Ag<sup>1+</sup> incorporation <i>via</i> a Zr<sup>4+</sup>-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCO<sub>2</sub>RR-to-CO activity.
Li, Liang-Jun; Mu, Wen-Lei; Tian, Yi-Qi; Yu, Wei-Dong; Li, Lan-Yan; Yan, Jun; Liu, Chao; Chemical science 15 (2024) 7643–7650; doi:10.1039/d3sc07005k

data_1571293
_publ_section_title
;
 Ag<sup>1+</sup> incorporation <i>via</i> a Zr<sup>4+</sup>-anchored
 metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic
 clusters for enhanced eCO<sub>2</sub>RR-to-CO activity.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              7643
_journal_page_last               7650
_journal_paper_doi               10.1039/d3sc07005k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '2(C87 H92 Ag3 O11 S8 Zr)'
_chemical_formula_sum            'C174 H184 Ag6 O22 S16 Zr2'
_chemical_formula_weight         3969.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-07-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-25 deposited with the CCDC.	2024-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.152(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.2954(4)
_cell_length_b                   42.6550(9)
_cell_length_c                   26.1848(5)
_cell_measurement_reflns_used    76420
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      56.6720
_cell_measurement_theta_min      1.8580
_cell_volume                     22468.6(8)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            39326
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        52.982
_diffrn_reflns_theta_max         52.982
_diffrn_reflns_theta_min         2.113
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    4.467
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       block
_exptl_crystal_F_000             8088
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.485
_refine_diff_density_min         -1.058
_refine_diff_density_rms         0.174
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1933
_refine_ls_number_reflns         39326
_refine_ls_number_restraints     2156
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.1801
_refine_ls_R_factor_gt           0.1535
_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^)+(0.0500P)^2^+120.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3093
_refine_ls_wR_factor_ref         0.3258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                28277
_reflns_number_total             39326
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc07005k2.cif
_cod_data_source_block           ZrAg3
_cod_depositor_comments
'Adding full bibliography for 1571291--1571294.cif.'
_cod_database_code               1571293
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.47(2)
 0.53(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C150-C170 = C150-C145 = C150-C146 = C9-C96 = C71-C96 = C69-C96 = C168-C174 =
 C162-C174 = C45-C174 = C63-C144 = C143-C144 = C144-C148 = C154-C172 = C108-
 C154 = C161-C154 = C140-C90 = C100-C90 = C158-C90 = C147-C152 = C113-C152 =
 C105-C152 = C138-C43 = C171-C138 = C173-C138 = C165-C163 = C41-C163 = C83-C163
 = C167-C85 = C167-C169 = C167-C21 = C160-C139 = C139-C137 = C142-C139 = C15-
 C98 = C176-C98 = C103-C98 = C123-C38 = C86-C38 = C106-C38 = C127-C117 = C37-
 C117 = C117-C73 = C23-C141 = C29-C23 = C35-C23 = C166-C164 = C81-C164 = C31-
 C164
 1.5 with sigma of 0.02
 C156-C134
 1.5 with sigma of 0.02
 O17-C156 = C156-O21
 1.25 with sigma of 0.02
