Two new Cu-based borate catalysts with cubic supramolecular cages for efficient catalytic hydrogen evolution.
Liu, Wen-Fang; Qiu, Qi-Ming; Zhang, Mo; Su, Zhao-Min; An, Qingqing; Lv, Hongjin; Jia, Zhiyu; Yang, Guo-Yu; Dalton transactions (Cambridge, England : 2003) 49 (2020) 10156–10161; doi:10.1039/d0dt01994a

data_7704731
_publ_section_title
;
 Two new Cu-based borate catalysts with cubic supramolecular cages for
 efficient catalytic hydrogen evolution.
;
_journal_issue                   29
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10156
_journal_page_last               10161
_journal_paper_doi               10.1039/d0dt01994a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'B5 Cu H8 K0.535 Na0.465 O13.25, 2.25[H2O]'
_chemical_formula_sum            'B5 Cu H12.5 K0.54 Na0.47 O15.5'
_chemical_formula_weight         410.11
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-06-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-06-23 deposited with the CCDC.	2020-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.1973(11)
_cell_length_b                   18.1973(11)
_cell_length_c                   10.6676(8)
_cell_measurement_reflns_used    3421
_cell_measurement_temperature    299(2)
_cell_measurement_theta_max      27.8220
_cell_measurement_theta_min      4.3245
_cell_volume                     3532.5(4)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SAINT'
_computing_data_reduction        'SADABS (University of Gottingen, 1996)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXL-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      299.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'hybrid pixel array detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0997
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            23332
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.022
_diffrn_reflns_theta_max         25.022
_diffrn_reflns_theta_min         2.238
_exptl_absorpt_coefficient_mu    1.437
_exptl_absorpt_correction_T_max  0.976
_exptl_absorpt_correction_T_min  0.798
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(<i>SADABS</i>; Bruker, 2007)'
_exptl_crystal_colour            'dark green'
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description       block
_exptl_crystal_F_000             1647
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.58(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3130
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0540
_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/[\s^2^(Fo^2^)+(0.1010P)^2^+6.0012P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1496
_refine_ls_wR_factor_ref         0.1559
_reflns_Friedel_coverage         0.886
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2833
_reflns_number_total             3130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01994a2.cif
_cod_data_source_block           b
_cod_depositor_comments
'Adding full bibliography for 7704730--7704731.cif.'
_cod_original_cell_volume        3532.5(5)
_cod_original_formula_sum        'B5 H12.50 Cu K0.54 Na0.47 O15.50'
_cod_database_code               7704731
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.42(3)
 0.58(3)
2. Fixed Uiso
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
3. Shared sites
{Na1, K1}
4. Restrained distances
 O5-H5
 0.85 with sigma of 0.01
 B3-H5
 1.852889 with sigma of 0.02
5. Rigid bond restraints
 Cu1A, O9A, B5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cu1B, O9B, B5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
O10A \\sim Cu1B \\sim O9B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cu1B \\sim O9B \\sim B5: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cu1A \\sim O9A \\sim B5: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O10A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Na1) = Uanis(K1)
7. Rigid body (RIGU) restrains
 O10A, Cu1B, O9B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(Cu1B)=Sof(O9B)=1-FVAR(1)
 Sof(Cu1A)=Sof(O9A)=FVAR(1)
 Sof(Na1)=1-FVAR(2)
 Sof(K1)=FVAR(2)
 Fixed Sof: O10A(0.25)
9.a Riding coordinates:
 O9(H9A,H9B), O3W(H3WA,H3WB), O2W(H2WA,H2WB)
9.b Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 182 electrons were 
found in a volume of 1114\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 9[H2O] per Formula Unit 
which account for 180 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              73641
_shelx_hkl_checksum              98975
_shelx_fab_checksum              60546
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'