Organic-inorganic hybrid Co-containing polyoxoniobates as hydrogen evolution catalysts in alkaline media.
Chen, Chun-Xia; Duan, Shui-Lin; Zhang, Xiao-Yue; Sun, Rong-Zhi; Cai, Ping-Wei; Sun, Cai; Zheng, Shou-Tian; Dalton transactions (Cambridge, England : 2003) 54 (2025) 3591–3596; doi:10.1039/d4dt03071k

data_7717810
_publ_section_title
;
 Organic-inorganic hybrid Co-containing polyoxoniobates as hydrogen
 evolution catalysts in alkaline media.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3591
_journal_page_last               3596
_journal_paper_doi               10.1039/d4dt03071k
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'3(C6 H24 Co N6), 6(H2 O), Nb8 O28 Ti2, 1[OH], 4[H2O], 1[H2O]'
_chemical_formula_sum            'C18 H95 Co3 N18 Nb8 O40 Ti2'
_chemical_formula_weight         2219.98
_chemical_name_systematic        Co3-Ti2Nb8
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-01-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-01-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.796(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1776(4)
_cell_length_b                   38.7820(14)
_cell_length_c                   14.7815(6)
_cell_measurement_reflns_used    21984
_cell_measurement_temperature    170
_cell_measurement_theta_max      28.9590
_cell_measurement_theta_min      2.1300
_cell_volume                     6857.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      170
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.837
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -99.00  -1.00   0.50   25.50    --   -9.60  53.00 -10.00  196
  2  \w    -99.00  79.00   0.50   25.50    --   -9.60  55.00-120.00  356
  3  \w    -58.00 -33.00   0.50   25.50    --   -9.60  43.00  30.00   50
  4  \w     38.00  68.00   0.50   25.50    --   -9.60  43.00  30.00   60
  5  \w     18.00  43.00   0.50   25.50    --   -9.60  53.00 -10.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0583446000
_diffrn_orient_matrix_UB_12      -0.0025144000
_diffrn_orient_matrix_UB_13      -0.0144398000
_diffrn_orient_matrix_UB_21      0.0105405000
_diffrn_orient_matrix_UB_22      -0.0143340000
_diffrn_orient_matrix_UB_23      -0.0269578000
_diffrn_orient_matrix_UB_31      -0.0004438000
_diffrn_orient_matrix_UB_32      -0.0110872000
_diffrn_orient_matrix_UB_33      0.0380755000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.837
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            62174
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.837
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.424
_diffrn_reflns_theta_min         2.000
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.305
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84474
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    2.150
_exptl_crystal_description       block
_exptl_crystal_F_000             4408
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.479
_refine_diff_density_min         -1.347
_refine_diff_density_rms         0.227
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1144
_refine_ls_number_reflns         15898
_refine_ls_number_restraints     1182
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0830
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0543P)^2^+171.4755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1941
_refine_ls_wR_factor_ref         0.2048
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11975
_reflns_number_total             15898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03071k2.cif
_cod_data_source_block           Co3-Ti2Nb8
_cod_depositor_comments
'Adding full bibliography for 7717809--7717810.cif.'
