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_7713556
_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         'C60 H114 Br2 Cu2 O34 Ti8'
_chemical_formula_sum            'C60 H114 Br2 Cu2 O34 Ti8'
_chemical_formula_weight         2049.61
_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             2023-04-12
_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                 91.041(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6608(2)
_cell_length_b                   19.3473(4)
_cell_length_c                   20.8404(3)
_cell_measurement_reflns_used    12325
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      54.5340
_cell_measurement_theta_min      2.7110
_cell_volume                     4700.92(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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_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 0.998
_diffrn_measured_fraction_theta_max 0.971
_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      0.00  71.00   0.50    0.60    --   76.57 -38.00   0.00  142
  2  \w     62.00 108.00   0.50    0.60    --   76.57-125.00 -90.00   92
  3  \w     40.00  96.00   0.50    0.60    --   76.57 -57.00 -30.00  112
  4  \w      9.00  70.00   0.50    0.60    --   76.57 -38.00  60.00  122
  5  \w     80.00 105.00   0.50    0.60    --   76.57 156.00-139.00   50
  6  \w     12.00  38.00   0.50    0.15    --   -0.78 -99.00 -90.00   52
  7  \w      2.00  39.00   0.50    0.15    --   -0.78 -99.00  60.00   74
  8  \w     -7.00  20.00   0.50    0.15    --   -0.78 -99.00-180.00   54
  9  \w   -102.00 -58.00   0.50    0.60    --  -78.14 120.00  64.00   88
 10  \w   -129.00-101.00   0.50    0.60    --  -78.14 156.00-139.00   56
 11  \w    -24.00  67.00   0.50    0.15    --   -0.78  57.00-180.00  182
 12  \w    -68.00 -26.00   0.50    0.60    --  -78.14  38.00  30.00   84
 13  \w   -151.00 -90.00   0.50    0.60    --  -78.14 -99.00  90.00  122
 14  \w   -136.00 -84.00   0.50    0.60    --  -78.14-125.00 120.00  104
 15  \w   -127.00-101.00   0.50    0.60    --  -78.14-120.00 -20.00   52
 16  \w   -135.00 -99.00   0.50    0.60    --  -78.14 -99.00   0.00   72
 17  \w   -115.00 -90.00   0.50    0.60    --  -78.14-125.00 -90.00   50
 18  \w   -142.00-117.00   0.50    0.60    --  -78.14-125.00 -90.00   50
 19  \w   -137.00 -63.00   0.50    0.60    --  -78.14-156.00-176.00  148
;
_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      0.0469930000
_diffrn_orient_matrix_UB_12      0.0631382000
_diffrn_orient_matrix_UB_13      0.0007028000
_diffrn_orient_matrix_UB_21      -0.0994211000
_diffrn_orient_matrix_UB_22      0.0267720000
_diffrn_orient_matrix_UB_23      0.0194741000
_diffrn_orient_matrix_UB_31      0.0332513000
_diffrn_orient_matrix_UB_32      -0.0092260000
_diffrn_orient_matrix_UB_33      0.0612540000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            34527
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         60.381
_diffrn_reflns_theta_min         2.710
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    6.971
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38194
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       block
_exptl_crystal_F_000             2100
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.924
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     610
_refine_ls_number_reflns         10422
_refine_ls_number_restraints     1168
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1316
_refine_ls_R_factor_gt           0.0886
_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^)+(0.1320P)^2^+8.9736P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2390
_refine_ls_wR_factor_ref         0.2675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6615
_reflns_number_total             10422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01718d2.cif
_cod_data_source_block           PTC-368
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7713556
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti Cu C O'
_shelx_estimated_absorpt_t_max   0.542
_shelx_estimated_absorpt_t_min   0.229
_reflns_odcompleteness_completeness 99.40
_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
 C17-C25
 1.54 with sigma of 0.01
 C15-C24
 1.54 with sigma of 0.02
 C24-C15
 1.54 with sigma of 0.01
 C19-C18
 1.54 with sigma of 0.01
 C14-C10
 1.54 with sigma of 0.01
 C26-C27
 1.54 with sigma of 0.02
 C31-C32
 1.54 with sigma of 0.01
 O17-C29
 1.5 with sigma of 0.02
 O18-C31
 1.5 with sigma of 0.02
 C34-C33
 1.54 with sigma of 0.01
 C21-C20
 1.54 with sigma of 0.01
 C36-C35
 1.54 with sigma of 0.01
 C36-C37
 1.54 with sigma of 0.01
 C35-C38
 1.54 with sigma of 0.01
 Ti4-O18
 2 with sigma of 0.02
 C30-C29
 1.54 with sigma of 0.01
 C23-C22
 1.54 with sigma of 0.01
 C1AA-C0AA
 1.54 with sigma of 0.01
 C3AA-C2AA
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38: within 3.8A with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O14) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(O18) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O17) \\sim Ueq, Uanis(O18) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C33) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C20)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C2AA) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C17) \\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: O14(0.6) C15(0.5) H15A(0.5) H15B(0.5) C17(0.5) H17A(0.5) H17B(0.5)
 C18(0.5) H18A(0.5) H18B(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C20(0.6)
 H20A(0.6) H20B(0.6) C21(0.6) H21A(0.6) H21B(0.6) H21C(0.6) C24(0.5) H24A(0.5)
 H24B(0.5) H24C(0.5) C25(0.5) H25A(0.5) H25B(0.5) H25C(0.5) C26(0.5) H26A(0.5)
 H26B(0.5) H26C(0.5) C27(0.5) H27A(0.5) H27B(0.5) O17(0.35) O18(0.65) C29(0.6)
 H29A(0.6) H29B(0.6) C30(0.6) H30A(0.6) H30B(0.6) H30C(0.6) C31(0.4) H31A(0.4)
 H31B(0.4) C32(0.4) H32A(0.4) H32B(0.4) H32C(0.4) C33(0.4) H33A(0.4) H33B(0.4)
 C34(0.4) H34A(0.4) H34B(0.4) H34C(0.4) C35(0.35) H35A(0.35) H35B(0.35)
 C36(0.65) H36A(0.65) H36B(0.65) H36C(0.65) C37(0.65) H37A(0.65) H37B(0.65)
 C38(0.35) H38A(0.35) H38B(0.35) H38C(0.35) C1AA(0.5) H1AA(0.5) H1AB(0.5)
 H1AC(0.5) C0AA(0.5) H0AB(0.5) H0AA(0.5) C2AA(0.5) H2AA(0.5) H2AB(0.5)
 C3AA(0.5) H3AA(0.5) H3AB(0.5) H3AC(0.5) O20(0.4)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C10(H10A,H10B), C12(H12A,H12B), C15(H15A,H15B),
 C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B), C22(H22A,H22B), C27(H27A,H27B),
  C29(H29A,H29B), C31(H31A,H31B), C33(H33A,H33B), C35(H35A,H35B), C37(H37A,
 H37B), C0AA(H0AB,H0AA), C2AA(H2AA,H2AB)
6.b Me refined with riding coordinates:
 C16(H16A,H16B,H16C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C36(H36A,
 H36B,H36C), C38(H38A,H38B,H38C), C3AA(H3AA,H3AB,H3AC)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C11(H11), C13(H13)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C19(H19A,H19B,H19C), C25(H25A,H25B,H25C), C28(H28A,H28B,
 H28C), C30(H30A,H30B,H30C), C1AA(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              71385
_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 1.582
_oxdiff_exptl_absorpt_empirical_full_min 0.697