Ligand-controlled exposure of active sites on the Pd<sub>1</sub>Ag<sub>14</sub> nanocluster surface to boost electrocatalytic CO<sub>2</sub> reduction.
Ma, Along; Ren, Yonggang; Zuo, Yang; Wang, Jiawei; Huang, Shutong; Ma, Xiaoshuang; Wang, Shuxin; Chemical communications (Cambridge, England) 60 (2024) 3162–3165; doi:10.1039/d4cc00152d

data_7132733
_publ_section_title
;
 Ligand-controlled exposure of active sites on the
 Pd<sub>1</sub>Ag<sub>14</sub> nanocluster surface to boost
 electrocatalytic CO<sub>2</sub> reduction.
;
_journal_issue                   23
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3162
_journal_page_last               3165
_journal_paper_doi               10.1039/d4cc00152d
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C183 H177 Ag14 O21 P7 Pd S6'
_chemical_formula_sum            'C183 H171 Ag14 O21 P7 Pd S6'
_chemical_formula_weight         4731.92
_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
_audit_creation_date             2024-01-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-01-10 deposited with the CCDC.	2024-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                82.006(16)
_cell_angle_beta                 74.854(18)
_cell_angle_gamma                84.149(17)
_cell_formula_units_Z            2
_cell_length_a                   19.457(14)
_cell_length_b                   20.805(15)
_cell_length_c                   27.840(19)
_cell_measurement_reflns_used    9283
_cell_measurement_temperature    170
_cell_measurement_theta_max      24.445
_cell_measurement_theta_min      2.192
_cell_volume                     10747(13)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2074
_diffrn_reflns_av_unetI/netI     0.1513
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            199150
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.914
_exptl_absorpt_coefficient_mu    1.488
_exptl_absorpt_correction_T_max  0.1512
_exptl_absorpt_correction_T_min  0.0538
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1631 before and 0.0969 after correction.
The Ratio of minimum to maximum transmission is 0.3558.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.462
_exptl_crystal_description       block
_exptl_crystal_F_000             4684
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.455
_refine_diff_density_min         -2.751
_refine_diff_density_rms         0.258
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1802
_refine_ls_number_reflns         37743
_refine_ls_number_restraints     3278
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.1750
_refine_ls_R_factor_gt           0.1038
_refine_ls_shift/su_max          0.052
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3052
_refine_ls_wR_factor_ref         0.3469
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18689
_reflns_number_total             37743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00152d2.cif
_cod_data_source_block           wsx0605c_0m
_cod_depositor_comments
'Adding full bibliography for 7132732--7132733.cif.'
_cod_database_code               7132733
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.890
_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
 C37-O14
 1.45 with sigma of 0.01
 O14-C54
 1.35 with sigma of 0.01
 O11-C20
 1.45 with sigma of 0.01
 O11-C38
 1.35 with sigma of 0.01
 O10-C130
 1.45 with sigma of 0.01
 O10-C147
 1.35 with sigma of 0.01
 C20-C38
 2.5 with sigma of 0.02
 O7-C67 = O7-C89
 1.45 with sigma of 0.01
 O14-C107
 1.45 with sigma of 0.01
 C46-C37
 2.8 with sigma of 0.02
 C121-C107
 2.8 with sigma of 0.02
 O2-C75
 1.45 with sigma of 0.01
 C32-C130
 2.8 with sigma of 0.02
 H37A-H46
 2.05 with sigma of 0.02
 H112-H60B
 2.05 with sigma of 0.01
 H72-H66C
 2.05 with sigma of 0.02
 H9-H23B
 2.05 with sigma of 0.02
 H14-H84B
 2.05 with sigma of 0.02
 H155-H51A
 2.05 with sigma of 0.02
 H145-H42B
 2.05 with sigma of 0.02
 H76A_$1-H51B_$2
 2.05 with sigma of 0.02
 C125-O11 \\sim O11-C126
 with sigma of 0.02
 C109-O4 \\sim O4-C160
 with sigma of 0.02
 C114-O10 \\sim O10-C32
 with sigma of 0.02
 H39B-H95 \\sim H95-H39A
 with sigma of 0.02
3. Restrained planarity
 O14, C15, C36, C46, C54, C83, C121
 with sigma of 0.1
 O11, C38, C49, C96, C125, C126
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
P5 \\sim C15 \\sim C83 \\sim C121 \\sim C54 \\sim C46 \\sim C36 \\sim O14 \\sim
C107 \\sim C37: within 3.8A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 3.8A
