Stepwise Assembly and Reversible Structure Transformation of Ligated Titanium Coated Bismuth-Oxo Cores: Shell Morphology Engineering for Enhanced Chemical Fixation of CO2
Zhang, Lei; Ding, Qing-Rong; Yu, Yinghua; Cao, Changsheng; Zhang, Jian; Chemical Science  (2022) –; doi:10.1039/D1SC06847D

data_1566245
_publ_section_title
;
 Stepwise Assembly and Reversible Structure Transformation of Ligated
 Titanium Coated Bismuth-Oxo Cores: Shell Morphology Engineering for
 Enhanced Chemical Fixation of CO2
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC06847D
_journal_year                    2022
_chemical_formula_moiety         'C334 H224 Bi38 O178 Ti16, 4(C2 H3 N)'
_chemical_formula_sum            'C342 H236 Bi38 N4 O178 Ti16'
_chemical_formula_weight         15956.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2021-08-20 deposited with the CCDC.	2022-02-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.6720(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.24030(10)
_cell_length_b                   43.6932(2)
_cell_length_c                   49.0721(3)
_cell_measurement_reflns_used    80433
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      60.4740
_cell_measurement_theta_min      2.3590
_cell_volume                     53751.6(5)
_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      100.00(14)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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     17.00 107.06   0.38    2.78    --   72.31-110.00-165.00  237
  2  \w     98.00 123.08   0.38    2.78    --   72.31 110.00 -70.00   66
  3  \w    -94.00 -21.80   0.38    2.78    --  -74.81 110.00 -70.00  190
  4  \w   -140.00-116.06   0.38    2.78    --  -74.81-110.00-165.00   63
  5  \w    -24.00  13.24   0.38    0.69    --   -1.25  77.00-120.00   98
  6  \w     46.00  71.08   0.38    0.69    --   -1.25  77.00-120.00   66
  7  \w    -16.00  20.86   0.38    0.69    --   -1.25  57.00  30.00   97
  8  \w     36.00  69.82   0.38    0.69    --   -1.25  57.00  30.00   89
  9  \w     60.00 140.94   0.38    2.78    --   72.31  77.00 -90.00  213
 10  \w     83.00 137.34   0.38    2.78    --   72.31 125.00 -30.00  143
 11  \w     60.00 130.30   0.38    2.78    --   72.31  57.00 -90.00  185
 12  \w   -146.00 -80.26   0.38    2.78    --  -74.81-125.00  90.00  173
 13  \w   -120.00 -91.88   0.38    2.78    --  -74.81 -99.00-180.00   74
 14  \w    -55.00  -3.70   0.38    2.78    --  -74.81  38.00 -90.00  135
 15  \w   -134.00-100.18   0.38    2.78    --  -74.81 -99.00 -90.00   89
;
_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      -0.0109588000
_diffrn_orient_matrix_UB_12      0.0140988000
_diffrn_orient_matrix_UB_13      0.0229289000
_diffrn_orient_matrix_UB_21      0.0181219000
_diffrn_orient_matrix_UB_22      0.0264028000
_diffrn_orient_matrix_UB_23      -0.0092379000
_diffrn_orient_matrix_UB_31      -0.0490263000
_diffrn_orient_matrix_UB_32      0.0065854000
_diffrn_orient_matrix_UB_33      -0.0120238000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            160943
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        52.932
_diffrn_reflns_theta_max         52.932
_diffrn_reflns_theta_min         2.246
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    18.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20711
_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            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.972
_exptl_crystal_description       spininess
_exptl_crystal_F_000             28984
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.929
_refine_diff_density_min         -4.006
_refine_diff_density_rms         0.326
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2447
_refine_ls_number_reflns         46869
_refine_ls_number_restraints     1219
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0896
_refine_ls_R_factor_gt           0.0669
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0980P)^2^+2951.0049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1720
_refine_ls_wR_factor_ref         0.1947
_reflns_Friedel_coverage         0.000
_reflns_number_gt                35372
_reflns_number_total             46869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06847d2.cif
_cod_data_source_block           284
