Ligands dependent structural diversity and optimizable CO2 chemical fixation activities of Cu-doped polyoxo-titanium clusters
Lin, Xin; Yu, Yinghua; Chen, Guang-Hui; Li, Qiao-Hong; Zhang, Lei; Zhang, Jian; Dalton Transactions  (2023) –; doi:10.1039/D3DT01718D

data_7713557
_publ_section_title
;
 Ligands dependent structural diversity and optimizable CO2 chemical
 fixation activities of Cu-doped polyoxo-titanium clusters
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01718D
_journal_year                    2023
_chemical_formula_moiety         'C91 H179 Cu3 O101 Ti29'
_chemical_formula_sum            'C91 H179 Cu3 O101 Ti29'
_chemical_formula_weight         4469.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-05-22 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.029(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.5562(14)
_cell_length_b                   29.6251(15)
_cell_length_c                   30.6831(17)
_cell_measurement_reflns_used    22860
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      58.5390
_cell_measurement_theta_min      1.9640
_cell_volume                     20835(2)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_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 0.999
_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    -11.00  14.00   0.50    1.20    --   -1.41 -98.00  39.00   50
  2  \w    -38.00 -13.00   0.50    1.20    --   -1.41  98.00 147.00   50
  3  \w     41.00 102.00   0.50    4.20    --   75.34 -98.00  39.00  122
  4  \w     91.00 150.00   0.50    4.20    --   75.34  98.00 147.00  118
  5  \w   -127.00-101.00   0.50    4.20    --  -78.15 -98.00  39.00   52
  6  \w    -84.00  -6.00   0.50    4.20    --  -78.15  98.00 147.00  156
  7  \w     -8.00  38.00   0.50    1.20    --   -1.41 -99.00 -60.00   92
  8  \w      4.00  37.00   0.50    1.20    --   -1.41 -99.00-150.00   66
  9  \w     -5.00  27.00   0.50    1.20    --   -1.41 -99.00 150.00   64
 10  \w      0.00  25.00   0.50    1.20    --   -1.41 -99.00-120.00   50
 11  \w     -6.00  30.00   0.50    1.20    --   -1.41 -99.00 -30.00   72
 12  \w     72.00 105.00   0.50    4.20    --   75.34-125.00   0.00   66
 13  \w     21.00  47.00   0.50    4.20    --   75.34-125.00   0.00   52
 14  \w      2.00  98.00   0.50    4.20    --   75.34 -77.00  60.00  192
 15  \w    -65.00 -39.00   0.50    4.20    --  -78.15  38.00 120.00   52
 16  \w    -70.00  -2.00   0.50    4.20    --  -78.15  38.00 -90.00  136
 17  \w   -120.00 -90.00   0.50    4.20    --  -78.15 -99.00  90.00   60
 18  \w   -126.00 -82.00   0.50    4.20    --  -78.15-125.00  90.00   88
 19  \w    -35.00  -6.00   0.50    4.20    --  -78.15  38.00 120.00   58
 20  \w   -120.00 -94.00   0.50    4.20    --  -78.15 -99.00 -60.00   52
 21  \w    -48.00  -9.00   0.50    4.20    --  -78.15  38.00 150.00   78
 22  \w   -147.00-104.00   0.50    4.20    --  -78.15 -99.00   0.00   86
 23  \w   -152.00 -94.00   0.50    4.20    --  -78.15 -99.00 120.00  116
;
_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      0.0378895000
_diffrn_orient_matrix_UB_12      0.0027918000
_diffrn_orient_matrix_UB_13      -0.0222158000
_diffrn_orient_matrix_UB_21      -0.0127350000
_diffrn_orient_matrix_UB_22      -0.0425031000
_diffrn_orient_matrix_UB_23      -0.0150741000
_diffrn_orient_matrix_UB_31      -0.0427831000
_diffrn_orient_matrix_UB_32      0.0151569000
_diffrn_orient_matrix_UB_33      -0.0382494000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.1006
_diffrn_reflns_av_unetI/netI     0.1026
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            170201
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         61.389
_diffrn_reflns_theta_min         2.119
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    7.764
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25536
_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            'metallic blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             9032
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.543
_refine_diff_density_min         -1.002
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2155
_refine_ls_number_reflns         46542
_refine_ls_number_restraints     3975
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.1878
_refine_ls_R_factor_gt           0.0957
_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^)+(0.1903P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2816
_refine_ls_wR_factor_ref         0.3430
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18304
_reflns_number_total             46542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01718d2.cif
_cod_data_source_block           PTC-370
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7713557
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti C N O'
_shelx_estimated_absorpt_t_max   0.511
_shelx_estimated_absorpt_t_min   0.204
_diffrn_oxdiff_digest_frames
;
019f809f9d1a050cd5476628115a831fc101928d283
;
_diffrn_oxdiff_digest_hkl
