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_7713558
_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         'C70 H150 Cu3 O57 Ti16'
_chemical_formula_sum            'C70 H150 Cu3 O57 Ti16'
_chemical_formula_weight         2860.91
_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             2023-05-04
_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                 94.1550(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.0885(4)
_cell_length_b                   44.2441(8)
_cell_length_c                   33.1200(4)
_cell_measurement_reflns_used    45362
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      60.0920
_cell_measurement_theta_min      2.3010
_cell_volume                     23513.6(8)
_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      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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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      2.00 103.84   0.38    0.05    --   76.22 -96.00 171.00  268
  2  \w     86.00 148.70   0.38    0.05    --   76.22  96.00 -80.00  165
  3  \w     79.00 148.92   0.38    0.05    --   76.22 125.00 -60.00  184
  4  \w     20.00 110.82   0.38    0.05    --   76.22-125.00-180.00  239
  5  \w     -8.00  37.98   0.38    0.04    --   -0.94 -99.00  30.00  121
  6  \w    -23.00  35.90   0.38    0.04    --   -0.94 -96.00 171.00  155
  7  \w   -105.00  -5.06   0.38    0.05    --  -78.10  96.00 -80.00  263
  8  \w    -39.00  21.80   0.38    0.04    --   -0.94  96.00 -80.00  160
  9  \w    -23.00  72.00   0.38    0.04    --   -0.94  57.00-180.00  250
 10  \w    -96.00  -5.18   0.38    0.05    --  -78.10  57.00 -90.00  239
 11  \w    -71.00  -2.22   0.38    0.05    --  -78.10  38.00 -90.00  181
 12  \w    -71.00  -2.22   0.38    0.05    --  -78.10  38.00  60.00  181
 13  \w    -68.00  -2.64   0.38    0.05    --  -78.10  38.00 120.00  172
 14  \w   -152.00 -89.30   0.38    0.05    --  -78.10 -99.00 150.00  165
 15  \w   -152.00 -86.26   0.38    0.05    --  -78.10 -96.00 171.00  173
 16  \w   -114.00 -88.92   0.38    0.05    --  -78.10 -99.00  90.00   66
 17  \w   -152.00 -89.30   0.38    0.05    --  -78.10 -99.00-150.00  165
;
_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      -0.0562434000
_diffrn_orient_matrix_UB_12      -0.0199263000
_diffrn_orient_matrix_UB_13      -0.0155545000
_diffrn_orient_matrix_UB_21      0.0607523000
_diffrn_orient_matrix_UB_22      -0.0201920000
_diffrn_orient_matrix_UB_23      -0.0040009000
_diffrn_orient_matrix_UB_31      -0.0103693000
_diffrn_orient_matrix_UB_32      -0.0104895000
_diffrn_orient_matrix_UB_33      0.0371940000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.1722
_diffrn_reflns_av_unetI/netI     0.1350
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -50
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            206641
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        50.000
_diffrn_reflns_theta_max         50.000
_diffrn_reflns_theta_min         2.090
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    8.914
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46072
_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 blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.616
_exptl_crystal_description       block
_exptl_crystal_F_000             11720
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.772
_refine_diff_density_min         -1.556
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2784
_refine_ls_number_reflns         36764
_refine_ls_number_restraints     4779
_refine_ls_restrained_S_all      10.206
_refine_ls_R_factor_all          0.1606
_refine_ls_R_factor_gt           0.0816
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1072P)^2^+76.3319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1983
