Construction of a homologous series of metal nanoclusters and implications for structure-activity correlations.
Li, Qinzhen; Jiang, Tingting; Yang, Sha; Chai, Jinsong; Yu, Haizhu; Zhu, Manzhou; Chemical science 16 (2025) 19669–19676; doi:10.1039/d5sc06282a

data_1575830
_publ_section_title
;
 Construction of a homologous series of metal nanoclusters and
 implications for structure-activity correlations.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              19669
_journal_page_last               19676
_journal_paper_doi               10.1039/d5sc06282a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C176 H238 Au22 Cd2 Cl2 O P2 S14, 5(C7 H8)'
_chemical_formula_sum            'C211 H278 Au22 Cd2 Cl2 O P2 S14'
_chemical_formula_weight         7970.06
_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             2024-08-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-08-22 deposited with the CCDC.	2025-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                96.568(2)
_cell_angle_beta                 92.621(2)
_cell_angle_gamma                91.671(2)
_cell_formula_units_Z            2
_cell_length_a                   17.6876(5)
_cell_length_b                   21.7743(6)
_cell_length_c                   30.2373(7)
_cell_measurement_reflns_used    36819
_cell_measurement_temperature    120
_cell_measurement_theta_max      70.14
_cell_measurement_theta_min      3.55
_cell_volume                     11550.0(5)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.953
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0776
_diffrn_reflns_av_unetI/netI     0.2296
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            79927
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        65.000
_diffrn_reflns_theta_max         65.000
_diffrn_reflns_theta_min         4.421
_exptl_absorpt_coefficient_mu    28.815
_exptl_crystal_density_diffrn    2.292
_exptl_crystal_description       block
_exptl_crystal_F_000             7348
_refine_diff_density_max         2.720
_refine_diff_density_min         -1.607
_refine_diff_density_rms         0.223
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.575
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2279
_refine_ls_number_reflns         37488
_refine_ls_number_restraints     1931
_refine_ls_restrained_S_all      0.564
_refine_ls_R_factor_all          0.0956
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17337
_reflns_number_total             37488
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06282a2.cif
_cod_data_source_block           au22cd2
_cod_depositor_comments
'Adding full bibliography for 1575828--1575830.cif.'
_cod_database_code               1575830
_shelx_shelxl_version_number     2017/1
_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
 H142_$1-H0BA
 2.2 with sigma of 0.01
3. Restrained planarity
 C13, C6, C7EA, C8EA
 with sigma of 0.1
4. Rigid bond restraints
 C3, C6, C13, C7EA, C5, C61, C8EA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C0EA \\sim C1EA \\sim C70 \\sim C2EA \\sim C3EA \\sim C93 \\sim C4EA \\sim C5EA
\\sim C6EA \\sim C100: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 1.7A
C39 \\sim C48 \\sim C66 \\sim C88 \\sim C96 \\sim C104 \\sim C152 \\sim C168
\\sim C183 \\sim C132: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 1.7A
C20 \\sim C35 \\sim C47 \\sim C77 \\sim C161 \\sim C89: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C16 \\sim C18 \\sim C26 \\sim C8DA \\sim C9DA \\sim C2FA \\sim C4FA \\sim C3FA