;
01a819a30fdfd72eb5279a5590ed932c3c5162
;
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     56.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C62-C63
 1.54 with sigma of 0.01
 C79-C80
 1.54 with sigma of 0.01
 C83-C77
 1.54 with sigma of 0.01
 C84-C85
 1.54 with sigma of 0.02
 C83-C85
 1.54 with sigma of 0.02
 O64-C77
 1.45 with sigma of 0.02
 C76-C77
 1.54 with sigma of 0.02
 C88-C77
 1.54 with sigma of 0.02
 C97-C95
 1.54 with sigma of 0.02
 C99-C95
 1.54 with sigma of 0.02
 C96-C95
 1.54 with sigma of 0.02
 C98-C95
 1.54 with sigma of 0.02
 C78-C66
 1.54 with sigma of 0.01
 C93-C87
 1.54 with sigma of 0.01
 C79-C100
 1.54 with sigma of 0.01
 C72-C70
 1.54 with sigma of 0.01
 C76-C77 = C77-C88
 1.54 with sigma of 0.02
 C93-C81
 1.54 with sigma of 0.01
 C102-C101
 1.54 with sigma of 0.01
 C82-C102
 1.54 with sigma of 0.01
 C80-C79 = C79-C100
 1.54 with sigma of 0.02
 C79-C103
 1.54 with sigma of 0.01
 O42-C70
 1.5 with sigma of 0.02
 C71-C70
 1.54 with sigma of 0.01
 C90-C89
 1.54 with sigma of 0.02
 C86-C89 = C89-C90
 1.54 with sigma of 0.02
 C65-C66
 1.54 with sigma of 0.01
 O101-C79
 1.3 with sigma of 0.02
 C73-C74
 1.54 with sigma of 0.01
 C75-C74
 1.54 with sigma of 0.01
 O32-C74
 1.45 with sigma of 0.02
 C64-C63
 1.54 with sigma of 0.01
 H72A-H73A
 2.15 with sigma of 0.01
 C76-C88
 2.515 with sigma of 0.04
 C80-C100
 2.515 with sigma of 0.04
 C86-C90
 2.515 with sigma of 0.04
3. Rigid bond restraints
 O38, C95, C98, C96, C99, C97
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C85) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(O64)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C76) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C8) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C94) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C88) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C63) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O76) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C82) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O42) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C71)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O97) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C57)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O42) \\sim Ueq, Uanis(C70) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O80) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C86)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O98) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C66) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(O101) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C100)
\\sim Ueq, Uanis(C103) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(O32) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C86)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O102) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C62)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5) C76(0.5) H76A(0.5)
 H76B(0.5) H76C(0.5) C77(0.5) H77(0.5) H79(0.5) H79A(0.5) C80(0.5) H80A(0.5)
 H80B(0.5) H80C(0.5) C81(0.55) H81A(0.55) H81B(0.55) H81C(0.55) C82(0.45)
 H82A(0.45) H82B(0.45) H82C(0.45) C83(0.5) H83A(0.5) H83B(0.5) H83C(0.5)
 C84(0.5) H84A(0.5) H84B(0.5) H84C(0.5) C85(0.5) H85(0.5) C87(0.55) H87A(0.55)
 H87B(0.55) H87C(0.55) C88(0.5) H88A(0.5) H88B(0.5) H88C(0.5) C93(0.55)
 H93(0.55) C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) H95(0.5) H95A(0.5) C96(0.5)
 H96A(0.5) H96B(0.5) H96C(0.5) C97(0.5) H97A(0.5) H97B(0.5) H97C(0.5) C98(0.5)
 H98A(0.5) H98B(0.5) H98C(0.5) C99(0.5) H99A(0.5) H99B(0.5) H99C(0.5)
 C101(0.45) H10D(0.45) H10E(0.45) H10F(0.45) C102(0.45) H102(0.45) C103(0.5)
 H10G(0.5) H10H(0.5) H10I(0.5)
7.a Ternary CH refined with riding coordinates:
 C19(H19), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C52(H52),
 C63(H63), C66(H66), C67(H67), C70(H70), C74(H74), C77(H77), C79(H79),
 C79(H79A), C85(H85), C89(H89), C93(H93), C95(H95), C95(H95A), C102(H102)
7.b Me refined with riding coordinates:
 C44(H44A,H44B,H44C), C57(H57A,H57B,H57C), C61(H61A,H61B,H61C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C76(H76A,H76B,H76C), C80(H80A,H80B,H80C), C86(H86A,
 H86B,H86C), C87(H87A,H87B,H87C), C90(H90A,H90B,H90C), C96(H96A,H96B,H96C),
 C98(H98A,H98B,H98C), C100(H10A,H10B,H10C), C103(H10G,H10H,H10I)
7.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C),
 C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C58(H58A,
 H58B,H58C), C59(H59A,H59B,H59C), C62(H62A,H62B,H62C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,
 H73C), C75(H75A,H75B,H75C), C78(H78A,H78B,H78C), C81(H81A,H81B,H81C), C82(H82A,
 H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C88(H88A,H88B,H88C),
 C94(H94A,H94B,H94C), C97(H97A,H97B,H97C), C99(H99A,H99B,H99C), C101(H10D,H10E,
 H10F)
;
_shelx_res_checksum              58840
_shelx_fab_checksum              4494
_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 2.662
_oxdiff_exptl_absorpt_empirical_full_min 0.481