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_1569653
_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         'C538 H654 Bi40 Mo2 N6 O98'
_chemical_formula_sum            'C538 H654 Bi40 Mo2 N6 O98'
_chemical_formula_weight         17323.71
_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
_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                92.631(4)
_cell_angle_beta                 103.905(4)
_cell_angle_gamma                115.578(3)
_cell_formula_units_Z            1
_cell_length_a                   22.5724(15)
_cell_length_b                   23.0297(14)
_cell_length_c                   36.361(2)
_cell_measurement_reflns_used    9631
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      57.000
_cell_measurement_theta_min      1.953
_cell_volume                     16306.2(18)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      173.02
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker D8 VENTURE'
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_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_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1527
_diffrn_reflns_av_unetI/netI     0.1566
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            179869
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        64.146
_diffrn_reflns_theta_max         64.146
_diffrn_reflns_theta_min         2.494
_exptl_absorpt_coefficient_mu    21.469
_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    1.764
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             8112
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.832
_refine_diff_density_min         -1.508
_refine_diff_density_rms         0.259
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3083
_refine_ls_number_reflns         52651
_refine_ls_number_restraints     17793
_refine_ls_restrained_S_all      0.901
_refine_ls_R_factor_all          0.1633
_refine_ls_R_factor_gt           0.0895
_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^)+(0.0960P)^2^+291.3215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2026
_refine_ls_wR_factor_ref         0.2364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28550
_reflns_number_total             52651
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02924g2.cif
_cod_data_source_block           1_sq_sq_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1569648--1569653.cif.'
_cod_database_code               1569653
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.099
_shelx_estimated_absorpt_t_min   0.079
_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
 Bi18-O46
 2.622 with sigma of 0.01
 Bi20-O49
 2.741 with sigma of 0.01
 H21I-H122
 1.8 with sigma of 0.02
 C244-C139 \\sim C177-C171 \\sim C167-C156 \\sim C188-C125 \\sim C192-C146
\\sim C205-C174 \\sim C242-
 C166 \\sim C210-C160 \\sim C185-C100 \\sim C71-C63 \\sim C191-C147 \\sim
C195-C105 \\sim C182-C130 ~
 C81-C179 \\sim C189-C170 \\sim C103-C101 \\sim C98-C110 \\sim C95-C184 \\sim
C229-C168 \\sim C213-C169
 \\sim C178-C163 \\sim C87-C114 \\sim C56-C181 \\sim C208-C206
 with sigma of 0.01
 C239-C185 \\sim C250-C185 \\sim C226-C185 \\sim C230-C210 \\sim C249-C210
\\sim C265-C210 \\sim C205-
