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_1576216
_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         'C88 H146 N2 O36 P6 Ti8'
_chemical_formula_sum            'C88 H146 N2 O36 P6 Ti8'
_chemical_formula_weight         2377.08
_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     iterative
_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                93.7650(10)
_cell_angle_beta                 104.8040(10)
_cell_angle_gamma                96.7100(10)
_cell_formula_units_Z            1
_cell_length_a                   11.33000(10)
_cell_length_b                   12.8285(2)
_cell_length_c                   19.9795(2)
_cell_measurement_reflns_used    25619
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.6460
_cell_measurement_theta_min      2.4190
_cell_volume                     2774.50(6)
_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    'olex2.solve 1.5-beta (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_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 0.945
_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    -24.00  19.00   0.50    0.05    --   46.56 -77.00-150.00   86
  2  \w     24.00  68.00   0.50    0.05    --   46.56 -77.00-150.00   88
  3  \w    -20.00  60.00   0.50    0.05    --   46.56 -57.00 -90.00  160
  4  \w    -10.00  28.00   0.50    0.05    --   46.56 -29.00 -79.00   76
  5  \w    -27.00  30.00   0.50    0.05    --   46.56 -38.00 150.00  114
  6  \w     75.00 111.00   0.50    0.05    --  106.13-125.00 150.00   72
  7  \w     38.00  64.00   0.50    0.05    --  106.13-125.00 150.00   52
  8  \w     41.00  67.00   0.50    0.05    --  106.13-125.00  60.00   52
  9  \w     83.00 112.00   0.50    0.05    --  106.13-125.00  60.00   58
 10  \w     38.00 100.00   0.50    0.05    --  106.13-125.00  30.00  124
 11  \w     37.00  97.00   0.50    0.05    --  106.13 -95.00 -60.00  120
 12  \w     73.00 110.00   0.50    0.05    --  106.13-125.00-180.00   74
 13  \w     75.00 105.00   0.50    0.05    --  106.13 -95.00-180.00   60
 14  \w     38.00  63.00   0.50    0.05    --  106.13 -61.00 -60.00   50
 15  \w     34.00  97.00   0.50    0.05    --  106.13 -77.00   0.00  126
 16  \w     76.00 101.00   0.50    0.05    --  106.13 -77.00  30.00   50
 17  \w     38.00  85.00   0.50    0.05    --  106.13 -77.00  90.00   94
 18  \w     39.00  64.00   0.50    0.05    --  106.13 -77.00  30.00   50
 19  \w     33.00  58.00   0.50    0.05    --  106.13 -61.00  60.00   50
 20  \w    129.00 175.00   0.50    0.05    --  106.13  45.00 150.00   92
 21  \w     93.00 124.00   0.50    0.05    --  106.13  45.00 150.00   62
 22  \w     96.00 172.00   0.50    0.05    --  106.13  29.00  81.00  152
 23  \w     89.00 175.00   0.50    0.05    --  106.13  15.00-180.00  172
 24  \w     36.00 122.00   0.50    0.05    --   46.56  29.00  81.00  172
 25  \w    -31.00  -6.00   0.50    0.05    --  -46.56  29.00  81.00   50
 26  \w    -54.00 -24.00   0.50    0.05    --  -97.00  45.00  90.00   60
 27  \w   -105.00 -62.00   0.50    0.05    --  -97.00  77.00   0.00   86
 28  \w    -51.00 -25.00   0.50    0.05    --  -97.00  45.00 -30.00   52
 29  \w    -54.00 -29.00   0.50    0.05    --  -97.00  45.00 -90.00   50
 30  \w    -53.00 -27.00   0.50    0.05    --  -97.00  61.00 -90.00   52
 31  \w    -53.00 -27.00   0.50    0.05    --  -97.00  45.00-120.00   52
 32  \w    -54.00 -24.00   0.50    0.05    --  -97.00  45.00-180.00   60
 33  \w   -108.00 -36.00   0.50    0.05    --  -97.00  77.00-120.00  144
 34  \w    -53.00 -24.00   0.50    0.05    --  -97.00  45.00   0.00   58
 35  \w    -54.00 -25.00   0.50    0.05    --  -97.00  45.00  60.00   58
 36  \w   -114.00 -88.00   0.50    0.05    --  -97.00 -95.00-120.00   52