_cod_database_code               7717810
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.802
_shelx_estimated_absorpt_t_min   0.545
_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,H) groups
2. Restrained distances
 C1-C2 = C6-C5 = C3-C4 = C11-C12 = C9-C10 = C8-C7 = C13-C14 = C16-C15 = C18-C17
 1.54 with sigma of 0.01
 N13-C13 = N14-C14 = N15-C15 = N16-C16 = N18-C18 = N17-C17 = N4-C4 = N3-C3 =
 N1-C1 = N2-C2 = N5-C5 = N6-C6 = N11-C11 = N12-C12 = N8-C8 = N7-C7 = N9-C9 =
 N10-C10
 1.47 with sigma of 0.01
 N24-C24 = N23-C23 = N19-C19 = N20-C20 = N21-C21 = N22-C22
 1.54 with sigma of 0.01
 C22-C21 = C20-C19 = C23-C24
 1.47 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim Co2 \\sim N19 \\sim
N20 \\sim N21 \\sim N22 \\sim N23 \\sim N24: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Co4 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim N13 \\sim
N14 \\sim N15 \\sim N16 \\sim N17 \\sim N18: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Co3 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim N7 \\sim N8
\\sim N9 \\sim N10 \\sim N11 \\sim N12 \\sim C7A \\sim C8A \\sim C9A \\sim C10A
\\sim C11A \\sim C12A \\sim N7A \\sim N8A \\sim N9A \\sim N10A \\sim N11A \\sim
N12A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Co1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim N1 \\sim N2
\\sim N3 \\sim N4 \\sim N5 \\sim N6 \\sim C1A \\sim C2A \\sim C3A \\sim C4A
\\sim C5A \\sim C6A \\sim N1A \\sim N2A \\sim N3A \\sim N4A \\sim N5A \\sim
N6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O30A \\sim O30: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(Co2) \\sim Ueq,
Uanis(N19) \\sim Ueq, Uanis(N20) \\sim Ueq, Uanis(N21) \\sim Ueq, Uanis(N22)
\\sim Ueq, Uanis(N23) \\sim Ueq, Uanis(N24) \\sim Ueq, Uanis(Co4) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(N13) \\sim Ueq,
Uanis(N14) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(N16) \\sim Ueq, Uanis(N17)
\\sim Ueq, Uanis(N18) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(O35) \\sim Ueq, Uanis(O24) \\sim Ueq, Uanis(O39) \\sim Ueq, Uanis(O36)
\\sim Ueq, Uanis(O37) \\sim Ueq, Uanis(O40) \\sim Ueq, Uanis(O41) \\sim Ueq,
Uanis(C2A) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(N2A)
\\sim Ueq, Uanis(O42) \\sim Ueq, Uanis(O30) \\sim Ueq, Uanis(O30A) \\sim Ueq,
Uanis(O43) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{Co3, C7A, C8A, C9A, C10A, C11A, C12A, N7A, N8A, N9A, N10A, N11A, N12A} sigma
for 1-2: 0.01, 1-3: 0.01
as in
{Co3, C7, C8, C9, C10, C11, C12, N7, N8, N9, N10, N11, N12}
{Co1, C1A, C2A, C3A, C4A, C5A, C6A, N1A, N2A, N3A, N4A, N5A, N6A} sigma for
1-2: 0.01, 1-3: 0.01
as in
{Co1, C1, C2, C3, C4, C5, C6, N1, N2, N3, N4, N5, N6}
5. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=
 Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=
 Sof(H6AA)=Sof(H6AB)=Sof(N1A)=Sof(H1AC)=Sof(H1AD)=Sof(N2A)=Sof(H2AC)=Sof(H2AD)=
 Sof(N3A)=Sof(H3AC)=Sof(H3AD)=Sof(N4A)=Sof(H4AC)=Sof(H4AD)=Sof(N5A)=Sof(H5AC)=
 Sof(H5AD)=Sof(N6A)=Sof(H6AC)=Sof(H6AD)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(N1)=Sof(H1C)=Sof(H1D)=Sof(N2)=Sof(H2C)=Sof(H2D)=Sof(N3)=Sof(H3C)=Sof(H3D)=
 Sof(N4)=Sof(H4C)=Sof(H4D)=Sof(N5)=Sof(H5C)=Sof(H5D)=Sof(N6)=Sof(H6C)=Sof(H6D)=
 FVAR(1)
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(C10A)=Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11E)=Sof(H11F)=
