Precisely tailoring Lewis pairs in polyoxotitanium clusters for efficient photocatalytic production of hydrogen peroxide.
Gao, Mengke; Zhang, Shiming; Yan, Yayu; Qian, Zehao; Qin, Liyang; Liu, Xiaoyu; Ding, Qing-Rong; Li, Qiaohong; Wu, Xin; Zhang, Jian; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9016–9020; doi:10.1039/d5dt00085h

data_7718660
_publ_section_title
;
 Precisely tailoring Lewis pairs in polyoxotitanium clusters for efficient
 photocatalytic production of hydrogen peroxide.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9016
_journal_page_last               9020
_journal_paper_doi               10.1039/d5dt00085h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C43 H61 Co N2 O16 P3 Ti3, 0.5[], 1[]'
_chemical_formula_sum            'C42 H62 Co N3 O16 P3 Ti3'
_chemical_formula_weight         1160.48
_chemical_name_systematic        'Ti3Co cluster'
_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   geom
_audit_creation_date             2024-12-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-12-04 deposited with the CCDC.	2025-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.004(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.5030(4)
_cell_length_b                   19.9604(3)
_cell_length_c                   12.5665(2)
_cell_measurement_reflns_used    20159
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      77.4210
_cell_measurement_theta_min      2.8800
_cell_volume                     5822.67(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.947
_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    -64.00  25.00   0.50    0.83    --  -47.76  60.00 -64.00  178
  2  \w    -85.00 -59.00   0.50    0.83    --  -47.76 -60.00 156.00   52
  3  \w     46.00 117.00   0.50    0.83    --   47.76  60.00 -64.00  142
  4  \w    -23.00  62.00   0.50    0.83    --   47.76 -60.00 156.00  170
  5  \w   -174.00 -88.00   0.50    4.50    -- -105.00 -60.00 156.00  172
  6  \w    -70.00 -35.00   0.50    4.50    -- -105.00  60.00 -64.00   70
  7  \w    146.00 175.00   0.50    4.50    --  113.25  60.00 -64.00   58
  8  \w     41.00  68.00   0.50    4.50    --  113.25 -60.00 156.00   54
  9  \w   -117.00 -73.00   0.50    0.83    --  -47.76-125.00 -60.00   88
 10  \w   -114.00 -78.00   0.50    0.83    --  -47.76-125.00 -90.00   72
 11  \w    -66.00 -34.00   0.50    4.50    -- -105.00  61.00  60.00   64
 12  \w   -116.00 -87.00   0.50    4.50    -- -105.00 -61.00  30.00   58
 13  \w    -69.00 -41.00   0.50    4.50    -- -105.00  61.00  90.00   56
 14  \w   -168.00-125.00   0.50    4.50    -- -105.00 -61.00  30.00   86
 15  \w    -71.00 -46.00   0.50    4.50    -- -105.00  61.00-120.00   50
 16  \w    -64.00 -39.00   0.50    4.50    -- -105.00  61.00 120.00   50
 17  \w   -168.00 -87.00   0.50    4.50    -- -105.00 -61.00-120.00  162
 18  \w     41.00  66.00   0.50    4.50    --  113.25 -61.00  90.00   50
 19  \w     41.00  68.00   0.50    4.50    --  113.25 -61.00  60.00   54
 20  \w     99.00 176.00   0.50    4.50    --  113.25  30.00  60.00  154
 21  \w    114.00 143.00   0.50    4.50    --  113.25  30.00-150.00   58
 22  \w    148.00 175.00   0.50    4.50    --  113.25  30.00-150.00   54
 23  \w     41.00  71.00   0.50    4.50    --  113.25 -61.00 -60.00   60
 24  \w     41.00  66.00   0.50    4.50    --  113.25 -61.00-150.00   50
 25  \w    109.00 134.00   0.50    4.50    --  113.25  45.00-120.00   50
 26  \w     63.00 104.00   0.50    4.50    --  113.25 -77.00 -60.00   82
 27  \w     45.00  82.00   0.50    4.50    --  113.25 -95.00 120.00   74
 28  \w    114.00 173.00   0.50    4.50    --  113.25  30.00 -90.00  118
