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_1569648
_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         'C90 H112 Bi4 N2 O10'
_chemical_formula_sum            'C90 H112 Bi4 N2 O10'
_chemical_formula_weight         2217.73
_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             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                90
_cell_angle_beta                 106.94(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.93(6)
_cell_length_b                   13.52(3)
_cell_length_c                   30.86(7)
_cell_measurement_reflns_used    13667
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      25.000
_cell_measurement_theta_min      1.953
_cell_volume                     10349(4)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.982
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker D8 VENTURE'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0996
_diffrn_reflns_av_unetI/netI     0.0613
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            132456
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.264
_diffrn_reflns_theta_min         2.355
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    6.827
_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    1.423
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4312
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.517
_refine_diff_density_min         -1.904
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     979
_refine_ls_number_reflns         18394
_refine_ls_number_restraints     2809
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0568P)^2^+69.8597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1112
_refine_ls_wR_factor_ref         0.1235
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13667
_reflns_number_total             18394
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02924g2.cif
_cod_data_source_block           houbs210123_3_0m_sq
_cod_depositor_comments
'Adding full bibliography for 1569648--1569653.cif.'
_cod_original_cell_volume        10351(41)
_cod_database_code               1569648
_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
 C77-C15
 1.45 with sigma of 0.01
 C37-C22 \\sim C22-C35 \\sim C19-C22 \\sim C39-C81 \\sim C81-C21 \\sim C81-C41
\\sim C69-C83 \\sim C85-C83
 \\sim C89-C83 \\sim C50-C48 \\sim C52-C48 \\sim C75-C48 \\sim C25-C79 \\sim
C73-C79 \\sim C49-C79 \\sim C84-
 C82 \\sim C86-C82 \\sim C88-C82 \\sim C71-C87 \\sim C11-C87 \\sim C43-C87
\\sim C65-C9 \\sim C65-C5 \\sim C33-
 C65
 with sigma of 0.02
 C5-C33 \\sim C9-C5 \\sim C9-C33 \\sim C71-C43 \\sim C43-C11 \\sim C71-C11
\\sim C86-C84 \\sim C88-C86 ~
 C88-C84 \\sim C73-C25 \\sim C73-C49 \\sim C49-C25 \\sim C89-C85 \\sim C85-C69
\\sim C89-C69 \\sim C37-C19
 \\sim C37-C35 \\sim C35-C19 \\sim C39-C21 \\sim C41-C39 \\sim C41-C21 \\sim
C52-C50 \\sim C75-C50 \\sim C75-C52
 with sigma of 0.02
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 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 N1 \\sim N2: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.03 within 3.8A
4. Rigid body (RIGU) restrains
 C85, C83, C89, C69
 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), C14(H14A,H14B), C15(H15A,H15B), C28(H28A,H28B),
 C31(H31A,H31B), C40(H40A,H40B), C55(H55A,H55B), C58(H58A,H58B), C68(H68A,H68B),
  C77(H77A,H77B), C90(H90A,H90B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C10(H10), C18(H18), C23(H23), C24(H24), C32(H32), C36(H36),
 C44(H44), C51(H51), C53(H53), C54(H54), C63(H63), C67(H67), C76(H76), C80(H80)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C19(H19A,H19B,H19C),
 C21(H21A,H21B,H21C), C25(H25A,H25B,H25C), C33(H33A,H33B,H33C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C43(H43A,
 H43B,H43C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C),
 C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C75(H75A,H75B,
 H75C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C88(H88A,
 H88B,H88C), C89(H89A,H89B,H89C)
;
_shelx_res_checksum              79552
_shelx_fab_checksum              1564
_olex2_submission_special_instructions 'No special instructions were received'