Regulating Ag-Cu synergy effect <i>via</i> Cu doping numbers to boost CO<sub>2</sub> electroreduction on Ag<sub>14</sub> nanoclusters.
Ma, Along; Ren, Yonggang; Zuo, Yang; Zhao, Jiaqi; Zhang, Shuo; Ma, Xiaoshuang; Wang, Shuxin; Chemical communications (Cambridge, England) 61 (2025) 10772–10775; doi:10.1039/d5cc02587g

data_7134735
_publ_section_title
;
 Regulating Ag-Cu synergy effect <i>via</i> Cu doping numbers to boost
 CO<sub>2</sub> electroreduction on Ag<sub>14</sub> nanoclusters.
;
_journal_issue                   58
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10772
_journal_page_last               10775
_journal_paper_doi               10.1039/d5cc02587g
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'C156 H84 Ag10 Cu4 F60 O12 P4 S12, 1[CH2Cl2], 3[CH3OH]'
_chemical_formula_sum            'C160 H98 Ag10 Cl2 Cu4 F60 O15 P4 S12'
_chemical_formula_weight         5312.74
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-31 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                89.531(2)
_cell_angle_beta                 89.166(2)
_cell_angle_gamma                85.539(2)
_cell_formula_units_Z            2
_cell_length_a                   18.7192(11)
_cell_length_b                   19.3113(13)
_cell_length_c                   25.7905(17)
_cell_measurement_reflns_used    9465
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.205
_cell_measurement_theta_min      2.368
_cell_volume                     9293.6(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            193338
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.907
_exptl_absorpt_coefficient_mu    1.790
_exptl_absorpt_correction_T_max  0.1137
_exptl_absorpt_correction_T_min  0.0825
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.899
_exptl_crystal_description       block
_exptl_crystal_F_000             5180
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.184
_refine_diff_density_min         -0.771
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2247
_refine_ls_number_reflns         32726
_refine_ls_number_restraints     4766
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0676P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24274
_reflns_number_total             32726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02587g2.cif
_cod_data_source_block           mal20241025a
_cod_depositor_comments
'Adding full bibliography for 7134735--7134737.cif.'
_cod_database_code               7134735
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.814
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O11-C73 = O13-C163
 1.45 with sigma of 0.001
 O7-C11 = O2-C153
 1.45 with sigma of 0.001
 C165-C163
 2.5 with sigma of 0.01
 O3-C159
 1.4 with sigma of 0.02
 C81-O3
 1.45 with sigma of 0.001
 O13-C165 = O11-C127
 1.4 with sigma of 0.001
3. Rigid bond restraints
 Ag11, S8
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 Cu4, S12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag3, S6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cu4, S9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag3, S10
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 Cu3, S8
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 Cu2, S10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C167 \\sim C21 \\sim C169 \\sim C41 \\sim C165 \\sim C83 \\sim O13 \\sim C163:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C151 \\sim C19 \\sim C147 \\sim C37 \\sim C149 \\sim C75: within 2A with sigma
of 0.001 and sigma for terminal atoms of 0.002 within 2A
C81 \\sim O3 \\sim C159 \\sim C79 \\sim C157 \\sim C39 \\sim C161 \\sim C5:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C77 \\sim O5 \\sim C151 \\sim C75 \\sim C149 \\sim C37 \\sim C147 \\sim C19:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
O11 \\sim C73 \\sim C127 \\sim C63 \\sim C125 \\sim C31 \\sim C129 \\sim C2:
within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C147, C19, C37, C151, C149, C75
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(Ag9)=Sof(O2)=Sof(C31)=Sof(H31)=Sof(C125)=Sof(H125)=Sof(C63)=Sof(H63)=
 Sof(C127)=Sof(C2)=Sof(H2)=Sof(C129)=Sof(O5)=Sof(C131)=Sof(H131)=Sof(C33)=
 Sof(C133)=Sof(H133)=Sof(C67)=Sof(C135)=Sof(H135)=Sof(C17)=Sof(H17)=Sof(O11)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C147)=Sof(C37)=Sof(H37)=Sof(C149)=
 Sof(H149)=Sof(C75)=Sof(H75)=Sof(C151)=Sof(C19)=Sof(H19)=Sof(C153)=Sof(H15A)=
 Sof(H15B)=Sof(H15C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(P2)=1-FVAR(1)
 Sof(P3)=Sof(C39)=Sof(H39)=Sof(C157)=Sof(H157)=Sof(C79)=Sof(H79)=Sof(C159)=
 Sof(C5)=Sof(H5)=Sof(C161)=Sof(O3)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 Sof(O13)=Sof(C163)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C41)=Sof(H41)=Sof(C165)=
 Sof(C83)=Sof(H83)=Sof(C167)=Sof(C21)=Sof(H21)=Sof(C169)=Sof(H169)=Sof(O7)=
 Sof(C85)=Sof(C171)=Sof(H171)=Sof(C43)=Sof(C173)=Sof(H173)=Sof(C87)=Sof(H87)=
 Sof(C175)=Sof(H175)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(Ag5)=FVAR(1)
7.a Riding coordinates:
 C153(H15A,H15B,H15C), C163(H16A,H16B,H16C)
7.b Aromatic/amide H refined with riding coordinates:
 C40(H40), C44(H44), C46(H46), C48(H48), C52(H52), C56(H56), C58(H58),
 C60(H60), C64(H64), C66(H66), C68(H68), C72(H72), C74(H74), C78(H78), C80(H80),
  C82(H82), C88(H88), C92(H92), C94(H94), C96(H96), C100(H100), C104(H104),
 C106(H106), C108(H108), C112(H112), C116(H116), C118(H118), C120(H120),
 C124(H124), C128(H128), C130(H130), C132(H132), C136(H136), C140(H140),
 C142(H142), C144(H144), C31(H31), C125(H125), C63(H63), C2(H2), C131(H131),
 C133(H133), C135(H135), C17(H17), C37(H37), C149(H149), C75(H75), C19(H19),
 C39(H39), C157(H157), C79(H79), C5(H5), C41(H41), C83(H83), C21(H21),
 C169(H169), C171(H171), C173(H173), C87(H87), C175(H175)
7.c Fitted hexagon refined as free rotating group:
 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), C115(C29,C117,C59,C119,C15), C31(C125,C63,C127,C2,C129), C131(C33,C133,
 C67,C135,C17), C139(C35,C141,C71,C143,C9), C147(C37,C149,C75,C151,C19),
 C39(C157,C79,C159,C5,C161), C41(C165,C83,C167,C21,C169), C85(C171,C43,C173,C87,
 C175)
7.d Idealised Me refined as rotating group:
 C57(H57A,H57B,H57C), C121(H12A,H12B,H12C), C61(H61A,H61B,H61C), C123(H12D,
 H12E,H12F), C65(H65A,H65B,H65C), C137(H13A,H13B,H13C), C69(H69A,H69B,H69C),
 C145(H14A,H14B,H14C), C73(H73A,H73B,H73C), C77(H77A,H77B,H77C), C155(H15D,H15E,
 H15F), C81(H81A,H81B,H81C), C11(H11A,H11B,H11C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 194 electrons were 
found in a volume of 1414\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CH2Cl2], 3[CH3OH] per formula unit 
which account for 192 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6612
_shelx_hkl_checksum              30139
_shelx_fab_checksum              95495
_olex2_submission_special_instructions 'No special instructions were received'