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_1569652
_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         'C264 H312 Bi20 N O47'
_chemical_formula_sum            'C264 H312 Bi20 N O47'
_chemical_formula_weight         8430.73
_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
_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                 100.421(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.208(2)
_cell_length_b                   37.888(4)
_cell_length_c                   44.949(4)
_cell_measurement_reflns_used    9743
_cell_measurement_temperature    290.56
_cell_measurement_theta_max      63.996
_cell_measurement_theta_min      3.072
_cell_volume                     37197(6)
_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 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0643
_diffrn_reflns_av_unetI/netI     0.0496
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            297755
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        64.136
_diffrn_reflns_theta_max         64.136
_diffrn_reflns_theta_min         2.023
_exptl_absorpt_coefficient_mu    18.543
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             15756
_refine_diff_density_max         3.262
_refine_diff_density_min         -6.544
_refine_diff_density_rms         0.242
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3049
_refine_ls_number_reflns         61522
_refine_ls_number_restraints     11897
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0826P)^2^+860.1859P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1712
_refine_ls_wR_factor_ref         0.1794
_reflns_Friedel_coverage         0.000
_reflns_number_gt                51876
_reflns_number_total             61522
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02924g2.cif
_cod_data_source_block           1_sq_CCDC2
_cod_depositor_comments
'Adding full bibliography for 1569648--1569653.cif.'
_cod_database_code               1569652
_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
 N71-O46
 1.5 with sigma of 0.01
 H21D-H163
 1.8 with sigma of 0.02
 H26H-H252
 1.8 with sigma of 0.02
 H21P-H56
 1.8 with sigma of 0.02
 HA-H117
 1.8 with sigma of 0.02
 C190-C179 \\sim C195-C190 \\sim C206-C190 \\sim C230-C191 \\sim C191-C181
\\sim C248-C191 \\sim C93-
 C240 \\sim C93-C239 \\sim C93-C256 \\sim C244-C224 \\sim C224-C209 \\sim
C254-C224 \\sim C91-C169 ~
 C91-C188 \\sim C91-C220 \\sim C237-C168 \\sim C241-C168 \\sim C226-C168 \\sim
C89-C218 \\sim C89-C233
 \\sim C89-C235 \\sim C255-C147 \\sim C227-C147 \\sim C262-C147 \\sim C234-C194
\\sim C243-C194 \\sim C259-
 C194 \\sim C251-C192 \\sim C205-C192 \\sim C225-C192 \\sim C223-C214 \\sim
C242-C214 \\sim C253-C214 ~
 C94-C236 \\sim C94-C204 \\sim C95-C94 \\sim C187-C142 \\sim C166-C142 \\sim
C167-C142 \\sim C258-C118
 \\sim C264-C118 \\sim C228-C118 \\sim C189-C160 \\sim C215-C160 \\sim
C212-C160 \\sim C238-C213 \\sim C229-
 C213 \\sim C221-C213 \\sim C265-C197 \\sim C257-C197 \\sim C261-C197 \\sim
C260-C217 \\sim C263-C217 ~
 C90-C217 \\sim C222-C186 \\sim C232-C186 \\sim C199-C186 \\sim C266-C170 \\sim
C216-C170 \\sim C185-
 C170 \\sim C231-C148 \\sim C201-C148 \\sim C203-C148 \\sim C250-C136 \\sim
C246-C136 \\sim C198-C136 ~
 C247-C146 \\sim C245-C146 \\sim C249-C146 \\sim C211-C155 \\sim C210-C155
\\sim C202-C155
 with sigma of 0.02
 C254-C209 \\sim C254-C244 \\sim C244-C209 \\sim C256-C240 \\sim C256-C239
\\sim C240-C239 \\sim C206-
 C179 \\sim C195-C179 \\sim C206-C195 \\sim C230-C181 \\sim C248-C181 \\sim
C248-C230 \\sim C220-C169 ~
 C188-C169 \\sim C220-C188 \\sim C235-C218 \\sim C233-C218 \\sim C235-C233
\\sim C249-C245 \\sim C249-
 C247 \\sim C247-C245 \\sim C250-C246 \\sim C250-C198 \\sim C246-C198 \\sim
C222-C199 \\sim C232-C222 ~
 C232-C199 \\sim C231-C201 \\sim C203-C201 \\sim C231-C203 \\sim C265-C257
\\sim C261-C257 \\sim C265-
 C261 \\sim C229-C221 \\sim C238-C229 \\sim C238-C221 \\sim C215-C212 \\sim
C215-C189 \\sim C212-C189 ~
 C264-C258 \\sim C258-C228 \\sim C264-C228 \\sim C210-C202 \\sim C211-C210
\\sim C211-C202 \\sim C187-
 C167 \\sim C187-C166 \\sim C167-C166 \\sim C237-C226 \\sim C241-C237 \\sim
