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_1569651
_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         'C352 H416 Bi24 O55, 4(O)'
_chemical_formula_sum            'C352 H416 Bi24 O59'
_chemical_formula_weight         10606.34
_space_group_crystal_system      tetragonal
_space_group_IT_number           142
_space_group_name_Hall           '-I 4bd 2c'
_space_group_name_H-M_alt        'I 41/a c d :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-01-13 deposited with the CCDC.	2023-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   35.3979(8)
_cell_length_b                   35.3979(8)
_cell_length_c                   67.034(3)
_cell_measurement_reflns_used    9181
_cell_measurement_temperature    290(2)
_cell_measurement_theta_max      63.618
_cell_measurement_theta_min      2.824
_cell_volume                     83994(5)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      290.56
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0867
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       77
_diffrn_reflns_limit_l_min       -77
_diffrn_reflns_number            183395
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        63.865
_diffrn_reflns_theta_max         63.865
_diffrn_reflns_theta_min         2.823
_exptl_absorpt_coefficient_mu    19.745
_exptl_crystal_density_diffrn    1.677
_exptl_crystal_description       block
_exptl_crystal_F_000             39936
_refine_diff_density_max         1.919
_refine_diff_density_min         -1.116
_refine_diff_density_rms         0.230
_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     1004
_refine_ls_number_reflns         17336
_refine_ls_number_restraints     3313
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0895
_refine_ls_R_factor_gt           0.0566
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0996P)^2^+2645.0886P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1608
_refine_ls_wR_factor_ref         0.1886
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12354
_reflns_number_total             17336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02924g2.cif
_cod_data_source_block           1_sq_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1569648--1569653.cif.'
_cod_original_sg_symbol_H-M      'I 41/a c d'
_cod_database_code               1569651
_shelx_shelxl_version_number     2016/4
_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
 H5-H51C
 1.9 with sigma of 0.02
 C82-C77 \\sim C81-C77 \\sim C83-C77 \\sim C51-C39 \\sim C50-C39 \\sim C47-C39
\\sim C70-C61 \\sim C61-C55
 \\sim C72-C61 \\sim C79-C67 \\sim C75-C67 \\sim C78-C67 \\sim C64-C62 \\sim
C69-C62 \\sim C63-C62 \\sim C74-
 C60 \\sim C73-C60 \\sim C80-C60 \\sim C52-C45 \\sim C53-C45 \\sim C54-C45
\\sim C76-C59 \\sim C71-C59 ~
 C68-C59
 with sigma of 0.02
 C69-C64 \\sim C69-C63 \\sim C64-C63 \\sim C80-C73 \\sim C74-C73 \\sim C80-C74
\\sim C79-C75 \\sim C78-C75
 \\sim C79-C78 \\sim C54-C52 \\sim C53-C52 \\sim C54-C53 \\sim C70-C55 \\sim
C72-C55 \\sim C72-C70 \\sim C51-
 C50 \\sim C50-C47 \\sim C51-C47 \\sim C83-C82 \\sim C82-C81 \\sim C83-C81
\\sim C76-C71 \\sim C71-C68 ~
 C76-C68
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9
\\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O16 \\sim 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 O1W: within 3.8A with sigma
of 0.01 and sigma for terminal atoms of 0.03
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C17(H17A,H17B), C29(H29A,H29B), C36(H36A,H36B), C40(H40A,H40B),
 C85(H85A,H85B), C86(H86A,H86B), C88(H88A,H88B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C11(H11), C19(H19), C21(H21), C22(H22), C25(H25), C26(H26), C28(H28),
 C30(H30), C31(H31), C34(H34), C35(H35), C42(H42), C44(H44), C66(H66), C84(H84)
4.c Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C63(H63A,
 H63B,H63C), C64(H64A,H64B,H64C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,
 H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C78(H78A,
 H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C82(H82A,H82B,H82C), C83(H83A,H83B,H83C)
;
_shelx_res_checksum              77999
_shelx_fab_checksum              67909
_olex2_submission_special_instructions 'No special instructions were received'