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_7718661
_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 H59.799 Mn N2 O16 P3 Ti3'
_chemical_formula_sum            'C43 H62 Mn N2 O16 P3 Ti3'
_chemical_formula_weight         1154.49
_chemical_name_systematic        'Ti3Mn 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
_atom_sites_solution_primary     dual
_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                 99.326(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.4156(6)
_cell_length_b                   20.0918(4)
_cell_length_c                   12.5358(3)
_cell_measurement_reflns_used    20834
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      77.7100
_cell_measurement_theta_min      2.8770
_cell_volume                     5819.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.949
_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   -118.00 -36.00   0.50    1.91    --  -47.60 -44.00-122.00  164
  2  \w    -26.00   0.00   0.50    1.91    --  -47.60  44.00  28.00   52
  3  \w    -14.00  50.00   0.50    1.91    --   47.60 -44.00-122.00  128
  4  \w   -116.00 -90.00   0.50    7.63    -- -105.00 -44.00-122.00   52
  5  \w   -154.00-128.00   0.50    7.63    -- -105.00 -44.00-122.00   52
  6  \w     99.00 176.00   0.50    7.63    --  113.25  44.00  28.00  154
  7  \w     14.00  56.00   0.50    1.91    --   47.60-125.00-180.00   84
  8  \w      0.00  25.00   0.50    1.91    --   47.60 -38.00  90.00   50
  9  \w     34.00 110.00   0.50    1.91    --   47.60  44.00  28.00  152
 10  \w    -20.00  22.00   0.50    1.91    --   47.60 -19.00  90.00   84
 11  \w    -69.00 -36.00   0.50    7.63    -- -105.00  61.00-180.00   66
 12  \w    -94.00 -54.00   0.50    7.63    -- -105.00  77.00 150.00   80
 13  \w    -62.00 -35.00   0.50    7.63    -- -105.00  61.00 150.00   54
 14  \w    -95.00 -39.00   0.50    7.63    -- -105.00  77.00  60.00  112
 15  \w    -62.00 -32.00   0.50    7.63    -- -105.00  61.00-120.00   60
 16  \w    -57.00 -32.00   0.50    7.63    -- -105.00  77.00 -60.00   50
 17  \w    -68.00 -33.00   0.50    7.63    -- -105.00  61.00 120.00   70
 18  \w   -170.00-143.00   0.50    7.63    -- -105.00 -61.00 -30.00   54
 19  \w   -118.00 -88.00   0.50    7.63    -- -105.00 -61.00 -30.00   60
 20  \w    -70.00 -44.00   0.50    7.63    -- -105.00  61.00  30.00   52
 21  \w    -71.00 -46.00   0.50    7.63    -- -105.00  61.00-150.00   50
 22  \w   -104.00 -73.00   0.50    7.63    -- -105.00  77.00 -60.00   62
 23  \w     42.00  71.00   0.50    7.63    --  113.25 -77.00-150.00   58
 24  \w     57.00 105.00   0.50    7.63    --  113.25 -95.00 -60.00   96
 25  \w     42.00 102.00   0.50    7.63    --  113.25 -77.00-120.00  120
 26  \w     73.00 104.00   0.50    7.63    --  113.25 -95.00  60.00   62
 27  \w     41.00  71.00   0.50    7.63    --  113.25 -95.00  60.00   60
 28  \w     41.00  66.00   0.50    7.63    --  113.25 -61.00 -30.00   50
 29  \w     97.00 175.00   0.50    7.63    --  113.25  15.00 150.00  156
 30  \w     41.00  66.00   0.50    7.63    --  113.25 -61.00-120.00   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      -0.0619642000
_diffrn_orient_matrix_UB_12      -0.0281882000
_diffrn_orient_matrix_UB_13      -0.0203889000
_diffrn_orient_matrix_UB_21      -0.0114781000
_diffrn_orient_matrix_UB_22      0.0306695000
_diffrn_orient_matrix_UB_23      0.1072172000
_diffrn_orient_matrix_UB_31      -0.0216797000
_diffrn_orient_matrix_UB_32      0.0643770000
_diffrn_orient_matrix_UB_33      -0.0600464000
_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  0.0443
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44446
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.057
_diffrn_reflns_theta_min         1.912
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.396
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47128
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       block
_exptl_crystal_F_000             2392
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.323
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         12049
_refine_ls_number_restraints     432
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0860
_refine_ls_R_factor_gt           0.0717
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1169P)^2^+7.9723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2030
_refine_ls_wR_factor_ref         0.2150
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9649
_reflns_number_total             12049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00085h2.cif
_cod_data_source_block           3-49-11_auto
_cod_depositor_comments
'Adding full bibliography for 7718660--7718661.cif.'