C241-C226 \\sim C259-C234 ~
 C259-C243 \\sim C243-C234 \\sim C225-C205 \\sim C251-C205 \\sim C251-C225
\\sim C266-C185 \\sim C216-
 C185 \\sim C266-C216 \\sim C263-C260 \\sim C90-C263 \\sim C90-C260 \\sim
C255-C227 \\sim C262-C255 ~
 C262-C227 \\sim C242-C223 \\sim C253-C223 \\sim C253-C242 \\sim C236-C204
\\sim C95-C204 \\sim C95-C236
 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 C267 \\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 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
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 C117 \\sim C118 \\sim C119 \\sim
C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim
C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim
C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139 \\sim C140 \\sim
C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146 \\sim C147 \\sim
C148 \\sim C149 \\sim C150 \\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 C171 \\sim C172 \\sim C173 \\sim C174 \\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: within
3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
Uanis(N71) \\sim Ueq, Uanis(O46) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.005
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C11(H11A,H11B), C25(H25A,H25B), C34(H34A,H34B), C38(H38A,H38B),
 C53(H53A,H53B), C57(H57A,H57B), C65(H65A,H65B), C69(H69A,H69B), C104(H10A,
 H10B), C105(H10C,H10D), C107(H10E,H10F), C111(H11C,H11D), C113(H11E,H11F),
 C121(H12A,H12B), C122(H12C,H12D), C127(H12E,H12F), C132(H13A,H13B), C134(H13C,
 H13D), C153(H15A,H15B), C156(H15C,H15D), C159(H15E,H15F), C177(H17A,H17B),
 C200(H20A,H20B)
4.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C26(H26), C36(H36), C40(H40), C44(H44), C47(H47), C50(H50),
 C52(H52), C55(H55), C56(H56), C60(H60), C67(H67), C68(H68), C74(H74), C77(H77),
  C78(H78), C80(H80), C82(H82), C83(H83), C86(H86), C88(H88), C98(H98),
 C102(H102), C112(H112), C114(H114), C116(H116), C117(H117), C124(H124),
 C125(H125), C128(H128), C130(H130), C131(H131), C133(H133), C140(H140),
 C141(H141), C144(H144), C150(H150), C154(H154), C157(H157), C163(H163),
 C164(H164), C174(H174), C176(H176), C178(H178), C193(H193), C208(H208),
 C219(H219), C252(H252)
4.c Fitted hexagon refined as free rotating group:
 C171(C172,C173,C174,C175,C176)
4.d Idealised Me refined as rotating group:
 C90(H90A,H90B,H90C), C95(H95A,H95B,H95C), C166(H16A,H16B,H16C), C167(H16D,
 H16E,H16F), C169(H16G,H16H,H16I), C179(H17C,H17D,H17E), C181(H18A,H18B,H18C),
 C185(H18D,H18E,H18F), C187(H18G,H18H,H18I), C188(H18J,H18K,H18L), C189(H18M,
 H18N,H18O), C195(H19A,H19B,H19C), C198(H19D,H19E,H19F), C199(H19G,H19H,H19I),
 C201(H20C,H20D,H20E), C202(H20F,H20G,H20H), C203(H20I,H20J,H20K), C204(H20L,
 H20M,H20N), C205(H20O,H20P,H20Q), C206(H20R,H20S,H20T), C209(H20U,H20V,H20W),
 C210(H21A,H21B,H21C), C211(H21D,H21E,H21F), C212(H21G,H21H,H21I), C215(H21J,
 H21K,H21L), C216(H21M,H21N,H21O), C218(H21P,H21Q,H21R), C220(H22A,H22B,H22C),
 C221(H22D,H22E,H22F), C222(H22G,H22H,H22I), C223(H22J,H22K,H22L), C225(H22M,
 H22N,H22O), C226(H22P,H22Q,H22R), C227(H22S,H22T,H22U), C228(H22V,H22W,H22X),
 C229(H22Y,H,HA), C230(H23A,H23B,H23C), C231(H23D,H23E,H23F), C232(H23G,H23H,
 H23I), C233(H23J,H23K,H23L), C234(H23M,H23N,H23O), C235(H23P,H23Q,H23R),
 C236(H23S,H23T,H23U), C237(H23V,H23W,H23X), C238(H23Y,HB,HC), C239(H23Z,HD,HE),
  C240(H24A,H24B,H24C), C241(H24D,H24E,H24F), C242(H24G,H24H,H24I), C243(H24J,
 H24K,H24L), C244(H24M,H24N,H24O), C245(H24P,H24Q,H24R), C246(H24S,H24T,H24U),
 C247(H24V,H24W,H24X), C248(H24Y,HF,HG), C249(H24Z,HH,HI), C250(H25C,H25D,H25E),
  C251(H25F,H25G,H25H), C253(H25I,H25J,H25K), C254(H25L,H25M,H25N), C255(H25O,
 H25P,H25Q), C256(H25R,H25S,H25T), C257(H25U,H25V,H25W), C258(H25X,H25Y,HJ),
 C259(H25Z,HK,HL), C260(H26A,H26B,H26C), C261(H26D,H26E,H26F), C262(H26G,H26H,
 H26I), C263(H26J,H26K,H26L), C264(H26M,H26N,H26O), C265(H26P,H26Q,H26R),
 C266(H26S,H26T,H26U)
;
_shelx_res_checksum              47893
_shelx_fab_checksum              32727
_olex2_submission_special_instructions 'No special instructions were received'