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_7249414
_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
'C10 H11 Ge K2 N2 O42 W9.001 Zn2, C10 H18 N2 O7 Zn, C5 H4 N O, 0.5(H6 O3 Zn), 2(H2 O)'
_chemical_formula_sum            'C25 H42.5 Ge K2 N5 O53.5 W9 Zn3.5'
_chemical_formula_weight         3303.37
_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
_audit_creation_date             2024-02-24
_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                67.382(4)
_cell_angle_beta                 76.551(3)
_cell_angle_gamma                87.841(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7109(3)
_cell_length_b                   15.5844(6)
_cell_length_c                   19.2261(8)
_cell_measurement_reflns_used    19127
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.3940
_cell_measurement_theta_min      1.7880
_cell_volume                     3145.0(2)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0614
_diffrn_reflns_av_unetI/netI     0.0688
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_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            31183
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.791
_exptl_absorpt_coefficient_mu    18.413
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    3.488
_exptl_crystal_description       plate
_exptl_crystal_F_000             2993
_exptl_crystal_size_max          1.5
_exptl_crystal_size_mid          1
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.930
_refine_diff_density_min         -3.152
_refine_diff_density_rms         0.491
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     930
_refine_ls_number_reflns         11072
_refine_ls_number_restraints     169
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0875
_refine_ls_R_factor_gt           0.0620
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1374P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1792
_refine_ls_wR_factor_ref         0.2039
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8084
_reflns_number_total             11072
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00873a2.cif
_cod_data_source_block           a_sq
_cod_depositor_comments
'Adding full bibliography for 7249413--7249414.cif.'
_cod_original_formula_sum        'C25 H42.50 Ge K2 N5 O53.50 W9 Zn3.50'
_cod_database_code               7249414
_shelx_shelxl_version_number     2018/3
_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
W12: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(O52) \\sim Ueq, Uanis(O55) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.0025
Uanis(O31) \\sim Ueq, Uanis(O37) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.0025
Uanis(O8) \\sim Ueq, Uanis(O35) \\sim Ueq, Uanis(O39) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.0025
Uanis(O18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.0025
Uanis(C24) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.0025
Uanis(O20) \\sim Ueq, Uanis(O40) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.025
Uanis(O20) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.001
Uanis(C22) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.0025
Uanis(N3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.0025
Uanis(W7) \\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
Uanis(O43) \\sim Ueq, Uanis(O42) \\sim Ueq, Uanis(O21) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.0025
Uanis(O22) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.0025
Uanis(O13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
Uanis(O3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.0025
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
Uanis(C16) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O21) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O54) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 1*[Sof(W10)+Sof(W12)]+1*[Sof(W1)+Sof(W2)]=1 with esd of 0.001
 Sof(W10)=Sof(W12)=FVAR(1)
 Sof(W1)=Sof(W2)=FVAR(2)
 Fixed Sof: W7(0.93) W7A(0.07) W8(0.63) W8A(0.37) O43(0.5) H43A(0.5) H43B(0.5)
 O41(0.5) H41A(0.5) H41B(0.5) O42(0.5) H42A(0.5) H42B(0.5)
4.a Riding coordinates:
 O53(H53A,H53B), O55(H55A,H55B)
4.b Rotating group:
 O52(H52A,H52B), O35(H35A,H35B), O37(H37A,H37B), O36(H36A,H36B), O39(H39A,
 H39B), O40(H40A,H40B), O41(H41A,H41B), O42(H42A,H42B), O54(H54A,H54B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C10(H10), C1(H1), C9(H9), C12(H12), C15(H15), C14(H14),
 C20(H20), C19(H19), C18(H18), C17(H17), C8(H8), C4(H4), C7(H7), C25(H25),
 C24(H24), C22(H22), C21(H21)
4.d Fitted hexagon refined as free rotating group:
 C13(C12,C11,N3,C15,C14), C16(C20,C19,N4,C18,C17)
4.e X=CH2 refined with riding coordinates:
 O43(H43A,H43B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              51637
_shelx_hkl_checksum              2605
_shelx_fab_checksum              881
_olex2_submission_special_instructions 'No special instructions were received'