Boosting alkaline hydrogen evolution via cobalt functionalization of organic-inorganic hybrid germanoniobate electrocatalysts
Jin, Xinrong; Li, Jin-Yang; Wang, Yong-Jiang; Sun, Yan-Qiong; Li, Xin-Xiong; Zheng, Shou-Tian; CrystEngComm  (2025) –; doi:10.1039/D5CE00954E

data_7251274
_publ_section_title
;
 Boosting alkaline hydrogen evolution via cobalt functionalization of
 organic-inorganic hybrid germanoniobate electrocatalysts
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D5CE00954E
_journal_year                    2025
_chemical_formula_moiety
'C4 H20 Co3 Ge8 N4 Na2 Nb32 O122, 4(C6 H24 Co N6), 2(C6 H22 Co N6), 8(O), 4(H2 O), 4(H O)'
_chemical_formula_sum            'C40 H Co9 Ge8 N40 Na2 Nb32 O138'
_chemical_formula_weight         7380.00
_chemical_name_common            CCoGeNNaNbO
_chemical_name_systematic        {Co9(Ge4Nb16)2}
_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     iterative
_audit_creation_date             2025-09-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-09-19 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                92.648(2)
_cell_angle_beta                 99.053(2)
_cell_angle_gamma                114.473(2)
_cell_formula_units_Z            1
_cell_length_a                   15.0280(7)
_cell_length_b                   17.2493(8)
_cell_length_c                   23.3720(12)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    170
_cell_measurement_theta_max      25.07
_cell_measurement_theta_min      2.38
_cell_volume                     5403.6(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            93934
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.109
_diffrn_reflns_theta_max         25.109
_diffrn_reflns_theta_min         1.902
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    3.488
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5737
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0824 before and 0.0646 after correction.
The Ratio of minimum to maximum transmission is 0.7699.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.268
_exptl_crystal_description       block
_exptl_crystal_F_000             3458
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.972
_refine_diff_density_min         -2.060
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1226
_refine_ls_number_reflns         19087
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0399P)^2^+36.1703P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0984
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16760
_reflns_number_total             19087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00954e2.cif
_cod_data_source_block           1
_cod_database_code               7251274
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.680
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Rigid bond restraints
 Co1
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.04
3. Uiso/Uaniso restraints and constraints
O59 \\sim Co1 \\sim O51: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C16 \\sim C11: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C11 \\sim C16: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C16 \\sim N1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C12 \\sim N9: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Co1 \\sim O32 \\sim O59: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O27) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O59) \\sim Ueq, Uanis(O67) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
4.a Free rotating group:
 O33(H33A,H33B), O35(H35), O61(H61A,H61B), O65(H65)
4.b Rotating group:
 O60(H60A,H60B)
4.c Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2C,H2D), N3(H3A,H3B), N4(H4A,H4B), N5(H5C,H5D), N6(H6C,H6D),
 N7(H7A,H7B), N8(H8A,H8B), N9(H9C,H9D), N10(H10A,H10B), N12(H12A,H12B),
 N13(H13A,H13B), N14(H14A,H14B), N15(H15A,H15B), N16(H16A,H16B), N17(H17A,H17B),
  N18(H18C,H18D), N19(H19A,H19B), N20(H20A,H20B), C1(H1C,H1D), C2(H2A,H2B),
 C3(H3C,H3D), C4(H4C,H4D), C5(H5A,H5B), C6(H6A,H6B), C7(H7C,H7D), C8(H8C,H8D),
 C9(H9A,H9B), C10(H10C,H10D), C11(H11A,H11B), C12(H12C,H12D), C13(H13C,H13D),
 C14(H14C,H14D), C15(H15C,H15D), C16(H16C,H16D), C17(H17C,H17D), C18(H18A,H18B),
  C19(H19C,H19D), C20(H20C,H20D)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              88277
_shelx_fab_checksum              72116
_olex2_submission_special_instructions 'No special instructions were received'