\\sim C5FA \\sim C6FA: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 1.7A
C30 \\sim C33 \\sim C36 \\sim C49 \\sim C51 \\sim C55 \\sim C65 \\sim C78 \\sim
C137 \\sim C177: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.008 within 1.7A
C29 \\sim C74 \\sim C94 \\sim C127 \\sim C140 \\sim C163: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C82 \\sim C115 \\sim C123 \\sim C164 \\sim C170 \\sim C198 \\sim C7BA \\sim
C8BA \\sim C9BA \\sim C42: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C59 \\sim C86 \\sim C153 \\sim C172 \\sim C179 \\sim C188 \\sim C101 \\sim C6BA
\\sim C126 \\sim C130: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 1.7A
C27 \\sim C31 \\sim C40 \\sim C60 \\sim C67 \\sim C79 \\sim C117 \\sim C174
\\sim C187 \\sim C7AA: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008 within 1.7A
C50 \\sim C106 \\sim C114 \\sim C148 \\sim C162 \\sim C8AA \\sim C9AA \\sim
C0BA \\sim C72 \\sim C158: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68)
\\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C82) \\sim Ueq,
Uanis(C86) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C99) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq,
Uanis(C109) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C114) \\sim Ueq,
Uanis(C115) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C123) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C127) \\sim Ueq,
Uanis(C128) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C135) \\sim Ueq,
Uanis(C137) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C142) \\sim Ueq,
Uanis(C147) \\sim Ueq, Uanis(C148) \\sim Ueq, Uanis(C152) \\sim Ueq,
Uanis(C153) \\sim Ueq, Uanis(C158) \\sim Ueq, Uanis(C159) \\sim Ueq,
Uanis(C160) \\sim Ueq, Uanis(C161) \\sim Ueq, Uanis(C162) \\sim Ueq,
Uanis(C163) \\sim Ueq, Uanis(C164) \\sim Ueq, Uanis(C167) \\sim Ueq,
Uanis(C168) \\sim Ueq, Uanis(C170) \\sim Ueq, Uanis(C172) \\sim Ueq,
Uanis(C173) \\sim Ueq, Uanis(C174) \\sim Ueq, Uanis(C175) \\sim Ueq,
Uanis(C177) \\sim Ueq, Uanis(C179) \\sim Ueq, Uanis(C180) \\sim Ueq,
Uanis(C182) \\sim Ueq, Uanis(C183) \\sim Ueq, Uanis(C185) \\sim Ueq,
Uanis(C187) \\sim Ueq, Uanis(C188) \\sim Ueq, Uanis(C190) \\sim Ueq,
Uanis(C196) \\sim Ueq, Uanis(C198) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C1BA)
\\sim Ueq, Uanis(C7BA) \\sim Ueq, Uanis(C2BA) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C3BA) \\sim Ueq, Uanis(C1CA) \\sim Ueq, Uanis(C1AA) \\sim Ueq,
Uanis(C4BA) \\sim Ueq, Uanis(C2AA) \\sim Ueq, Uanis(C6AA) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(C8AA) \\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C9AA) \\sim Ueq,
Uanis(C0AA) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C83)
\\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C5BA) \\sim Ueq, Uanis(C87) \\sim Ueq,
Uanis(C89) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C8BA) \\sim Ueq, Uanis(C5AA)
\\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C0CA) \\sim Ueq, Uanis(C101) \\sim Ueq,
Uanis(C7AA) \\sim Ueq, Uanis(C2CA) \\sim Ueq, Uanis(C9BA) \\sim Ueq,
Uanis(C0BA) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C6BA) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C130) \\sim Ueq, Uanis(C3CA) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C0DA)
\\sim Ueq, Uanis(C1DA) \\sim Ueq, Uanis(C2DA) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C4CA) \\sim Ueq, Uanis(C5CA) \\sim Ueq, Uanis(C9CA) \\sim Ueq,
