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_7134737
_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 Ag12 Cu2 F60 O12 P4 S12, 3[CH2Cl2], 6.5[CH3OH]'
_chemical_formula_sum            'C165.5 H116 Ag12 Cl6 Cu2 F60 O18.5 P4 S12'
_chemical_formula_weight         5683.40
_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     iterative
_audit_creation_date             2024-12-22
_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                89.783(2)
_cell_angle_beta                 88.6660(10)
_cell_angle_gamma                87.6930(10)
_cell_formula_units_Z            2
_cell_length_a                   18.7706(7)
_cell_length_b                   19.9187(9)
_cell_length_c                   25.5916(12)
_cell_measurement_reflns_used    9513
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.733
_cell_measurement_theta_min      2.194
_cell_volume                     9558.0(7)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      170
_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  0.0683
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            327789
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         1.948
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.784
_exptl_absorpt_correction_T_max  0.1159
_exptl_absorpt_correction_T_min  0.0737
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1439 before and 0.0587 after correction.
The Ratio of minimum to maximum transmission is 0.6549.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic yellowish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.975
_exptl_crystal_description       block
_exptl_crystal_F_000             5546
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.140
_refine_diff_density_min         -1.444
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2338
_refine_ls_number_reflns         39570
_refine_ls_number_restraints     4061
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0628
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0628P)^2^+9.9888P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1242
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29435
_reflns_number_total             39570
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02587g2.cif
_cod_data_source_block           mal20241108a
_cod_depositor_comments
'Adding full bibliography for 7134735--7134737.cif.'
_cod_original_formula_sum        'C165.50 H116 Ag12 Cl6 Cu2 F60 O18.50 P4 S12'
_cod_database_code               7134737
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.842
_shelx_estimated_absorpt_t_min   0.717
_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. Shared sites
{Ag13, Cu13}
{Ag12, Cu12}
{Ag2, Cu2}
{Ag14, Cu14}
3. Rigid bond restraints
 Ag7, S2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag9, S10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag9, S11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ag11, S3
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 Ag11, S8
 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
Uanis(Ag13) = Uanis(Cu13)
Uanis(Ag12) = Uanis(Cu12)
Uanis(Ag2) = Uanis(Cu2)
Uanis(Ag14) = Uanis(Cu14)
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
6. Others
 1*[Sof(Ag13)+Sof(Cu13)]+1*[Sof(Ag12)+Sof(Cu12)]+1*[Sof(Ag2)+Sof(Cu2)]+1*
 [Sof(Ag14)+Sof(Cu14)]=2 with esd of 0.0001
 Sof(Cu13)=1-FVAR(1)
 Sof(Ag13)=FVAR(1)
 Sof(Cu12)=1-FVAR(2)
 Sof(Ag12)=FVAR(2)
 Sof(Cu2)=1-FVAR(3)
 Sof(Ag2)=FVAR(3)
 Sof(Cu14)=1-FVAR(4)
 Sof(Ag14)=FVAR(4)
7.a Riding coordinates:
 C19(H19A,H19B,H19C)
7.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C38(H38), C50(H50), C62(H62), C64(H64), C80(H80), C86(H86),
 C94(H94), C96(H96), C108(H108), C114(H114), C124(H124), C126(H126), C132(H132),
  C138(H138), C148(H148), C79(H79), C81(H81), C41(H41), C21(H21), C43(H43),
 C45(H45), C91(H91), C23(H23), C103(H103), C105(H105), C55(H55), C7(H7),
 C113(H113), C115(H115), C59(H59), C119(H119), C61(H61), C31(H31), C125(H125),
 C63(H63), C65(H65), C131(H131), C17(H17), C143(H143), C73(H73), C147(H147),
 C37(H37), C149(H149), C151(H151), C153(H153), C77(H77), C155(H155)
7.c Idealised Me refined as rotating group:
 C100(H10A,H10B,H10C), C83(H83A,H83B,H83C), C89(H89A,H89B,H89C), C49(H49A,H49B,
 H49C), C99(H99A,H99B,H99C), C57(H57A,H57B,H57C), C129(H12A,H12B,H12C),
 C35(H35A,H35B,H35C), C9(H9A,H9B,H9C), C145(H14A,H14B,H14C), C75(H75A,H75B,H75C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 486 electrons were 
found in a volume of 1792\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[CH2Cl2], 6.5[CH3OH] per formula unit 
which account for 486 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              64327
_shelx_hkl_checksum              2210
_shelx_fab_checksum              68862
_olex2_submission_special_instructions 'No special instructions were received'