Organic–inorganic hybrid Co-containing polyoxotungstate as an oxygen evolution catalyst
Chen, Zhe-Hong; Zhang, Xiao-Yue; Li, Da-Huan; Li, Xin-Xiong; Sun, Yan-Qiong; Sun, Cai; Zheng, Shou-Tian; CrystEngComm 26 (2024) 5840–5844; doi:10.1039/D4CE00873A

data_7249413
_publ_section_title
;
 Organic--inorganic hybrid Co-containing polyoxotungstate as an oxygen
 evolution catalyst
;
_journal_issue                   41
_journal_name_full               CrystEngComm
_journal_page_first              5840
_journal_page_last               5844
_journal_paper_doi               10.1039/D4CE00873A
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety
'Co2 Ge H4 K2 O40 W9, C10 H18 Co N2 O7, C10 H8 N2 O1.863, C5 H4 N O, Co0.5 H3 O2, H2 O, H O, 0.137(O)'
_chemical_formula_sum            'C25 H40 Co3.5 Ge K2 N5 O54 W9'
_chemical_formula_weight         3286.31
_chemical_name_systematic        zxy48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-19
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2024-05-14 deposited with the CCDC.	2024-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                67.274(2)
_cell_angle_beta                 76.636(2)
_cell_angle_gamma                87.587(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7657(3)
_cell_length_b                   15.6126(3)
_cell_length_c                   19.2536(4)
_cell_measurement_reflns_used    6080
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      23.9640
_cell_measurement_theta_min      1.8493
_cell_volume                     3169.44(13)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            32809
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         1.781
_exptl_absorpt_coefficient_mu    17.863
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    3.444
_exptl_crystal_description       plate
_exptl_crystal_F_000             2975
_exptl_crystal_size_max          1.5
_exptl_crystal_size_mid          1
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.507
_refine_diff_density_min         -2.870
_refine_diff_density_rms         0.402
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     984
_refine_ls_number_reflns         11136
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0526
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0904P)^2^+72.8714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1605
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8563
_reflns_number_total             11136
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00873a2.cif
_cod_data_source_block           a
_cod_depositor_comments
'Adding full bibliography for 7249413--7249414.cif.'
_cod_original_cell_volume        3169.45(13)
_cod_original_formula_sum        'C25 H40 Co3.50 Ge K2 N5 O54 W9'
_cod_database_code               7249413
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.124
_shelx_estimated_absorpt_t_min   0.015
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O50) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.0025
Uanis(O43) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(O44) \\sim Ueq, Uanis(O45)
\\sim Ueq, Uanis(O53) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.005
Uanis(W4) \\sim Ueq, Uanis(O55) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.0025
Uanis(W4) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.0005
Uanis(O55) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.0005
Uanis(W7A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.0005
: with sigma of 0.0005 and sigma for terminal atoms of 0.00025
Uanis(W8A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.0005
Uanis(W2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O52) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(W2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(W1) = Uanis(W1A)
Uanis(W2) = Uanis(W2A)
Uanis(O46) = Uanis(O46A)
3. Rigid body (RIGU) restrains
 W1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O46A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O53A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(W1A)=1-FVAR(1)
 Sof(W1)=FVAR(1)
 Sof(W2A)=1-FVAR(2)
 Sof(W2)=FVAR(2)
 Sof(O53A)=1-FVAR(3)
 Sof(O53)=FVAR(3)
 Sof(O45A)=1-FVAR(4)
 Sof(O45)=FVAR(4)
 Sof(O46A)=1-FVAR(5)
 Sof(O46)=FVAR(5)
 Fixed Sof: W4(0.95) W4A(0.05) W5(0.91) W5A(0.09) W7(0.95) W7A(0.05) W8(0.94)
 W8A(0.06) W9(0.86) W9A(0.14) O43(0.5) H43A(0.5) H43B(0.5) H45A(0.5) H45B(0.5)
 O44(0.5) H44A(0.5) H44B(0.5) H53A(0.5) H53B(0.5)
5.a Riding coordinates:
 O53(H53A,H53B)
5.b Free rotating group:
 O51(H51A,H51B)
5.c Rotating group:
 O36(H36A,H36B), O37(H37A,H37B), O39(H39A,H39B), O38(H38A,H38B), O40(H40A,
 H40B), O43(H43A,H43B), O45(H45A,H45B), O44(H44A,H44B), O50(H50A,H50B),
 O49(H49A,H49B)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C7(H7), C4(H4), C1(H1), C8(H8), C9(H9), C19(H19), C10(H10),
 C15(H15), C17(H17), C14(H14), C18(H18), C22(H22), C21(H21), C20(H20), C12(H12),
  C11(H11), C24(H24), C25(H25)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              59608
_shelx_hkl_checksum              2412
_shelx_fab_checksum              24978
_olex2_submission_original_sample_id zxy48
_olex2_submission_special_instructions 'No special instructions were received'