_refine_ls_wR_factor_ref         0.2432
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19585
_reflns_number_total             36764
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01718d2.cif
_cod_data_source_block           PTC-369
_cod_original_cell_volume        23513.5(7)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7713558
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ti Cu C O'
_shelx_estimated_absorpt_t_max   0.469
_shelx_estimated_absorpt_t_min   0.175
_diffrn_oxdiff_digest_frames
;
0136bbee3dd0cc6c5a450bcc0d98b892d4031473e19
;
_diffrn_oxdiff_digest_hkl
;
01ee1869a53be1e5e4244c7432999624f507fa
;
_reflns_odcompleteness_completeness 99.98
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 O57-C32
 1.3 with sigma of 0.02
 O113-C123
 1.3 with sigma of 0.02
 C64-C62
 1.54 with sigma of 0.02
 C133-C124
 1.54 with sigma of 0.02
 C112-C140
 1.54 with sigma of 0.02
 C112-C139
 1.54 with sigma of 0.02
 C128-C119
 1.54 with sigma of 0.02
 C132-C131
 1.54 with sigma of 0.02
 C138-C133
 1.54 with sigma of 0.02
 C115-C121
 1.54 with sigma of 0.02
 C41-C145
 1.54 with sigma of 0.01
 C64-C146
 1.54 with sigma of 0.01
 C147-C124
 1.54 with sigma of 0.01
 C143-C132
 1.54 with sigma of 0.01
 C137-C136
 1.54 with sigma of 0.02
 C144-C137
 1.54 with sigma of 0.02
 C66-C62
 1.54 with sigma of 0.02
 C66-C146
 1.54 with sigma of 0.01
 H11H-H67A
 2.1 with sigma of 0.01
 H13B-H70A_$1
 2.1 with sigma of 0.01
3. Rigid bond restraints
 C67, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O13, C68, C48, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O13, C68, C47, C48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. 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 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97
\\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104
\\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111
\\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118
\\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125
\\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132
\\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139
\\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146
\\sim C147 \\sim C148 \\sim C149 \\sim C150: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C132) \\sim Ueq, Uanis(C131) \\sim Ueq, Uanis(C109) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(C119) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(O86)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C32) \\sim Ueq, Uanis(O57) \\sim Ueq, Uanis(O56) \\sim Ueq, Uanis(C67)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C75) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C139)
\\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C85) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(O13) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C133) \\sim Ueq, Uanis(C147) \\sim Ueq, Uanis(C148) \\sim Ueq,
Uanis(C124) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O99) \\sim Ueq, Uanis(C150) \\sim Ueq, Uanis(C134) \\sim Ueq, Uanis(C115)
\\sim Ueq, Uanis(C121) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(C70) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C135) \\sim Ueq, Uanis(C144) \\sim Ueq, Uanis(C136) \\sim Ueq,
Uanis(C137) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C62) \\sim Ueq, Uanis(C146) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C66)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O16) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C19)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O92) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C113)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C124) = Uanis(C149)
