A bioinspired polyoxo-titanium cluster for efficient photocatalytic CO<sub>2</sub> reduction assisted by hydrogen bonding.
Zhang, Shiming; Zhao, Guoxiang; Yan, Yayu; Li, Qiao-Hong; Zhang, Hai-Xia; Wu, Xin; Zhang, Jian; Materials horizons 13 (2026) 1313–1319; doi:10.1039/d5mh01657f

data_1576217
_publ_section_title
;
 A bioinspired polyoxo-titanium cluster for efficient photocatalytic
 CO<sub>2</sub> reduction assisted by hydrogen bonding.
;
_journal_issue                   3
_journal_name_full               'Materials horizons'
_journal_page_first              1313
_journal_page_last               1319
_journal_paper_doi               10.1039/d5mh01657f
_journal_volume                  13
_journal_year                    2026
_chemical_formula_moiety         'C76 H118 Co2 N2 O32 P6 Ti6'
_chemical_formula_sum            'C76 H118 Co2 N2 O32 P6 Ti6'
_chemical_formula_weight         2162.80
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-29
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-06-29 deposited with the CCDC.	2025-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                99.4230(10)
_cell_angle_beta                 106.406(2)
_cell_angle_gamma                100.218(2)
_cell_formula_units_Z            2
_cell_length_a                   15.5362(3)
_cell_length_b                   16.5431(3)
_cell_length_c                   20.2811(3)
_cell_measurement_reflns_used    24598
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      54.4920
_cell_measurement_theta_min      2.0350
_cell_volume                     4793.16(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.978
_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   -136.00 -38.00   0.50    0.29    --  -67.27 -77.00-120.00  196
  2  \w    -75.00  22.00   0.50    0.07    --   -1.25 -57.00 -60.00  194
  3  \w     79.00 104.00   0.50    0.29    --   64.77-125.00 -60.00   50
  4  \w     35.00  74.00   0.50    0.29    --   64.77-125.00 -60.00   78
  5  \w     16.00 100.00   0.50    0.29    --   64.77-107.00 -23.00  168
  6  \w     26.00 108.00   0.50    0.29    --   64.77-125.00-180.00  164
  7  \w   -141.00 -44.00   0.50    0.29    --  -67.27 -57.00 150.00  194
  8  \w      5.00  92.00   0.50    0.29    --   64.77 -77.00 -30.00  174
  9  \w     10.00  54.00   0.50    0.29    --   64.77 -38.00  30.00   88
 10  \w     47.00  73.00   0.50    0.29    --   64.77  38.00 120.00   52
 11  \w     -8.00  76.00   0.50    0.29    --   64.77 -57.00-180.00  168
 12  \w    107.00 136.00   0.50    0.29    --   64.77 125.00   0.00   58
 13  \w     88.00 115.00   0.50    0.29    --   64.77 107.00  74.00   54
 14  \w    100.00 142.00   0.50    0.29    --   64.77  38.00 120.00   84
 15  \w    -20.00  22.00   0.50    0.07    --   -1.25  38.00  90.00   84
 16  \w    -46.00 -21.00   0.50    0.29    --  -67.27 125.00 120.00   50
 17  \w   -107.00 -81.00   0.50    0.29    --  -67.27 125.00 120.00   52
 18  \w    -92.00  -9.00   0.50    0.29    --  -67.27 107.00  74.00  166
 19  \w     27.00  76.00   0.50    0.07    --   -1.25  38.00  90.00   98
 20  \w   -131.00-106.00   0.50    0.29    --  -67.27 -99.00  60.00   50
 21  \w   -119.00 -86.00   0.50    0.29    --  -67.27-125.00 150.00   66
 22  \w   -138.00-113.00   0.50    0.29    --  -67.27-107.00 -23.00   50
 23  \w   -139.00 -88.00   0.50    0.29    --  -67.27 -99.00 -90.00  102
 24  \w   -138.00-106.00   0.50    0.29    --  -67.27 -99.00-150.00   64
 25  \w   -132.00 -83.00   0.50    0.29    --  -67.27-125.00-120.00   98
 26  \w     -6.00  25.00   0.50    0.07    --   -1.25 -99.00-180.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0395642000
_diffrn_orient_matrix_UB_12      -0.0177134000
_diffrn_orient_matrix_UB_13      0.0620147000
_diffrn_orient_matrix_UB_21      -0.0512890000
_diffrn_orient_matrix_UB_22      0.0419067000
_diffrn_orient_matrix_UB_23      0.0291667000
_diffrn_orient_matrix_UB_31      -0.0659999000
_diffrn_orient_matrix_UB_32      -0.0711485000
_diffrn_orient_matrix_UB_33      -0.0172591000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            57043
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         54.839
_diffrn_reflns_theta_min         2.027
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    5.656
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light blue'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       block
_exptl_crystal_F_000             2240
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.392
_refine_diff_density_min         -1.254
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1242
_refine_ls_number_reflns         17816
_refine_ls_number_restraints     24642
_refine_ls_restrained_S_all      0.758
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0688
_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^)+(0.0607P)^2^+31.4746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1755
_refine_ls_wR_factor_ref         0.1817
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14824
_reflns_number_total             17816
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01657f2.cif
_cod_data_source_block           BQTiCo
_cod_depositor_comments
'Adding full bibliography for 1576215--1576217.cif.'