 C19-C167 = C23-C109 = C79-C139 = C90-C89 = C154-C49 = C152-C2 = C164-C136 =
 C163-C118 = C138-C58 = C144-C129 = C98-C61 = C38-C28 = C96-C84 = C174-C88 =
 C150-C131
 1.5 with sigma of 0.02
 H8-H15B
 2.1 with sigma of 0.02
 H14D-H55
 2.1 with sigma of 0.02
 H51-H12D
 2.1 with sigma of 0.02
 H78-H14Q
 2.1 with sigma of 0.02
 O17-O21
 2.165 with sigma of 0.04
 C146-C170 \\sim C146-C131 \\sim C146-C145 \\sim C170-C131 \\sim C170-C145
\\sim C131-C145
 with sigma of 0.04
 C154-C172 \\sim C154-C49 \\sim C154-C161 \\sim C154-C108
 with sigma of 0.02
 C176-C103 \\sim C176-C15 \\sim C103-C15 \\sim C87-C175 \\sim C87-C11 \\sim
C175-C11
 with sigma of 0.04
 C172-C49 \\sim C172-C161 \\sim C172-C108 \\sim C49-C161 \\sim C49-C108 \\sim
C161-C108
 with sigma of 0.04
 C98-C176 \\sim C98-C103 \\sim C98-C15 \\sim C98-C61 \\sim C98-C87 \\sim
C98-C175 \\sim C98-C11
 with sigma of 0.02
 C150-C146 \\sim C150-C170 \\sim C150-C131 \\sim C150-C145
 with sigma of 0.02
 C109-C29 \\sim C109-C35 \\sim C109-C141 \\sim C29-C35 \\sim C29-C141 \\sim
C35-C141
 with sigma of 0.04
 C23-C109 \\sim C23-C29 \\sim C23-C35 \\sim C23-C141
 with sigma of 0.02
 C19-C21 \\sim C19-C169 \\sim C19-C85 \\sim C21-C169 \\sim C21-C85 \\sim
C169-C85
 with sigma of 0.04
 C167-C19 \\sim C167-C21 \\sim C167-C169 \\sim C167-C85
 with sigma of 0.02
 C118-C41 \\sim C118-C165 \\sim C118-C83 \\sim C41-C165 \\sim C41-C83 \\sim
C165-C83
 with sigma of 0.04
 C163-C118 \\sim C163-C41 \\sim C163-C165 \\sim C163-C83
 with sigma of 0.02
 C127-C73 \\sim C127-C37 \\sim C127-C20 \\sim C73-C37 \\sim C73-C20 \\sim
C37-C20
 with sigma of 0.04
 C176-C103 \\sim C176-C15 \\sim C176-C61 \\sim C103-C15 \\sim C103-C61 \\sim
C15-C61
 with sigma of 0.04
 C84-C69 \\sim C84-C71 \\sim C84-C9 \\sim C69-C71 \\sim C69-C9 \\sim C71-C9
 with sigma of 0.04
 C148-C63 \\sim C148-C129 \\sim C148-C143 \\sim C63-C143
 with sigma of 0.04
 C105-C113 \\sim C105-C2 \\sim C105-C147 \\sim C113-C2 \\sim C113-C147 \\sim
C2-C147
 with sigma of 0.04
 C28-C86 \\sim C28-C106 \\sim C28-C123 \\sim C86-C106 \\sim C86-C123 \\sim
C106-C123
 with sigma of 0.04
 C162-C168 \\sim C162-C45 \\sim C162-C88 \\sim C168-C45 \\sim C168-C88 \\sim
C45-C88
 with sigma of 0.04
 C100-C140 \\sim C100-C158 \\sim C100-C89 \\sim C140-C158 \\sim C140-C89 \\sim
C158-C89
 with sigma of 0.04
 C58-C171 \\sim C58-C43 \\sim C58-C173 \\sim C171-C43 \\sim C171-C173 \\sim
C43-C173
 with sigma of 0.04
 C90-C100 \\sim C90-C140 \\sim C90-C158 \\sim C90-C89
 with sigma of 0.02
 C138-C58 \\sim C138-C171 \\sim C138-C43 \\sim C138-C173
 with sigma of 0.02
 C152-C105 \\sim C152-C113 \\sim C152-C2 \\sim C152-C147
 with sigma of 0.02
 C139-C160 \\sim C139-C137 \\sim C139-C79 \\sim C139-C142
 with sigma of 0.02
 C144-C148 \\sim C144-C63 \\sim C144-C129 \\sim C144-C143
 with sigma of 0.02
 C98-C176 \\sim C98-C103 \\sim C98-C15 \\sim C98-C61
 with sigma of 0.02
 C38-C28 \\sim C38-C86 \\sim C38-C106 \\sim C38-C123
 with sigma of 0.02
 C117-C127 \\sim C117-C73 \\sim C117-C37 \\sim C117-C20
 with sigma of 0.02
 C166-C31 \\sim C166-C81 \\sim C166-C136 \\sim C31-C81 \\sim C31-C136 \\sim
C81-C136
 with sigma of 0.04
 C174-C162 \\sim C174-C168 \\sim C174-C45 \\sim C174-C88
 with sigma of 0.02
 C164-C166 \\sim C164-C31 \\sim C164-C81 \\sim C164-C136
 with sigma of 0.02
 C96-C84 \\sim C96-C69 \\sim C96-C71 \\sim C96-C9
 with sigma of 0.02
 C160-C137 \\sim C160-C79 \\sim C160-C142 \\sim C137-C79 \\sim C137-C142 \\sim
C79-C142
 with sigma of 0.04
4. Restrained planarity