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: H41(0.7) H41A(0.3) H47A(0.5) H47B(0.5) H47C(0.5) H47D(0.5)
 H47E(0.5) H47F(0.5) H48A(0.5) H48B(0.5) H48C(0.5) H48D(0.5) H48E(0.5)
 H48F(0.5) C62(0.6) H62(0.6) H64A(0.6) H64B(0.6) H64C(0.6) H64D(0.4) H64E(0.4)
 H64F(0.4) C65(0.7) H65A(0.7) H65B(0.7) H65C(0.7) H66A(0.6) H66B(0.6) H66C(0.6)
 H66D(0.4) H66E(0.4) H66F(0.4) C68(0.5) H68(0.5) H10V(0.5) H10W(0.5) H10X(0.5)
 H10Y(0.5) HB(0.5) HC(0.5) C115(0.8) H115(0.8) C119(0.5) H119(0.5) H12D(0.8)
 H12E(0.8) H12F(0.8) H12G(0.2) H12H(0.2) H12I(0.2) H12J(0.5) H12K(0.5)
 H12L(0.5) H12M(0.5) H12N(0.5) H12O(0.5) C124(0.45) H12P(0.45) H12Q(0.45)
 H12R(0.45) H12Z(0.5) HF(0.5) HG(0.5) HH(0.5) HI(0.5) HJ(0.5) C131(0.5)
 H131(0.5) H13D(0.5) H13E(0.5) H13F(0.5) H13G(0.5) H13H(0.5) H13I(0.5)
 C133(0.55) H133(0.55) H13J(0.8) H13K(0.8) H13L(0.8) H13M(0.2) H13N(0.2)
 H13O(0.2) H13P(0.5) H13Q(0.5) H13R(0.5) H13S(0.5) H13T(0.5) H13U(0.5)
 C136(0.5) H136(0.5) H13V(0.5) H13W(0.5) H13X(0.5) H13Y(0.5) HM(0.5) HN(0.5)
 C138(0.55) H13Z(0.55) HO(0.55) HP(0.55) C141(0.5) H141(0.5) C142(0.5)
 H142(0.5) C143(0.5) H143(0.5) C144(0.5) H144(0.5) C145(0.3) H14M(0.3)
 H14N(0.3) H14O(0.3) C146(0.4) H146(0.4) C147(0.45) H147(0.45) C148(0.45)
 H14D(0.45) H14E(0.45) H14F(0.45) C149(0.55) H14G(0.55) H14H(0.55) H14I(0.55)
 C150(0.2) H150(0.2)
7.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6), C9(H9), C11(H11), C12(H0AA), C13(H1AA), C15(H15), C16(H16),
 C20(H20), C21(H21), C23(H23), C26(H26), C28(H28), C37(H37), C41(H41),
 C41(H41A), C53(H53), C62(H62), C68(H68), C74(H74), C78(H78), C80(H80),
 C81(H81), C86(H86), C88(H88), C97(H97), C98(H98), C99(H99), C104(H104),
 C105(H105), C112(H112), C115(H115), C116(H116), C119(H119), C131(H131),
 C133(H133), C136(H136), C141(H141), C142(H142), C143(H143), C144(H144),
 C146(H146), C147(H147), C150(H150)
7.b Me refined with riding coordinates:
 C14(H14J,H14K,H14L), C18(H18A,H18B,H18C), C47(H47A,H47B,H47C), C47(H47D,H47E,
 H47F), C64(H64A,H64B,H64C), C64(H64D,H64E,H64F), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C66(H66D,H66E,H66F), C67(H67A,H67B,H67C), C70(H70A,H70B,H70C),
 C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C103(H10J,H10K,
 H10L), C113(H11G,H11H,H11I), C121(H12G,H12H,H12I), C124(H12P,H12Q,H12R),
 C130(H13A,H13B,H13C), C132(H13D,H13E,H13F), C132(H13G,H13H,H13I), C134(H13J,
 H13K,H13L), C134(H13M,H13N,H13O), C135(H13P,H13Q,H13R), C135(H13S,H13T,H13U),
 C137(H13V,H13W,H13X), C137(H13Y,HM,HN), C145(H14M,H14N,H14O)
7.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10Z,H,HA), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C),
 C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C48(H48D,
 H48E,H48F), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C69(H69A,H69B,H69C),
 C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C85(H85A,H85B,H85C), C87(H87A,H87B,H87C), C89(H89A,H89B,H89C), C90(H90A,
 H90B,H90C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C100(H10A,H10B,H10C),
 C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C106(H10M,H10N,H10O), C107(H10P,
 H10Q,H10R), C108(H10S,H10T,H10U), C109(H10V,H10W,H10X), C109(H10Y,HB,HC),
 C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C114(H11J,H11K,H11L), C117(H11M,
 H11N,H11O), C118(H11P,H11Q,H11R), C120(H12A,H12B,H12C), C121(H12D,H12E,H12F),
 C122(H12J,H12K,H12L), C122(H12M,H12N,H12O), C125(H12S,H12T,H12U), C126(H12V,
 H12W,H12X), C127(H12Y,HD,HE), C128(H12Z,HF,HG), C128(HH,HI,HJ), C129(H12,HK,
 HL), C138(H13Z,HO,HP), C139(H13,HQ,HR), C140(H14A,H14B,H14C), C148(H14D,H14E,
 H14F), C149(H14G,H14H,H14I)
;
_shelx_res_checksum              93310
_shelx_fab_checksum              66378
_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 2.400
_oxdiff_exptl_absorpt_empirical_full_min 0.603