P3 \\sim C101 \\sim C31 \\sim C129 \\sim C47 \\sim O8 \\sim C66 \\sim C72 \\sim
C57: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3.8A
P7 \\sim C55 \\sim C85 \\sim C34 \\sim C29 \\sim O2 \\sim C75 \\sim C117 \\sim
C8: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3.8A
S3 \\sim C119 \\sim C25 \\sim C33 \\sim C78 \\sim C52 \\sim C48: within 3.8A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
P5 \\sim C26 \\sim C56 \\sim C79 \\sim C50 \\sim C9 \\sim C143 \\sim O3 \\sim
C23: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
3.8A
C74 \\sim S1 \\sim C133 \\sim C100 \\sim C106 \\sim C10 \\sim C146: within 3.8A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
C54 \\sim O14 \\sim C37 \\sim C107 \\sim C46 \\sim C36 \\sim C15 \\sim C83
\\sim C121: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C16 \\sim C49 \\sim C126 \\sim C38 \\sim O11 \\sim C20 \\sim C125 \\sim C96:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Ag4 \\sim P1 \\sim C173 \\sim C171 \\sim C110 \\sim C53 \\sim C112 \\sim C181
\\sim O12 \\sim C60 \\sim C69 \\sim C118 \\sim C6 \\sim C73 \\sim C59 \\sim
C124 \\sim O6 \\sim C63: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C128 \\sim C139 \\sim C155 \\sim C157 \\sim C134 \\sim C150 \\sim O5 \\sim C51:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C14 \\sim C97 \\sim C27 \\sim C43 \\sim C98 \\sim C105 \\sim O17 \\sim C84:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Fixed Sof: C37(0.5) H37A(0.5) H37B(0.5) H37C(0.5) C67(0.5) H67A(0.5)
 H67B(0.5) H67C(0.5) C89(0.5) H89A(0.5) H89B(0.5) H89C(0.5) C107(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5)
7.a Riding coordinates:
 C20(H20A,H20B,H20C), C75(H75A,H75B,H75C), C89(H89A,H89B,H89C), C107(H10A,H10B,
 H10C)
7.b Aromatic/amide H refined with riding coordinates:
 C109(H109), C148(H148), C162(H162), C160(H160), C117(H117), C8(H8), C85(H85),
 C34(H34), C30(H30), C142(H142), C120(H120), C18(H18), C7(H7), C129(H129),
 C31(H31), C57(H57), C72(H72), C52(H52), C78(H78), C33(H33), C25(H25), C48(H48),
  C56(H56), C79(H79), C9(H9), C143(H143), C58(H58), C22(H22), C28(H28),
 C65(H65), C81(H81), C137(H137), C149(H149), C151(H151), C45(H45), C77(H77),
 C94(H94), C21(H21), C92(H92), C145(H145), C136(H136), C153(H153), C95(H95),
 C138(H138), C13(H13), C164(H164), C14(H14), C27(H27), C43(H43), C98(H98),
 C106(H106), C100(H100), C133(H133), C146(H146), C10(H10), C108(H108),
 C159(H159), C174(H174), C170(H170), C110(H110), C171(H171), C181(H181),
 C112(H112), C118(H118), C124(H124), C59(H59), C6(H6), C121(H121), C83(H83),
 C36(H36), C46(H46), C122(H122), C64(H64), C2(H2), C123(H123), C82(H82),
 C125(H125), C96(H96), C49(H49), C126(H126), C102(H102), C62(H62), C12(H12),
 C99(H99), C134(H134), C150(H150), C139(H139), C155(H155), C140(H140), C80(H80),
  C154(H154), C152(H152), C156(H156), C172(H172), C71(H71), C4(H4), C90(H90),
 C166(H166), C178(H178), C175(H175), C179(H179), C167(H167), C180(H180),
 C183(H183), C158(H158), C111(H111), C182(H182), C88(H88), C44(H44), C35(H35),
 C186(H186), C165(H165), C32(H32), C114(H114)
7.c Fitted hexagon refined as free rotating group:
 C5(C109,C148,C19,C162,C160), C29(C117,C8,C55,C85,C34), C30(C24,C142,C120,C18,
 C7), C47(C129,C31,C101,C57,C72), C52(C78,C33,C25,C119,C48), C56(C79,C50,C9,
 C143,C26), C70(C58,C22,C68,C28,C65), C81(C135,C137,C149,C127,C151), C91(C45,
 C77,C17,C94,C21), C92(C103,C145,C136,C141,C153), C95(C138,C115,C13,C164,C185),
 C105(C14,C27,C97,C43,C98), C106(C100,C74,C133,C146,C10), C108(C161,C159,C174,
 C168,C170), C110(C171,C173,C181,C112,C53), C118(C69,C124,C59,C73,C6), C121(C83,
 C15,C36,C46,C54), C122(C64,C2,C86,C123,C82), C125(C96,C16,C49,C126,C38),
 C132(C102,C62,C144,C12,C99), C134(C150,C128,C139,C155,C157), C140(C80,C116,
 C154,C152,C156), C163(C172,C71,C169,C4,C90), C176(C166,C178,C175,C179,C167),
 C177(C180,C183,C113,C158,C111), C184(C182,C88,C11,C44,C35), C186(C104,C165,C32,
 C147,C114)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C23(H23A,H23B,H23C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C51(H51A,H51B,
 H51C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C66(H66A,
 H66B,H66C), C76(H76A,H76B,H76C), C84(H84A,H84B,H84C), C93(H93A,H93B,H93C),
 C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C37(H37A,H37B,H37C), C67(H67A,H67B,
 H67C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              95867
_shelx_hkl_checksum              2725
_shelx_fab_checksum              57823
_olex2_submission_special_instructions 'No special instructions were received'