_cod_database_code               1566245
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         CHONTiBi
_shelx_estimated_absorpt_t_max   0.462
_shelx_estimated_absorpt_t_min   0.073
_diffrn_oxdiff_digest_frames
;
01526e0044bf2eee7511a5eb7e343c1aab019180fe4
;
_diffrn_oxdiff_digest_hkl
;
011ad9ef7874bfd6e9f765ba512f7d251aeac6
;
_reflns_odcompleteness_completeness 98.69
_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
 O54-C107 = O01W-C107
 1.3 with sigma of 0.02
 O02P-C1BA
 1.3 with sigma of 0.02
 O54-Bi0A = O54-C107
 1.5 with sigma of 0.02
 C77-C107
 1.45 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C05F \\sim C94 \\sim C051: within 3.8A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C99 \\sim C051 \\sim C30: within 3.8A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C73 \\sim C9AA \\sim C66: within 3.8A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C117 \\sim C100 \\sim C87: within 3.8A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(C253) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O54) \\sim Ueq, Uanis(O54) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O54) \\sim Ueq, Uanis(O54) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C25)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C73) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C051) \\sim Ueq, Uanis(C051) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C94) \\sim Ueq, Uanis(C94) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C117) \\sim Ueq, Uanis(C117) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C169) \\sim Ueq, Uanis(C169) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C05V) \\sim Ueq, Uanis(C05V) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C66) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C87) \\sim Ueq, Uanis(C87) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9AA) \\sim Ueq, Uanis(C9AA) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C100) \\sim Ueq, Uanis(C100) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C103) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1BA) = Uanis(C77) = Uanis(C96) = Uanis(C253) = Uanis(C244) = Uanis(C105)
= Uanis(C107)
5.a Riding coordinates:
 C336(H33A,H33B,H33C)
5.b Ternary CH refined with riding coordinates:
 C047(H047), C048(H048), C04G(H04G), C05G(H05G), C0AA(H0AA), C2AA(H2AA)
5.c Secondary CH2 refined with riding coordinates:
 C031(H03A,H03B), C03X(H03C,H03D), C045(H04A,H04B), C05J(H05A,H05H), C065(H06A,
 H06B), C2(H2A,H2B)
5.d Aromatic/amide H refined with riding coordinates:
 C02W(H02W), C02Y(H02Y), C034(H034), C037(H037), C039(H039), C03F(H03F),
 C03G(H03G), C03M(H03M), C03O(H03O), C03P(H03P), C03T(H03T), C03U(H03U),
 C041(H041), C044(H044), C7AA(H7AA), C87(H87), C117(H117), C100(H100),
 C04A(H04C), C04E(H04E), C04F(H04F), C04L(H04L), C04P(H04P), C04Q(H04Q),
 C04T(H04T), C04W(H04W), C04X(H04X), C051(H051), C05F(H05F), C94(H94),
 C169(H169), C30(H30), C052(H052), C054(H054), C055(H055), C057(H057),
 C058(H058), C05B(H05B), C05C(H05C), C05D(H05D), C05E(H05E), C05I(H05I),
 C05K(H05K), C05L(H05L), C05R(H05R), C05U(H05U), C05V(H05V), C05Z(H05Z),
 C060(H060), C93(H93), C25(H25), C103(H103), C72(H72), C062(H062), C9AA(H9AA),
 C73(H73), C66(H66), C101(H101), C069(H069), C03Q(H03Q), C02T(H02T), C55(H55),
 C03R(H03R), C45(H45), C47(H47), C51(H51), C67(H67), C196(H196), C90(H90),
 C70(H70), C61(H61), C65(H65), C69(H69), C79(H79), C84(H84), C64(H64), C86(H86),
  C334(H334), C6AA(H6AA), C8AA(H8AA), C41(H41), C0BA(H0BA), C16(H16), C88(H88),
 C105(H105), C244(H244), C253(H253), C96(H96), C108(H108), C369(H369),
 C03Y(H03Y), C62(H62), C179(H179), C184(H184)
5.e Fitted hexagon refined as free rotating group:
 C046(C04Z,C7AA,C87,C117,C100), C051(C05F,C94,C169,C30,C99), C061(C05N,C93,C25,
 C103,C72), C063(C4AA,C9AA,C73,C66,C101), C39(C03Q,C02T,C55,C03R,C42), C58(C67,
 C196,C90,C70,C54), C056(C64,C86,C334,C6AA,C50), C4(C10,C8AA,C41,C0BA,C16),
 C77(C1BA,C105,C244,C253,C96), C108(C369,C03Y,C62,C537,C345)
5.f Idealised Me refined as rotating group:
 C05M(H05J,H05M,H05N)
;
_shelx_res_checksum              7676
_shelx_hkl_checksum              13033
_shelx_fab_checksum              43909
_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 3.565
_oxdiff_exptl_absorpt_empirical_full_min 0.346