 37  \w   -115.00 -82.00   0.50    0.05    --  -97.00 -29.00 -79.00   66
 38  \w   -165.00-125.00   0.50    0.05    --  -97.00 -29.00 -79.00   80
 39  \w   -120.00 -93.00   0.50    0.05    --  -46.56 -29.00 -79.00   54
 40  \w   -126.00 -88.00   0.50    0.05    --  -97.00 -45.00 150.00   76
 41  \w   -159.00-134.00   0.50    0.05    --  -97.00 -45.00 150.00   50
 42  \w   -108.00 -40.00   0.50    0.05    --  -97.00 112.00-113.58  136
 43  \w    -52.00 -23.00   0.50    0.05    --  -46.56 125.00 -30.00   58
 44  \w    -74.00 -32.00   0.50    0.05    --  -97.00 143.00 -14.79   84
 45  \w   -125.00-100.00   0.50    0.05    --  -97.00 143.00 -14.79   50
 46  \w    -81.00 -55.00   0.50    0.05    --  -46.56 125.00 -30.00   52
 47  \w   -124.00 -98.00   0.50    0.05    --  -97.00 142.00 174.80   52
 48  \w    -88.00 -34.00   0.50    0.05    --  -97.00 142.00 174.80  108
 49  \w    -92.00 -48.00   0.50    0.05    --  -97.00 125.00 150.00   88
;
_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      0.0346500000
_diffrn_orient_matrix_UB_12      0.1030238000
_diffrn_orient_matrix_UB_13      -0.0303229000
_diffrn_orient_matrix_UB_21      -0.1265700000
_diffrn_orient_matrix_UB_22      0.0330448000
_diffrn_orient_matrix_UB_23      -0.0003676000
_diffrn_orient_matrix_UB_31      0.0542760000
_diffrn_orient_matrix_UB_32      0.0553281000
_diffrn_orient_matrix_UB_33      0.0741937000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            37018
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.326
_diffrn_reflns_theta_min         3.486
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.119
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64977
_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 colourless'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             1242
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.827
_refine_diff_density_min         -0.465
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         10993
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0303
_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^)+(0.0496P)^2^+1.4393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0853
_refine_ls_wR_factor_ref         0.0859
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10539
_reflns_number_total             10993
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01657f2.cif
_cod_data_source_block           BQTi
_cod_depositor_comments
'Adding full bibliography for 1576215--1576217.cif.'
_cod_database_code               1576216
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Ti P'
_olex2_refinement_description
;
1. Restrained distances
 C9-C21 \\sim C9-C21A
 with sigma of 0.02
 C9-C43 \\sim C9-C43A
 with sigma of 0.02
2. Others
 Sof(H9B)=Sof(C21A)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C43A)=Sof(H43D)=
 Sof(H43E)=Sof(H43F)=1-FVAR(1)
 Sof(H9A)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C12(H12), C14(H14), C16(H16), C18(H18), C28(H28), C32(H32), C35(H35), C9(H9B),
  C9(H9A)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C20(H20), C22(H22), C24(H24), C26(H26), C30(H30), C34(H34),
 C40(H40), C46(H46), C23(H23), C3(H3), C29(H29), C31(H31), C2(H2), C17(H17),
 C39(H39)
3.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C25(H25A,H25B,H25C), C13(H13A,H13B,H13C), C27(H27A,H27B,H27C), C7(H7A,
 H7B,H7C), C15(H15A,H15B,H15C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C),
 C19(H19A,H19B,H19C), C5(H5A,H5B,H5C), C41(H41A,H41B,H41C), C21(H21A,H21B,H21C),
  C43(H43A,H43B,H43C), C21A(H21D,H21E,H21F), C43A(H43D,H43E,H43F)
;
_shelx_res_checksum              65196
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.718