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_7713555
_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         'C52 H114 Cu3 O29 Ti6'
_chemical_formula_sum            'C52 H114 Cu3 O29 Ti6'
_chemical_formula_weight         1681.45
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-13
_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                87.179(2)
_cell_angle_beta                 82.799(2)
_cell_angle_gamma                72.186(2)
_cell_formula_units_Z            2
_cell_length_a                   12.9989(3)
_cell_length_b                   14.2479(3)
_cell_length_c                   23.6414(3)
_cell_measurement_reflns_used    12789
_cell_measurement_temperature    289.99(10)
_cell_measurement_theta_max      57.1240
_cell_measurement_theta_min      2.8380
_cell_volume                     4135.47(15)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      289.99(10)
_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 0.972
_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     80.00 150.00   0.50    0.20    --   76.57 125.00 -60.00  140
  2  \w     55.00 150.00   0.50    0.20    --   76.57  56.00  60.00  190
  3  \w     49.00 151.00   0.50    0.20    --   76.57  77.00 120.00  204
  4  \w    -10.00  71.00   0.50    0.05    --   -0.78  56.00  60.00  162
  5  \w    -95.00 -26.00   0.50    0.20    --  -78.13 125.00-180.00  138
  6  \w   -109.00 -25.00   0.50    0.20    --  -78.13 125.00  60.00  168
  7  \w   -107.00  -5.00   0.50    0.20    --  -78.13  77.00  60.00  204
  8  \w    -73.00 -48.00   0.50    0.20    --  -78.13  56.00  60.00   50
  9  \w   -136.00-110.00   0.50    0.20    --  -78.13 -99.00-150.00   52
 10  \w   -138.00 -86.00   0.50    0.20    --  -78.13-125.00-180.00  104
 11  \w   -130.00 -95.00   0.50    0.20    --  -78.13 -99.00  60.00   70
 12  \w   -139.00 -80.00   0.50    0.20    --  -78.13-125.00  90.00  118
 13  \w   -138.00 -91.00   0.50    0.20    --  -78.13-125.00  30.00   94
 14  \w   -136.00 -56.00   0.50    0.20    --  -78.13 -56.00 -81.00  160
 15  \w    -74.00  -2.00   0.50    0.05    --   -0.78 -56.00 -81.00  144
 16  \w     -7.00  39.00   0.50    0.05    --   -0.78 -99.00 -60.00   92
 17  \w     -8.00  19.00   0.50    0.05    --   -0.78 -99.00-120.00   54
 18  \w     32.00 110.00   0.50    0.20    --   76.57-125.00-180.00  156
 19  \w     41.00 105.00   0.50    0.20    --   76.57-125.00 -60.00  128
 20  \w     48.00 109.00   0.50    0.20    --   76.57-125.00 -30.00  122
 21  \w      8.00  42.00   0.50    0.20    --   76.57 -56.00 -81.00   68
 22  \w     61.00  93.00   0.50    0.20    --   76.57 -56.00 -81.00   64
 23  \w      2.00  29.00   0.50    0.20    --   76.57 -99.00 150.00   54
 24  \w     55.00  81.00   0.50    0.20    --   76.57 -99.00 150.00   52
;
_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      -0.0662617000
_diffrn_orient_matrix_UB_12      0.0755205000
_diffrn_orient_matrix_UB_13      0.0311365000
_diffrn_orient_matrix_UB_21      0.0799664000
_diffrn_orient_matrix_UB_22      0.0416707000
_diffrn_orient_matrix_UB_23      -0.0028989000
_diffrn_orient_matrix_UB_31      -0.0329314000
_diffrn_orient_matrix_UB_32      0.0480462000
_diffrn_orient_matrix_UB_33      -0.0477766000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0729
_diffrn_reflns_av_unetI/netI     0.0882
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            53823
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.529
_diffrn_reflns_theta_min         2.832
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    7.432
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16681
_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 light colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       block
_exptl_crystal_F_000             1754
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.661
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     973
_refine_ls_number_reflns         18446
_refine_ls_number_restraints     1170
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1524
_refine_ls_R_factor_gt           0.0844