 C190 \\sim C259-C205 \\sim C255-C205 \\sim C233-C192 \\sim C235-C192 \\sim
C212-C192 \\sim C256-C188 ~
 C245-C188 \\sim C251-C188 \\sim C260-C167 \\sim C257-C167 \\sim C262-C167
\\sim C261-C229 \\sim C264-
 C229 \\sim C229-C207 \\sim C244-C243 \\sim C263-C244 \\sim C248-C244 \\sim
C241-C177 \\sim C246-C177 ~
 C214-C177 \\sim C268-C242 \\sim C267-C242 \\sim C266-C242 \\sim C217-C114
\\sim C197-C114 \\sim C201-
 C114 \\sim C71-C203 \\sim C71-C209 \\sim C71-C186 \\sim C221-C178 \\sim
C202-C178 \\sim C218-C178 ~
 C234-C184 \\sim C232-C184 \\sim C211-C184 \\sim C196-C101 \\sim C194-C101
\\sim C180-C101 \\sim C224-
 C110 \\sim C228-C110 \\sim C216-C110 \\sim C253-C189 \\sim C227-C189 \\sim
C199-C189 \\sim C240-C182 ~
 C247-C182 \\sim C254-C182 \\sim C200-C179 \\sim C231-C179 \\sim C258-C179
\\sim C238-C195 \\sim C215-
 C195 \\sim C252-C195 \\sim C236-C191 \\sim C225-C191 \\sim C220-C191 \\sim
C269-C206 \\sim C223-C206 ~
 C206-C204 \\sim C222-C213 \\sim C219-C213 \\sim C237-C213 \\sim C187-C181
\\sim C198-C181 \\sim C193-
 C181
 with sigma of 0.01
 C223-C204 \\sim C246-C241 \\sim C246-C214 \\sim C241-C214 \\sim C198-C193
\\sim C193-C187 \\sim C198-
 C187 \\sim C269-C223 \\sim C269-C204 \\sim C258-C231 \\sim C258-C200 \\sim
C231-C200 \\sim C194-C180 ~
 C196-C194 \\sim C196-C180 \\sim C232-C211 \\sim C234-C232 \\sim C234-C211
\\sim C260-C257 \\sim C264-
 C207 \\sim C264-C261 \\sim C261-C207 \\sim C262-C260 \\sim C262-C257 \\sim
C248-C243 \\sim C263-C248 ~
 C263-C243 \\sim C256-C245 \\sim C251-C245 \\sim C256-C251 \\sim C235-C233
\\sim C233-C212 \\sim C235-
 C212 \\sim C259-C255 \\sim C259-C190 \\sim C255-C190 \\sim C250-C239 \\sim
C239-C226 \\sim C250-C226 ~
 C236-C225 \\sim C236-C220 \\sim C225-C220 \\sim C238-C215 \\sim C252-C238
\\sim C252-C215 \\sim C247-
 C240 \\sim C254-C240 \\sim C254-C247 \\sim C203-C186 \\sim C209-C186 \\sim
C209-C203 \\sim C253-C227 ~
 C227-C199 \\sim C253-C199 \\sim C217-C201 \\sim C217-C197 \\sim C201-C197
\\sim C265-C249 \\sim C249-
 C230 \\sim C265-C230 \\sim C268-C266 \\sim C267-C266 \\sim C268-C267 \\sim
C237-C222 \\sim C222-C219 ~
 C237-C219 \\sim C218-C202 \\sim C221-C202 \\sim C221-C218 \\sim C224-C216
\\sim C228-C216 \\sim C228-
 C224
 with sigma of 0.01
 C233-C146 \\sim C212-C146 \\sim C235-C146 \\sim C259-C174 \\sim C255-C174
\\sim C190-C174 \\sim C226-
 C100 \\sim C239-C100 \\sim C250-C100 \\sim C220-C147 \\sim C236-C147 \\sim
C225-C147 \\sim C252-C105 ~
 C238-C105 \\sim C215-C105 \\sim C81-C231 \\sim C81-C200 \\sim C81-C258 \\sim
C208-C204 \\sim C269-C208
 \\sim C223-C208 \\sim C199-C170 \\sim C227-C170 \\sim C253-C170 \\sim C56-C193
\\sim C56-C187 \\sim C56-
 C198 \\sim C98-C216 \\sim C98-C224 \\sim C98-C228 \\sim C207-C168 \\sim
C261-C168 \\sim C264-C168 ~
 C262-C156 \\sim C257-C156 \\sim C260-C156 \\sim C263-C139 \\sim C243-C139
\\sim C248-C139 \\sim C246-
 C171 \\sim C214-C171 \\sim C241-C171 \\sim C180-C103 \\sim C194-C103 \\sim
C196-C103 \\sim C87-C201 ~
 C87-C217 \\sim C87-C197 \\sim C221-C163 \\sim C218-C163 \\sim C202-C163 \\sim
C63-C186 \\sim C63-C209
 \\sim C63-C203 \\sim C254-C130 \\sim C240-C130 \\sim C247-C130 \\sim C256-C125
\\sim C245-C125 \\sim C251-
 C125 \\sim C249-C160 \\sim C230-C160 \\sim C265-C160 \\sim C267-C166 \\sim