 29  \w     45.00  70.00   0.50    4.50    --  113.25 -61.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0538659000
_diffrn_orient_matrix_UB_12      0.0370161000
_diffrn_orient_matrix_UB_13      -0.0248388000
_diffrn_orient_matrix_UB_21      -0.0376449000
_diffrn_orient_matrix_UB_22      0.0400304000
_diffrn_orient_matrix_UB_23      -0.0894182000
_diffrn_orient_matrix_UB_31      -0.0089883000
_diffrn_orient_matrix_UB_32      0.0546720000
_diffrn_orient_matrix_UB_33      0.0824425000
_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  0.0412
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44488
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.140
_diffrn_reflns_theta_min         1.903
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.866
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08096
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       plate
_exptl_crystal_F_000             2404
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.222
_refine_diff_density_min         -0.728
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         12055
_refine_ls_number_restraints     289
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1141P)^2^+2.3798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1662
_refine_ls_wR_factor_ref         0.1797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9972
_reflns_number_total             12055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00085h2.cif
_cod_data_source_block           hy-smart_sq
_cod_depositor_comments
'Adding full bibliography for 7718660--7718661.cif.'
_cod_database_code               7718660
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C O N P Ti Co'
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.935
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H2A,H2B,H2C} of C2, {H5A,H5B,H5C} of C5
 At 1.5 times of:
  {H01A,H01B,H01C} of C014, {H1A,H1B,H1C} of C1, {H2,HB,HC} of C01R, {H4,HF,
  HG} of C01T, {H3,HD,HE} of C01S, {H01V,H01W,H01X} of C01M, {H01Q,H01R,H01S}
  of C01J, {H01K,H01L,H01M} of C01H, {H01N,H01O,H01P} of C01I, {H5,HH,HI} of
  C01U, {H01Y,H,HA} of C01N
2. Restrained distances
 C01O-C1
 1.3 with sigma of 0.01
 C01K-C01U
 1.3 with sigma of 0.01
 C01U-C01K
 1.45 with sigma of 0.01
 H01T-HI
 1.9 with sigma of 0.01
 H01T-HA
 1.9 with sigma of 0.01
3. Rigid bond restraints
 C01U, C01K
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C01K, C01N
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C01O
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C01U) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C01R) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C01O) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: C2(0.5) H2A(0.5) H2B(0.5) H2C(0.5) C5(0.5) H5A(0.5) H5B(0.5)
 H5C(0.5)
6.a Ternary CH refined with riding coordinates:
 C00Z(H00Z), C015(H015), C018(H018), C01K(H01T), C01O(H01Z), C01P(H01)
6.b Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C010(H010), C011(H011),
 C012(H012), C013(H013), C016(H016), C017(H017), C019(H019), C01A(H01D),
 C01B(H01E), C01C(H01F), C01D(H01G), C01E(H01H), C01F(H01I), C01G(H01J),
 C01L(H01U), C01Q(H1)
6.c Idealised Me refined as rotating group:
 C014(H01A,H01B,H01C), C01H(H01K,H01L,H01M), C01I(H01N,H01O,H01P), C01J(H01Q,
 H01R,H01S), C01M(H01V,H01W,H01X), C01N(H01Y,H,HA), C01R(H2,HB,HC), C01S(H3,HD,
 HE), C01T(H4,HF,HG), C01U(H5,HH,HI), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C5(H5A,
 H5B,H5C)
;
_shelx_res_checksum              76786
_shelx_hkl_checksum              29579
_shelx_fab_checksum              41343
_platon_squeeze_void_probe_radius 1.20
_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 4.770
_oxdiff_exptl_absorpt_empirical_full_min 0.700