 Sof(C12A)=Sof(H12E)=Sof(H12F)=Sof(N7A)=Sof(H7AC)=Sof(H7AD)=Sof(N8A)=Sof(H8AC)=
 Sof(H8AD)=Sof(N9A)=Sof(H9AC)=Sof(H9AD)=Sof(N10A)=Sof(H10G)=Sof(H10H)=Sof(N11A)=
 Sof(H11G)=Sof(H11H)=Sof(N12A)=Sof(H12G)=Sof(H12H)=1-FVAR(2)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=
 Sof(H12B)=Sof(N7)=Sof(H7C)=Sof(H7D)=Sof(N8)=Sof(H8C)=Sof(H8D)=Sof(N9)=Sof(H9C)=
 Sof(H9D)=Sof(N10)=Sof(H10C)=Sof(H10D)=Sof(N11)=Sof(H11C)=Sof(H11D)=Sof(N12)=
 Sof(H12C)=Sof(H12D)=FVAR(2)
 Sof(O30A)=Sof(H30C)=Sof(H30D)=1-FVAR(3)
 Sof(O30)=Sof(H30A)=Sof(H30B)=FVAR(3)
 Fixed Sof: C13(0.5) H13A(0.5) H13B(0.5) C14(0.5) H14A(0.5) H14B(0.5) C15(0.5)
 H15A(0.5) H15B(0.5) C16(0.5) H16A(0.5) H16B(0.5) C17(0.5) H17A(0.5) H17B(0.5)
 C18(0.5) H18A(0.5) H18B(0.5) N13(0.5) H13C(0.5) H13D(0.5) N14(0.5) H14C(0.5)
 H14D(0.5) N15(0.5) H15C(0.5) H15D(0.5) N16(0.5) H16C(0.5) H16D(0.5) N17(0.5)
 H17C(0.5) H17D(0.5) N18(0.5) H18C(0.5) H18D(0.5) O24(0.25) H24E(0.25)
 H24F(0.25) O35(0.5) H35A(0.5) H35B(0.5) O37(0.5) H37A(0.5) H37B(0.5) O38(0.5)
 H38A(0.5) H38B(0.5) O39(0.5) H39A(0.5) H39B(0.5) O41(0.25) H41A(0.25)
 H41B(0.25) O36(0.5) H36A(0.5) H36B(0.5) O40(0.5) H40A(0.5) H40B(0.5) C19(0.5)
 H19A(0.5) H19B(0.5) C20(0.5) H20A(0.5) H20B(0.5) C21(0.5) H21A(0.5) H21B(0.5)
 C22(0.5) H22A(0.5) H22B(0.5) C23(0.5) H23A(0.5) H23B(0.5) C24(0.5) H24A(0.5)
 H24B(0.5) Co2(0.5) N19(0.5) H19C(0.5) H19D(0.5) N20(0.5) H20C(0.5) H20D(0.5)
 N21(0.5) H21C(0.5) H21D(0.5) N22(0.5) H22C(0.5) H22D(0.5) N23(0.5) H23C(0.5)
 H23D(0.5) N24(0.5) H24C(0.5) H24D(0.5) O42(0.25) H42A(0.25) H42B(0.25)
 O43(0.25) H43A(0.25) H43B(0.25)
6.a Riding coordinates:
 O24(H24E,H24F), O30(H30A,H30B), O31(H31A,H31B), O35(H35A,H35B), O37(H37A,
 H37B), O38(H38A,H38B), O39(H39A,H39B), O41(H41A,H41B), O36(H36A,H36B),
 O40(H40A,H40B), O42(H42A,H42B), O30A(H30C,H30D), O43(H43A,H43B)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 N1(H1C,H1D), N2(H2C,H2D), N3(H3C,H3D), N4(H4C,H4D), N5(H5C,H5D), N6(H6C,H6D),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), N7(H7C,H7D), N8(H8C,H8D), N9(H9C,H9D), N10(H10C,H10D),
 N11(H11C,H11D), N12(H12C,H12D), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
  C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), N13(H13C,H13D), N14(H14C,
 H14D), N15(H15C,H15D), N16(H16C,H16D), N17(H17C,H17D), N18(H18C,H18D),
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
  C24(H24A,H24B), N19(H19C,H19D), N20(H20C,H20D), N21(H21C,H21D), N22(H22C,
 H22D), N23(H23C,H23D), N24(H24C,H24D), C1A(H1AA,H1AB), C2A(H2AA,H2AB),
 C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), N1A(H1AC,H1AD),
  N2A(H2AC,H2AD), N3A(H3AC,H3AD), N4A(H4AC,H4AD), N5A(H5AC,H5AD), N6A(H6AC,
 H6AD), C7A(H7AA,H7AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C10A(H10E,H10F),
 C11A(H11E,H11F), C12A(H12E,H12F), N7A(H7AC,H7AD), N8A(H8AC,H8AD), N9A(H9AC,
 H9AD), N10A(H10G,H10H), N11A(H11G,H11H), N12A(H12G,H12H)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 212 electrons were 
found in a volume of 452\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
5[H2O], 1[H2O] per Asymmetric Unit 
which account for 212 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78568
_shelx_fab_checksum              91730
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.357
_oxdiff_exptl_absorpt_empirical_full_min 0.903