Electron delocalization of robust high-nuclear bismuth-oxo clusters for promoted CO<sub>2</sub> electroreduction.
Hou, Baoshan; Zheng, Haiyan; Zhang, Kunhao; Wu, Qi; Qin, Chao; Sun, Chunyi; Pan, Qinhe; Kang, Zhenhui; Wang, Xinlong; Su, Zhongmin; Chemical science 14 (2023) 8962–8969; doi:10.1039/d3sc02924g

data_1569649
_publ_section_title
;
 Electron delocalization of robust high-nuclear bismuth-oxo clusters for
 promoted CO<sub>2</sub> electroreduction.
;
_journal_issue                   33
_journal_name_full               'Chemical science'
_journal_page_first              8962
_journal_page_last               8969
_journal_paper_doi               10.1039/d3sc02924g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C93 H121 Bi4 N2 O13'
_chemical_formula_sum            'C93 H121 Bi4 N2 O13'
_chemical_formula_weight         2310.83
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-31
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-01-13 deposited with the CCDC.	2023-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                67.924(11)
_cell_angle_beta                 78.114(12)
_cell_angle_gamma                83.852(11)
_cell_formula_units_Z            2
_cell_length_a                   16.570(4)
_cell_length_b                   17.360(4)
_cell_length_c                   19.896(5)
_cell_measurement_reflns_used    14541
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      57.000
_cell_measurement_theta_min      1.953
_cell_volume                     5187(2)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      173.02
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker D8 VENTURE'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '0.60\ % \ w and 0.6\ % \ f scans'
_diffrn_radiation_collimation    '0.5 mm double- pinhole'
_diffrn_radiation_detector       'Bruker D8 VENTURE'
_diffrn_radiation_monochromator  'equatorially mounted graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_unetI/netI     0.0452
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            72620
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        64.050
_diffrn_reflns_theta_max         64.050
_diffrn_reflns_theta_min         2.436
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    13.492
_exptl_absorpt_correction_T_max  0.86
_exptl_absorpt_correction_T_min  0.84
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.479
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2258
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.558
_refine_diff_density_min         -2.667
_refine_diff_density_rms         0.210
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1035
_refine_ls_number_reflns         17011
_refine_ls_number_restraints     3771
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0415P)^2^+102.3428P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14541
_reflns_number_total             17011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02924g2.cif
_cod_data_source_block           1_sq_sq
_cod_depositor_comments
'Adding full bibliography for 1569648--1569653.cif.'
_cod_database_code               1569649
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.54
_shelx_estimated_absorpt_t_min   0.21
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O11-C79 \\sim O13-C84 \\sim O14-C94
 with sigma of 0.02
 Bi3-O14 \\sim Bi1-O13 \\sim Bi1-O11
 with sigma of 0.02
 C91-C68 \\sim C93-C68 \\sim C92-C68 \\sim C67-C60 \\sim C73-C60 \\sim C65-C60
\\sim C87-C71 \\sim C86-C71
 \\sim C90-C71 \\sim C72-C58 \\sim C64-C58 \\sim C85-C58 \\sim C82-C53 \\sim
C83-C53 \\sim C81-C53 \\sim C80-
 C62 \\sim C70-C62 \\sim C76-C62 \\sim C61-C45 \\sim C63-C45 \\sim C66-C45
\\sim C89-C69 \\sim C78-C69 ~
 C88-C69
 with sigma of 0.02
 C66-C63 \\sim C63-C61 \\sim C66-C61 \\sim C76-C70 \\sim C80-C76 \\sim C80-C70
\\sim C83-C82 \\sim C82-C81
 \\sim C83-C81 \\sim C72-C64 \\sim C85-C64 \\sim C85-C72 \\sim C89-C88 \\sim
C89-C78 \\sim C88-C78 \\sim C73-
 C67 \\sim C67-C65 \\sim C73-C65 \\sim C93-C91 \\sim C92-C91 \\sim C93-C92
\\sim C90-C87 \\sim C87-C86 ~
 C90-C86
 with sigma of 0.01
 C72-C16 \\sim C64-C16 \\sim C85-C16 \\sim C81-C54 \\sim C82-C54 \\sim C83-C54
\\sim C76-C39 \\sim C70-C39
 \\sim C80-C39 \\sim C66-C30 \\sim C61-C30 \\sim C63-C30 \\sim C78-C56 \\sim
C89-C56 \\sim C88-C56 \\sim C65-
 C51 \\sim C73-C51 \\sim C67-C51 \\sim C91-C59 \\sim C92-C59 \\sim C93-C59
\\sim C90-C52 \\sim C86-C52 ~
 C87-C52
 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 \\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 C76 \\sim C77 \\sim C78 \\sim C80 \\sim C81 \\sim C82 \\sim C83
\\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92
\\sim C93 \\sim C79 \\sim C84 \\sim C94 \\sim O1 \\sim O2 \\sim O3 \\sim O4
\\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9 \\sim O10 \\sim O11 \\sim O13
\\sim O14: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
within 3.8A
4. Rigid body (RIGU) restrains
 O14, C94
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), C6(H6A,H6B), C12(H12A,H12B), C19(H19A,H19B),
 C27(H27A,H27B), C33(H33A,H33B), C37(H37A,H37B), C49(H49A,H49B), C57(H57A,H57B),
  C74(H74A,H74B), C77(H77A,H77B)
5.b Me refined with riding coordinates:
 C92(H92A,H92B,H92C)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C17(H17), C20(H20), C25(H25), C26(H26), C28(H28), C29(H29),
 C38(H38), C40(H40), C42(H42), C44(H44), C46(H46), C48(H48), C50(H50), C55(H55)
5.d Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C70(H70A,H70B,H70C), C72(H72A,
 H72B,H72C), C73(H73A,H73B,H73C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C),
 C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,
 H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C),
 C93(H93A,H93B,H93C), C79(H79A,H79B,H79C), C84(H84A,H84B,H84C), C94(H94A,H94B,
 H94C)
;
_shelx_res_checksum              59975
_shelx_fab_checksum              74505
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'