_cod_database_code               7718661
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C O N P Ti Mn'
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.883
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C30-C31
 2.515 with sigma of 0.02
 C27B-C26 \\sim C27A-C26
 with sigma of 0.02
 C24B-C23 \\sim C24A-C23
 with sigma of 0.02
 C25-C24A \\sim C25-C24B
 with sigma of 0.02
 C3B-C2B \\sim C3A-C2A
 with sigma of 0.02
 C7-C2B \\sim C7-C2A
 with sigma of 0.02
 N2-C2B \\sim N2-C2A
 with sigma of 0.02
 C4-C3A \\sim C4-C3B
 with sigma of 0.02
 C5A-C4 \\sim C5B-C4
 with sigma of 0.02
 C6B-C5B \\sim C6A-C5A
 with sigma of 0.02
 C7-C6B \\sim C7-C6A
 with sigma of 0.02
3. Rigid bond restraints
 C27A, C27B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C37A, C37B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C29A \\sim C30A \\sim C31A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C24B \\sim C24A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C32 \\sim C33 \\sim C34 \\sim C32A \\sim C34A \\sim C33A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
O12 \\sim C33 \\sim C24B \\sim C34 \\sim C27A \\sim C32: within 2A with sigma
of 0.001 and sigma for terminal atoms of 0.002 within 2A
C32A \\sim C34A \\sim C33A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C51 \\sim C50 \\sim C52A \\sim C51A \\sim C52 \\sim C50A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C2B \\sim C5A \\sim C6A \\sim C3B \\sim C6B \\sim C5B \\sim C3A \\sim C2A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C27A) \\sim Ueq, : with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N2) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C5B) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C37A) \\sim Ueq, Uanis(C37B) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C27A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C37A) = Uanis(C37B)
5. Rigid body (RIGU) restrains
 C23, C24A, C25
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C24B, C23, C25
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C7, C6A, C5A, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C6B, C5B, C4, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C4, C3A, C2A, C7, N2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C4, C3B, C2B, C7, N2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Same fragment restrains
{O13, C50A, C51A, C52A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O13, C50, C51, C52}
{O12, C32A, C33A, C34A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O12, C32, C33, C34}
{O14, C29A, C30A, C31A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O14, C29, C30, C31}
{C24, C37A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C24, C37B}
7. Others
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=
 Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(1)
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(H31C)=FVAR(1)
 Sof(C24B)=Sof(H24B)=1-FVAR(2)
 Sof(H23)=Sof(H25)=Sof(C24A)=Sof(H24A)=FVAR(2)
 Sof(C37B)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(3)
 Sof(H24)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=FVAR(3)
 Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34A)=
 Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(4)
 Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(H34C)=FVAR(4)
 Sof(C27B)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(5)
 Sof(H26)=Sof(C27A)=Sof(H27G)=Sof(H27H)=Sof(H27I)=FVAR(5)
 Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52A)=
 Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(6)
 Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=
 Sof(H52B)=Sof(H52C)=FVAR(6)
 Sof(C6B)=Sof(H6B)=Sof(C5B)=Sof(H5B)=1-FVAR(7)
 Sof(H4)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=FVAR(7)
 Sof(C2B)=Sof(C3B)=Sof(H3B)=1-FVAR(8)
 Sof(C3A)=Sof(H3A)=Sof(C2A)=FVAR(8)
8.a Ternary CH refined with riding coordinates:
 C50(H50), C32(H32), C29(H29), C38(H38), C26(H26), C24(H24), C29A(H29A),
 C32A(H32A), C50A(H50A)
8.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C9(H9), C1(H1), C15(H15), C18(H18), C17(H17), C16(H16), C6B(H6B),
 C10(H10), C13(H13), C11(H11), C5B(H5B), C12(H12), C3B(H3B), C4(H4), C24B(H24B),
  C23(H23), C22(H22), C21(H21), C25(H25), C24A(H24A), C6A(H6A), C5A(H5A),
 C3A(H3A)
8.c Fitted hexagon refined as free rotating group:
 C24B(C23,C22,C21,C20,C25)
8.d Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C39(H39A,H39B,H39C),
 C37B(H37A,H37B,H37C), C40(H40A,H40B,H40C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C27B(H27D,H27E,H27F), C30A(H30D,H30E,H30F), C31A(H31D,H31E,H31F),
 C37A(H37D,H37E,H37F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F), C27A(H27G,
 H27H,H27I), C51A(H51D,H51E,H51F), C52A(H52D,H52E,H52F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              79331
_shelx_hkl_checksum              3454
_shelx_fab_checksum              91686
_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 1.661
_oxdiff_exptl_absorpt_empirical_full_min 0.690