C268-C166 \\sim C266-C166 ~
 C219-C169 \\sim C237-C169 \\sim C222-C169 \\sim C95-C232 \\sim C95-C211 \\sim
C95-C234
 with sigma of 0.01
3. Restrained planarity
 C42, C75, C80, C88, C143, C174, C205
 with sigma of 0.1
 C53, C61, C125, C131, C148, C153, C188
 with sigma of 0.1
 C14, C86, C124, C134, C146, C150, C192
 with sigma of 0.1
 C9, C19, C21, C108, C109, C206, C208
 with sigma of 0.1
 C16, C32, C37, C74, C127, C170, C189
 with sigma of 0.1
 C34, C66, C78, C117, C122, C171, C177
 with sigma of 0.1
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 C124 \\sim C134 \\sim
C146 \\sim C150 \\sim C86 \\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 C35 \\sim C36
\\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C75 \\sim C88
\\sim C174 \\sim C143 \\sim C80 \\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 C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim
C72 \\sim C73 \\sim C74 \\sim C76 \\sim C77 \\sim C78 \\sim C34 \\sim C66 \\sim
C171 \\sim C122 \\sim C117 \\sim C79 \\sim C81 \\sim C82 \\sim C83 \\sim C84
\\sim C85 \\sim C87 \\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 C118 \\sim C119 \\sim C120 \\sim C121 \\sim C123 \\sim C125 \\sim
C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim
C133 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139 \\sim C140 \\sim
C141 \\sim C142 \\sim C144 \\sim C145 \\sim C147 \\sim C148 \\sim C149 \\sim
C151 \\sim C152 \\sim C153 \\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim
C158 \\sim C159 \\sim C160 \\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim
C165 \\sim C166 \\sim C167 \\sim C168 \\sim C169 \\sim C170 \\sim C172 \\sim
C173 \\sim C175 \\sim C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim
C181 \\sim C182 \\sim C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim
C188 \\sim C189 \\sim C190 \\sim C191 \\sim C192 \\sim C193 \\sim C194 \\sim
C195 \\sim C196 \\sim C197 \\sim C198 \\sim C199 \\sim C200 \\sim C201 \\sim
C202 \\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207 \\sim C208 \\sim
C209 \\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim C215 \\sim
C216 \\sim C217 \\sim C218 \\sim C219 \\sim C220 \\sim C221 \\sim C222 \\sim
C223 \\sim C224 \\sim C225 \\sim C226 \\sim C227 \\sim C228 \\sim C229 \\sim
C230 \\sim C231 \\sim C232 \\sim C233 \\sim C234 \\sim C235 \\sim C236 \\sim
C237 \\sim C238 \\sim C239 \\sim C240 \\sim C241 \\sim C242 \\sim C243 \\sim
C244 \\sim C245 \\sim C246 \\sim C247 \\sim C248 \\sim C249 \\sim C250 \\sim
C251 \\sim C252 \\sim C253 \\sim C254 \\sim C255 \\sim C256 \\sim C257 \\sim
C258 \\sim C259 \\sim C260 \\sim C261 \\sim C262 \\sim C263 \\sim C264 \\sim
C265 \\sim C266 \\sim C267 \\sim C268 \\sim C269 \\sim N1 \\sim N2 \\sim N3
\\sim 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 O15 \\sim O16 \\sim
O17 \\sim O18 \\sim O19 \\sim O20 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim
O25 \\sim O26 \\sim O27 \\sim O28 \\sim O29 \\sim O30 \\sim O31 \\sim O32 \\sim
O33 \\sim O34 \\sim O35 \\sim O36 \\sim O37 \\sim O38 \\sim O39 \\sim O40 \\sim
O41 \\sim O42 \\sim O43 \\sim O44 \\sim O45 \\sim O47 \\sim O48 \\sim O46 \\sim
O49: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