 O17, O9, O21, C124, C126, C128, C130, C132, C134, C156
 with sigma of 0.1
5. Rigid bond restraints
 C1, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32,
 C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, C60, C62, C64,
  C66, C68, C70, C72, C74, C76, C78, C80, C82, C84, C86, C88, C90, C92, C94,
 C96, C98, C100, C102, C104, C106, C108, C110, C112, C114, C116, C118, C120,
 C122, C124, C126, C128, C130, C132, C134, C136, C138, C140, C142, C144, C146,
 C148, C150, C152, C154, C156, C158, C160, C162, C164, C166, C168, C170, C172,
 C174, C176, C177, C89, C45, C91, C23, C93, C47, C95, C3, C97, C49, C99, C25,
 C101, C51, C103, C13, C105, C53, C107, C27, C109, C55, C111, C7, C113, C57,
 C115, C29, C117, C59, C119, C15, C121, C61, C123, C31, C125, C63, C127, C2,
 C129, C65, C131, C33, C133, C67, C135, C17, C137, C69, C139, C35, C141, C71,
 C143, C9, C145, C73, C147, C37, C149, C75, C151, C19, C153, C77, C155, C39,
 C157, C79, C159, C5, C161, C81, C163, C41, C165, C83, C167, C21, C169, C85,
 C171, C43, C173, C87, C175, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O9, C124, C134, C128, C130, C132, O21, O17, C156, C126
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.02
 C37, C117, C73, C127
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C164, C166, C81, C31, C136, C1, C119, C94, C104, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C6 \\sim C8 \\sim C10 \\sim C12 \\sim C14 \\sim C16 \\sim C18
\\sim C20 \\sim C22 \\sim C24 \\sim C26 \\sim C28 \\sim C30 \\sim C32 \\sim C34
\\sim C36 \\sim C38 \\sim C40 \\sim C42 \\sim C44 \\sim C46 \\sim C48 \\sim C50
\\sim C52 \\sim C54 \\sim C56 \\sim C58 \\sim C60 \\sim C62 \\sim C64 \\sim C66
\\sim C68 \\sim C70 \\sim C72 \\sim C74 \\sim C76 \\sim C78 \\sim C80 \\sim C82
\\sim C84 \\sim C86 \\sim C88 \\sim C90 \\sim C92 \\sim C94 \\sim C96 \\sim C98
\\sim C100 \\sim C102 \\sim C104 \\sim C106 \\sim C108 \\sim C110 \\sim C112
\\sim C114 \\sim C116 \\sim C118 \\sim C120 \\sim C122 \\sim C124 \\sim C126
\\sim C128 \\sim C130 \\sim C132 \\sim C134 \\sim C136 \\sim C138 \\sim C140
\\sim C142 \\sim C144 \\sim C146 \\sim C148 \\sim C150 \\sim C152 \\sim C154
\\sim C156 \\sim C158 \\sim C160 \\sim C162 \\sim C164 \\sim C166 \\sim C168
\\sim C170 \\sim C172 \\sim C174 \\sim C176 \\sim C177 \\sim C89 \\sim C45
\\sim C91 \\sim C23 \\sim C93 \\sim C47 \\sim C95 \\sim C3 \\sim C97 \\sim C49
\\sim C99 \\sim C25 \\sim C101 \\sim C51 \\sim C103 \\sim C13 \\sim C105 \\sim
C53 \\sim C107 \\sim C27 \\sim C109 \\sim C55 \\sim C111 \\sim C7 \\sim C113
\\sim C57 \\sim C115 \\sim C29 \\sim C117 \\sim C59 \\sim C119 \\sim C15 \\sim
C121 \\sim C61 \\sim C123 \\sim C31 \\sim C125 \\sim C63 \\sim C127 \\sim C2
\\sim C129 \\sim C65 \\sim C131 \\sim C33 \\sim C133 \\sim C67 \\sim C135 \\sim
C17 \\sim C137 \\sim C69 \\sim C139 \\sim C35 \\sim C141 \\sim C71 \\sim C143
\\sim C9 \\sim C145 \\sim C73 \\sim C147 \\sim C37 \\sim C149 \\sim C75 \\sim
C151 \\sim C19 \\sim C153 \\sim C77 \\sim C155 \\sim C39 \\sim C157 \\sim C79
\\sim C159 \\sim C5 \\sim C161 \\sim C81 \\sim C163 \\sim C41 \\sim C165 \\sim
C83 \\sim C167 \\sim C21 \\sim C169 \\sim C85 \\sim C171 \\sim C43 \\sim C173
\\sim C87 \\sim C175 \\sim C11: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O17 \\sim C156 \\sim O21 \\sim C134 \\sim C130 \\sim C128 \\sim C126 \\sim C124
\\sim O9 \\sim C132: within 2A with sigma of 0.001 and sigma for terminal atoms
of 0.01 within 2A
O1 \\sim C112 \\sim C110 \\sim C118 \\sim C116 \\sim C114 \\sim C163 \\sim C165