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1078P)^2^+1.1764P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1932
_refine_ls_wR_factor_ref         0.2244
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10100
_reflns_number_total             18446
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01718d2.cif
_cod_data_source_block           PTC-367
_cod_database_code               7713555
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti Cu C O Br'
_shelx_estimated_absorpt_t_max   0.524
_shelx_estimated_absorpt_t_min   0.214
_diffrn_oxdiff_digest_frames
;
01f335e7c63bff6a876e78a36d4f76510d02788ef13
;
_diffrn_oxdiff_digest_hkl
;
010059e74459772a577f68d6ac309609a1d5cf
;
_reflns_odcompleteness_completeness 99.78
_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
 C15-C7
 1.54 with sigma of 0.02
 C47-C16
 1.54 with sigma of 0.02
 C34-C21
 1.54 with sigma of 0.02
 C37-C30
 1.54 with sigma of 0.01
 C50-C41
 1.54 with sigma of 0.01
 C54-C39
 1.54 with sigma of 0.01
 C55-C39
 1.54 with sigma of 0.01
 C46-C24
 1.54 with sigma of 0.01
 C31-C27
 1.54 with sigma of 0.01
 C49-C44
 1.54 with sigma of 0.01
 C57-C58
 1.54 with sigma of 0.01
 C45-C12
 1.54 with sigma of 0.01
 C60-C12
 1.54 with sigma of 0.01
 C1AA-C0AA
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C24) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O29) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(O14)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C22) \\sim Ueq, Uanis(C49) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O25) \\sim Ueq, Uanis(C44) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C8) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C12) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C44) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C57)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C24) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C1AA)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. 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
5. Others
 Fixed Sof: C24(0.5) H24A(0.5) H24B(0.5) C28(0.5) H28A(0.5) H28B(0.5)
 H28C(0.5) C33(0.5) H33A(0.5) H33B(0.5) H33C(0.5) C36(0.5) H36A(0.5) H36B(0.5)
 H36C(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5) H39A(0.5) H39(0.5) C40(0.5)
 H40A(0.5) H40B(0.5) H40C(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5) C44(0.5)
 H44A(0.5) H44B(0.5) C45(0.5) H45A(0.5) H45B(0.5) H45C(0.5) C46(0.5) H46A(0.5)
 H46B(0.5) H46C(0.5) C48(0.5) H48A(0.5) H48B(0.5) H48C(0.5) C49(0.5) H49A(0.5)
 H49B(0.5) H49C(0.5) C51(0.5) H51A(0.5) H51B(0.5) H51C(0.5) C52(0.5) H52A(0.5)
 H52B(0.5) H52C(0.5) C53(0.5) H53A(0.5) H53B(0.5) H53C(0.5) C54(0.4) H54A(0.4)
 H54B(0.4) H54C(0.4) C55(0.6) H55A(0.6) H55B(0.6) H55C(0.6) C56(0.5) H56A(0.5)
 H56B(0.5) H56C(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) C58(0.5) H58A(0.5)
 H58B(0.5) C59(0.5) H59A(0.5) H59B(0.5) H59C(0.5) C60(0.5) H60A(0.5) H60B(0.5)
 H60C(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C62(0.5) H62A(0.5) H62B(0.5)
 H62C(0.5) C63(0.5) H63A(0.5) H63B(0.5) H63C(0.5) C64(0.5) H64A(0.5) H64B(0.5)
 H64C(0.5) C0AA(0.5) H0AA(0.5) H0AB(0.5) C1AA(0.5) H1AA(0.5) H1AB(0.5) H1AC(0.5)
6.a Riding coordinates:
 C54(H54A,H54B,H54C)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C10(H10A,H10B), C11(H11A,H11B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C21(H21A,H21B), C24(H24A,H24B),
  C27(H27A,H27B), C30(H30A,H30B), C41(H41A,H41B), C44(H44A,H44B), C58(H58A,
 H58B), C0AA(H0AA,H0AB)
6.c Me refined with riding coordinates:
 C29(H29A,H29B,H29C), C50(H50A,H50B,H50C), C55(H55A,H55B,H55C)
6.d Aromatic/amide H refined with riding coordinates:
 C19(H19), C39(H39A), C39(H39)
6.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,
 H28B,H28C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), 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), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C53(H53A,H53B,H53C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C1AA(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              42207
_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 2.927
_oxdiff_exptl_absorpt_empirical_full_min 0.624