5.a Secondary CH2 refined with riding coordinates:
 N2(H2A,H2B), N3(H3A,H3B), C8(H8A,H8B), C27(H27A,H27B), C31(H31A,H31B),
 C35(H35A,H35B), C50(H50A,H50B), C55(H55A,H55B), C58(H58A,H58B), C68(H68A,H68B),
  C70(H70A,H70B), C76(H76A,H76B), C77(H77A,H77B), C82(H82A,H82B), C85(H85A,
 H85B), C89(H89A,H89B), C96(H96A,H96B), C104(H10A,H10B), C115(H11D,H11E),
 C116(H11F,H11G), C119(H11H,H11I), C121(H12A,H12B), C126(H12C,H12D), C132(H13A,
 H13B), C151(H15A,H15B), C175(H17A,H17B), C176(H17C,H17D), C183(H18D,H18E)
5.b Me refined with riding coordinates:
 C207(H20P,H20Q,H20R), C212(H21D,H21E,H21F), C235(H23P,H23Q,H23R), C237(H23V,
 H23W,H23X), C255(H25P,H25Q,H25R), C262(H26G,H26H,H26I), C266(H26S,H26T,H26U),
 C267(H26V,H26W,H26X), C269(H26Z,HL,HM)
5.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C134(H134), C150(H150), C17(H17), C23(H23), C25(H25),
 C36(H36), C41(H41), C88(H88), C143(H143), C47(H47), C54(H54), C57(H57),
 C60(H60), C64(H64), C65(H65), C67(H67), C72(H72), C74(H74), C66(H66),
 C122(H122), C79(H79), C92(H92), C93(H93), C99(H99), C102(H102), C106(H106),
 C108(H108), C109(H109), C111(H111), C112(H112), C118(H118), C127(H127),
 C131(H131), C135(H135), C138(H138), C140(H140), C142(H142), C145(H145),
 C148(H148), C149(H149), C152(H152), C155(H155), C157(H157), C161(H161),
 C164(H164), C172(H172), C173(H173)
5.d Fitted hexagon refined as free rotating group:
 C14(C124,C134,C146,C150,C86), C42(C75,C88,C174,C143,C80), C78(C34,C66,C171,
 C122,C117), C136(C137,C138,C139,C140,C141), C154(C155,C156,C157,C158,C159)
5.e Idealised Me refined with riding coordinates:
 C265(H26P,H26Q,H26R)
5.f Idealised Me refined as rotating group:
 C91(H91A,H91B,H91C), C113(H11A,H11B,H11C), C180(H18A,H18B,H18C), C186(H18F,
 H18G,H18H), C187(H18I,H18J,H18K), C190(H19A,H19B,H19C), C193(H19D,H19E,H19F),
 C194(H19G,H19H,H19I), C196(H19J,H19K,H19L), C197(H19M,H19N,H19O), C198(H19P,
 H19Q,H19R), C199(H19S,H19T,H19U), C200(H20A,H20B,H20C), C201(H20D,H20E,H20F),
 C202(H20G,H20H,H20I), C203(H20J,H20K,H20L), C204(H20M,H20N,H20O), C209(H20S,
 H20T,H20U), C211(H21A,H21B,H21C), C214(H21G,H21H,H21I), C215(H21J,H21K,H21L),
 C216(H21M,H21N,H21O), C217(H21P,H21Q,H21R), C218(H21S,H21T,H21U), C219(H21V,
 H21W,H21X), C220(H22A,H22B,H22C), C221(H22D,H22E,H22F), C222(H22G,H22H,H22I),
 C223(H22J,H22K,H22L), C224(H22M,H22N,H22O), C225(H22P,H22Q,H22R), C226(H22S,
 H22T,H22U), C227(H22V,H22W,H22X), C228(H22Y,H,HA), C230(H23A,H23B,H23C),
 C231(H23D,H23E,H23F), C232(H23G,H23H,H23I), C233(H23J,H23K,H23L), C234(H23M,
 H23N,H23O), C236(H23S,H23T,H23U), C238(H23Y,HB,HC), C239(H23Z,HD,HE),
 C240(H24A,H24B,H24C), C241(H24D,H24E,H24F), C243(H24G,H24H,H24I), C245(H24J,
 H24K,H24L), C246(H24M,H24N,H24O), C247(H24P,H24Q,H24R), C248(H24S,H24T,H24U),
 C249(H24V,H24W,H24X), C250(H25A,H25B,H25C), C251(H25D,H25E,H25F), C252(H25G,
 H25H,H25I), C253(H25J,H25K,H25L), C254(H25M,H25N,H25O), C256(H25S,H25T,H25U),
 C257(H25V,H25W,H25X), C258(H25Y,HF,HG), C259(H25Z,HH,HI), C260(H26A,H26B,H26C),
  C261(H26D,H26E,H26F), C263(H26J,H26K,H26L), C264(H26M,H26N,H26O), C268(H26Y,
 HJ,HK)
;
_shelx_res_checksum              49937
_shelx_fab_checksum              45158
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'