\\sim C41 \\sim C83: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C73 \\sim C117 \\sim C37 \\sim C127: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O19 \\sim C64 \\sim C66 \\sim C62: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C43) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C173) \\sim Ueq, Uanis(C171)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C164) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C166)
\\sim Ueq, Uanis(C136) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(C104) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C123)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C167) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C169)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C96) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C69)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
7. Others
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=Sof(C175)=Sof(H17J)=Sof(H17K)=
 Sof(H17L)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(1)
 Sof(C176)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C103)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Fixed X: C146(0.296909) C170(0.35019) C145(0.378921)
 Fixed Y: C146(0.51293) C170(0.46217) C145(0.5074)
 Fixed Z: C146(0.01423) C170(0.011311) C145(-0.03113)
8.a Riding coordinates:
 C108(H10J,H10K,H10L), C146(H14J,H14K,H14L), C170(H17M,H17N,H17O), C172(H17P,
 H17Q,H17R), C35(H35A,H35B,H35C), C145(H14S,H14T,H14U), C165(H16M,H16N,H16O),
 C21(H21A,H21B,H21C), C169(H16P,H16Q,H16R), C87(H87A,H87B,H87C), C175(H17J,H17K,
 H17L)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C8(H8), C12(H12), C18(H18), C22(H22), C24(H24), C30(H30), C32(H32),
 C42(H42), C44(H44), C46(H46), C48(H48), C52(H52), C56(H56), C60(H60), C70(H70),
  C76(H76), C78(H78), C116(H116), C120(H120), C122(H122), C126(H126),
 C128(H128), C130(H130), C132(H132), C177(H177), C91(H91), C97(H97), C99(H99),
 C51(H51), C27(H27), C55(H55), C119(H119), C125(H125), C33(H33), C17(H17),
 C151(H151), C153(H153), C157(H157), C159(H159)
8.c Fitted hexagon refined as free rotating group:
 C40(C42,C44,C46,C48,C50), C56(C58,C60,C62,C64,C66), C110(C112,C114,C116,C118,
 C120), C124(C126,C128,C130,C132,C134), C95(C3,C97,C49,C99,C25), C53(C107,C27,
 C109,C55,C111), C131(C33,C133,C67,C135,C17), C149(C75,C151,C19,C153,C77),
 C155(C39,C157,C79,C159,C5)
8.d Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C100(H10D,H10E,H10F), C106(H10G,H10H,H10I), C140(H14G,
 H14H,H14I), C142(H14A,H14B,H14C), C148(H14M,H14N,H14O), C158(H15D,H15E,H15F),
 C160(H16A,H16B,H16C), C162(H16D,H16E,H16F), C166(H16G,H16H,H16I), C168(H16J,
 H16K,H16L), C176(H17A,H17B,H17C), C45(H45A,H45B,H45C), C103(H10A,H10B,H10C),
 C105(H10M,H10N,H10O), C113(H11D,H11E,H11F), C29(H29A,H29B,H29C), C15(H15A,H15B,
 H15C), C123(H12A,H12B,H12C), C31(H31A,H31B,H31C), C63(H63A,H63B,H63C),
 C127(H12D,H12E,H12F), C137(H13A,H13B,H13C), C69(H69A,H69B,H69C), C141(H14D,
 H14E,H14F), C71(H71A,H71B,H71C), C143(H14P,H14Q,H14R), C9(H9A,H9B,H9C),
 C73(H73A,H73B,H73C), C147(H14V,H14W,H14X), C37(H37A,H37B,H37C), C161(H16S,H16T,
 H16U), C81(H81A,H81B,H81C), C41(H41A,H41B,H41C), C83(H83A,H83B,H83C), C85(H85A,
 H85B,H85C), C171(H17D,H17E,H17F), C43(H43A,H43B,H43C), C173(H17G,H17H,H17I),
 C11(H11A,H11B,H11C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19692
_shelx_fab_checksum              10689
_olex2_submission_special_instructions 'No special instructions were received'