
O4 Ho1 O4 80(3) 7_655 5_455 ?
O4 Ho1 O1 139.6(17) 7_655 . ?
O4 Ho1 O1 139.6(17) 5_455 . ?
O4 Ho1 O3 133.1(17) 7_655 4_455 ?
O4 Ho1 O3 61.4(16) 5_455 4_455 ?
O1 Ho1 O3 79.7(7) . 4_455 ?
O4 Ho1 O3 61.4(16) 7_655 2_755 ?
O4 Ho1 O3 133.1(17) 5_455 2_755 ?
O1 Ho1 O3 79.7(7) . 2_755 ?
O3 Ho1 O3 129.7(12) 4_455 2_755 ?
O4 Ho1 O2 58.6(19) 7_655 6_655 ?
O4 Ho1 O2 58.6(19) 5_455 6_655 ?
O1 Ho1 O2 126.2(19) . 6_655 ?
O3 Ho1 O2 78.2(9) 4_455 6_655 ?
O3 Ho1 O2 78.2(9) 2_755 6_655 ?
O4 Ho1 O5 75.6(16) 7_655 . ?
O4 Ho1 O5 123.5(16) 5_455 . ?
O1 Ho1 O5 83.7(8) . . ?
O3 Ho1 O5 147.5(8) 4_455 . ?
O3 Ho1 O5 73.3(8) 2_755 . ?
O2 Ho1 O5 133.5(10) 6_655 . ?
O4 Ho1 O5 123.5(16) 7_655 3_655 ?
O4 Ho1 O5 75.6(16) 5_455 3_655 ?
O1 Ho1 O5 83.7(8) . 3_655 ?
O3 Ho1 O5 73.3(8) 4_455 3_655 ?
O3 Ho1 O5 147.5(8) 2_755 3_655 ?
O2 Ho1 O5 133.5(10) 6_655 3_655 ?
O5 Ho1 O5 77.3(11) . 3_655 ?
C22 O3 Ho1 128(4) . 2_755 ?
C22 O4 Ho1 144(3) . 5_544 ?
C23 O7 C23 133(10) 3_655 . ?
C23 N1 C24 117(3) . . ?
C23 N1 C25 116(4) . . ?
C24 N1 C25 126(5) . . ?
O7 C23 N1 106(10) . . ?
C25 C25 N1 140(5) 3_655 . ?
O3 C22 C19 142(7) . . ?
O3 C22 O4 104(4) . . ?
C19 C22 O4 114(6) . . ?

_refine_diff_density_max         2.909
_refine_diff_density_min         -3.048
_refine_diff_density_rms         0.292

# SQUEEZE RESULTS (APPEND TO CIF)
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
1 -0.003 -0.003 -0.083 3425.0 1319.7
_platon_squeeze_details          
; ?
;


_shelxl_version_number           2013-2