_cod_database_code               1576217
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N P Co Ti'
_shelx_estimated_absorpt_t_max   0.602
_shelx_estimated_absorpt_t_min   0.602
_olex2_refinement_description
;
1. Restrained distances
 O9-C33 \\sim O9-C33A
 with sigma of 0.04
 O9-C65 \\sim O9-C65A
 with sigma of 0.02
 C65-C33 \\sim C65A-C33A
 with sigma of 0.02
 C65-C67 \\sim C65A-C67A
 with sigma of 0.02
 O9-C67 \\sim O9-C67A
 with sigma of 0.04
 C33-C67 \\sim C33A-C67A
 with sigma of 0.04
 P3-C34 \\sim P3-C34A
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A
 with sigma of 0.02
 C34-C44 \\sim C34A-C44A
 with sigma of 0.02
 C36-C44 \\sim C36A-C44A
 with sigma of 0.04
 C38-C42 \\sim C38A-C42A
 with sigma of 0.04
 C36-C38 \\sim C36A-C38A
 with sigma of 0.02
 C38-C40 \\sim C38A-C40A
 with sigma of 0.02
 C36-C40 \\sim C36A-C40A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.02
 C42-C44 \\sim C42A-C44A
 with sigma of 0.02
 C40-C44 \\sim C40A-C44A
 with sigma of 0.04
 P3-C36 \\sim P3-C36A
 with sigma of 0.04
 P3-C44 \\sim P3-C44A
 with sigma of 0.04
 C34-C38 \\sim C34A-C38A
 with sigma of 0.04
 C34-C42 \\sim C34A-C42A
 with sigma of 0.04
 C29-C63 \\sim C29A-C63A
 with sigma of 0.02
 O21-C31 \\sim O21-C31A
 with sigma of 0.04
 O21-C63 \\sim O21-C63A
 with sigma of 0.04
 C31-C63 \\sim C31A-C63A
 with sigma of 0.04
 O21-C29 \\sim O21-C29A
 with sigma of 0.02
 C29-C31 \\sim C29A-C31A
 with sigma of 0.02
 O31-C75 \\sim O31-C75A
 with sigma of 0.02
 C73-C75 \\sim C73-C75A
 with sigma of 0.02
 C37-C75 \\sim C37-C75A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 8.8A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 8.8A
3. Others
 Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C65A)=Sof(H65A)=Sof(C33A)=
 Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(C65)=Sof(H65)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(H67C)=FVAR(1)
 Sof(C34A)=Sof(C36A)=Sof(H36A)=Sof(C38A)=Sof(H38A)=Sof(C40A)=Sof(H40A)=
 Sof(C42A)=Sof(H42A)=Sof(C44A)=Sof(H44A)=1-FVAR(2)
 Sof(C34)=Sof(C36)=Sof(H36)=Sof(C38)=Sof(H38)=Sof(C40)=Sof(H40)=Sof(C42)=
 Sof(H42)=Sof(C44)=Sof(H44)=FVAR(2)
 Sof(C29A)=Sof(H29A)=Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C63A)=
 Sof(H63D)=Sof(H63E)=Sof(H63F)=1-FVAR(3)
 Sof(C29)=Sof(H29)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=FVAR(3)
 Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C75A)=
 Sof(H75A)=1-FVAR(4)
 Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C75)=Sof(H75)=
 FVAR(4)
4.a Ternary CH refined with riding coordinates:
 C52(H52), C66(H66), C72(H72), C39(H39), C41(H41), C3(H3), C49(H49), C53(H53),
 C29(H29), C65(H65), C35(H35), C75(H75), C65A(H65A), C29A(H29A), C75A(H75A)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C14(H14), C16(H16), C18(H18), C20(H20), C22(H22), C24(H24),
 C26(H26), C28(H28), C30(H30), C32(H32), C36(H36), C38(H38), C40(H40), C42(H42),
  C44(H44), C46(H46), C48(H48), C50(H50), C58(H58), C60(H60), C62(H62),
 C68(H68), C70(H70), C74(H74), C76(H76), C19(H19), C5(H5), C45(H45), C23(H23),
 C47(H47), C51(H51), C55(H55), C36A(H36A), C38A(H38A), C40A(H40A), C42A(H42A),
 C44A(H44A)
4.c Fitted hexagon refined as free rotating group:
 C34(C36,C38,C40,C42,C44), C34A(C36A,C38A,C40A,C42A,C44A)
4.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C64(H64A,H64B,H64C), C21(H21A,H21B,H21C), C43(H43A,H43B,
 H43C), C11(H11A,H11B,H11C), C25(H25A,H25B,H25C), C13(H13A,H13B,H13C), C27(H27A,
 H27B,H27C), C7(H7A,H7B,H7C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C15(H15A,H15B,H15C), C61(H61A,H61B,H61C), C31(H31A,H31B,H31C), C63(H63A,H63B,
 H63C), C2(H2A,H2B,H2C), C33(H33A,H33B,H33C), C67(H67A,H67B,H67C), C17(H17A,
 H17B,H17C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C9(H9A,H9B,H9C),
 C73(H73A,H73B,H73C), C73(H73D,H73E,H73F), C37(H37A,H37B,H37C), C37(H37D,H37E,
 H37F), C67A(H67D,H67E,H67F), C33A(H33D,H33E,H33F), C31A(H31D,H31E,H31F),
 C63A(H63D,H63E,H63F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              65378
_shelx_fab_checksum              82549
_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 2.092
_oxdiff_exptl_absorpt_empirical_full_min 0.579