Single-crystal-to-single-crystal metalation of a metal-organic framework: a route toward structurally well-defined catalysts.
Gonzalez, Miguel I.; Bloch, Eric D.; Mason, Jarad A.; Teat, Simon J.; Long, Jeffrey R.; Inorganic chemistry 54 (2015) 2995–3005; doi:10.1021/acs.inorgchem.5b00096

data_4346046
_publ_section_title
;
 Single-crystal-to-single-crystal metalation of a metal-organic framework:
 a route toward structurally well-defined catalysts.
;
_journal_issue                   6
_journal_name_full               'Inorganic chemistry'
_journal_page_first              2995
_journal_page_last               3005
_journal_paper_doi               10.1021/acs.inorgchem.5b00096
_journal_volume                  54
_journal_year                    2015
_chemical_formula_sum
'C70.56 H39.28 Cl8.34 Cu8.34 N11.76 O31.52 Zr6'
_chemical_formula_weight         2929.07
_chemical_name_common            Zr6O4(OH)4(bpydc)5.88(CuCl)8.34
_space_group_crystal_system      cubic
_space_group_IT_number           205
_space_group_name_Hall           '-P 2ac 2ab 3'
_space_group_name_H-M_alt        'P a -3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.1490(8)
_cell_length_b                   26.1490(8)
_cell_length_c                   26.1490(8)
_cell_measurement_reflns_used    9261
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      36.387
_cell_measurement_theta_min      2.547
_cell_volume                     17879.9(9)
_computing_cell_refinement       'Bruker SAINT v8.18c'
_computing_data_collection       'Bruker APEX 2'
_computing_data_reduction        'Bruker SAINT v8.18c'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    SHELXS-2014
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX II CCD diffractometer'
_diffrn_measurement_method       '\w/\q scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            234947
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         36.624
_diffrn_reflns_theta_min         1.899
_diffrn_source                   'Advanced Light Source station 11.3.1'
_exptl_absorpt_coefficient_mu    1.859
_exptl_absorpt_correction_T_max  0.9282
_exptl_absorpt_correction_T_min  0.8632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2008/1 Bruker AXS Madison WI USA'
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.087
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       octahedron
_exptl_crystal_F_000             5667
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.297
_refine_diff_density_min         -1.652
_refine_diff_density_rms         0.221
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.248
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         11627
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.251
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0722
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1281P)^2^+49.2571P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2341
_refine_ls_wR_factor_ref         0.2376
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10950
_reflns_number_total             11627
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b00096_si_006.cif
_cod_data_source_block           mig061s_0mb
_cod_original_cell_volume        17879.9(16)
_cod_database_code               4346046
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.929
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C7B-C8B \\sim C7A-C8A
 with sigma of 0.02
 C7B-C6 \\sim C7A-C6
 with sigma of 0.02
 C9-C8B \\sim C9-C8A
 with sigma of 0.02
 C9-C10A \\sim C9-C10B
 with sigma of 0.02
 N2A-C10A \\sim N2B-C10B
 with sigma of 0.02
 N2A-C6 \\sim N2B-C6
 with sigma of 0.02
 N1A-C1 \\sim N1B-C1
 with sigma of 0.02
 C1-C5B \\sim C1-C5A
 with sigma of 0.02
 C4B-C5B \\sim C4A-C5A
 with sigma of 0.02
 C3-C4B \\sim C3-C4A
 with sigma of 0.02
 C3-C2A \\sim C3-C2B
 with sigma of 0.02
 N1A-C2A \\sim N1B-C2B
 with sigma of 0.02
3. Rigid bond restraints
 Cu1B, Cu1A, Cl1B, Cl1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2B, C10B, C6, N2A, C10A, C9, C8A, C7A, C7B, N1B, C1, C2B, N1A, C2A, C3, C4A,
 C5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu2A, Cl2, Cu2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Cu1B \\sim Cu1A \\sim Cl1B \\sim Cl1A \\sim Cu2B \\sim Cl2 \\sim Cu2A: within
2.5A with sigma of 0.02 and sigma for terminal atoms of 0.04
N1B \\sim C1 \\sim C2B \\sim N1A \\sim C2A \\sim C4A \\sim C5A \\sim C3 \\sim
N2B \\sim C10B \\sim C6 \\sim N2A \\sim C10A \\sim C9 \\sim C8A \\sim C7A \\sim
C7B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C7B) = Uanis(C7A)
5. Others
 Fixed Sof: O1A(0.16667) O2A(0.5) O1B(0.16667) O2B(0.5) O3(0.98) O4(0.98)
 O5(0.98) O6(0.98) C1(0.98) C3(0.98) C6(0.98) C9(0.98) C11(0.98) C12(0.98)
 C2B(0.49) H2B(0.49) C4B(0.49) H4B(0.49) C5B(0.49) H5B(0.49) C7B(0.49)
 H7B(0.49) C8B(0.49) H8B(0.49) C10B(0.49) H10B(0.49) N1B(0.49) N2B(0.49)
 C2A(0.49) H2A(0.49) C4A(0.49) H4A(0.49) C5A(0.49) H5A(0.49) C7A(0.49)
 H7A(0.49) C8A(0.49) H8A(0.49) C10A(0.49) H10A(0.49) N1A(0.49) N2A(0.49)
 Cu1B(0.455) Cl1B(0.455) Cu1A(0.455) Cl1A(0.455) Cu2B(0.24) Cu2A(0.24) Cl2(0.48)
6.a Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C4B(H4B), C5B(H5B), C7B(H7B), C8B(H8B), C10B(H10B), C2A(H2A),
 C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C10A(H10A)
;
_shelx_res_checksum              96555
_shelx_hkl_checksum              64582
_olex2_submission_special_instructions 'No special instructions were received'