Uanis(C6CA) \\sim Ueq, Uanis(C7CA) \\sim Ueq, Uanis(C8CA) \\sim Ueq,
Uanis(C3DA) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C8DA) \\sim Ueq, Uanis(C9DA) \\sim Ueq, Uanis(C4DA) \\sim Ueq,
Uanis(C5DA) \\sim Ueq, Uanis(C0EA) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C1EA)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C6DA) \\sim Ueq, Uanis(C2EA) \\sim Ueq,
Uanis(C7DA) \\sim Ueq, Uanis(C3EA) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C4EA)
\\sim Ueq, Uanis(C5EA) \\sim Ueq, Uanis(C6EA) \\sim Ueq, Uanis(C100) \\sim Ueq,
Uanis(C2FA) \\sim Ueq, Uanis(C4FA) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C7FA)
\\sim Ueq, Uanis(C3FA) \\sim Ueq, Uanis(C5FA) \\sim Ueq, Uanis(C6FA) \\sim Ueq,
Uanis(C8FA) \\sim Ueq, Uanis(C9FA) \\sim Ueq, Uanis(C7GA) \\sim Ueq,
Uanis(C8GA) \\sim Ueq, Uanis(C3GA) \\sim Ueq, Uanis(C0GA) \\sim Ueq,
Uanis(C6GA) \\sim Ueq, Uanis(C9GA) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C1GA)
\\sim Ueq, Uanis(C2GA) \\sim Ueq, Uanis(C5GA) \\sim Ueq, Uanis(C4GA) \\sim Ueq,
Uanis(C2HA) \\sim Ueq, Uanis(C0HA) \\sim Ueq, Uanis(C1HA) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C7EA) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C8EA) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
6.a Riding coordinates:
 C13(H13C,H13D,H13E)
6.b Ternary CH refined with riding coordinates:
 C48(H48), C60(H60), C65(H65), C67(H67), C71(H71), C72(H72), C88(H88),
 C90(H90), C117(H117), C118(H118), C128(H128), C137(H137), C142(H142),
 C147(H147), C159(H159), C160(H160), C168(H168), C170(H170), C177(H177),
 C188(H188), C196(H196), C2BA(H2BA), C38(H38), C4BA(H4BA), C8AA(H8AA),
 C8BA(H8BA), C9BA(H9BA), C0BA(H0BA), C111(H111), C126(H126), C130(H130),
 C7CA(H7CA), C8CA(H8CA), C18(H18), C63(H63), C3EA(H3EA), C93(H93), C5EA(H5EA),
 C3FA(H3FA), C5FA(H5FA), C2GA(H2GA), C4GA(H4GA)
6.c Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,
 H33B), C36(H36A,H36B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
 C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C46(H46A,H46B), C49(H49A,H49B),
  C51(H51A,H51B), C55(H55A,H55B), C66(H66A,H66B), C68(H68A,H68B), C69(H69A,
 H69B), C79(H79A,H79B), C86(H86A,H86B), C96(H96A,H96B), C97(H97A,H97B),
 C106(H10A,H10B), C107(H10C,H10D), C113(H11A,H11B), C114(H11C,H11D), C115(H11E,
 H11F), C120(H12A,H12B), C121(H12C,H12D), C123(H12E,H12F), C132(H13A,H13B),
 C148(H14C,H14D), C152(H15A,H15B), C153(H15C,H15D), C158(H15E,H15F), C162(H16A,
 H16B), C164(H16C,H16D), C172(H17A,H17B), C173(H17C,H17D), C174(H17E,H17F),
 C179(H17G,H17H), C180(H18A,H18B), C182(H18C,H18D), C183(H18E,H18F), C187(H18G,
 H18H), C190(H19A,H19B), C198(H19C,H19D), C7BA(H7BA,H7BB), C3BA(H3BA,H3BB),
 C2AA(H2AA,H2AB), C3AA(H3AA,H3AB), C9AA(H9AA,H9AB), C75(H75A,H75B), C4AA(H4AA,
 H4AB), C83(H83A,H83B), C5BA(H5BA,H5BB), C91(H91A,H91B), C5AA(H5AA,H5AB),
 C98(H98A,H98B), C101(H10E,H10F), C7AA(H7AA,H7AB), C110(H11G,H11H), C6BA(H6BA,
 H6BB), C4CA(H4CA,H4CB), C5CA(H5CA,H5CB), C9CA(H9CA,H9CB), C6CA(H6CA,H6CB),
 C26(H26A,H26B), C8DA(H8DA,H8DB), C9DA(H9DA,H9DB), C1EA(H1EA,H1EB), C70(H70A,
 H70B), C6DA(H6DA,H6DB), C2EA(H2EA,H2EB), C7DA(H7DA,H7DB), C4EA(H4EA,H4EB),
 C6EA(H6EA,H6EB), C100(H10G,H10H), C2FA(H2FA,H2FB), C4FA(H4FA,H4FB), C6FA(H6FA,
 H6FB), C3GA(H3GA,H3GB), C5GA(H5GA,H5GB)
6.d Aromatic/amide H refined with riding coordinates:
 C20(H20), C29(H29), C35(H35), C45(H45), C54(H54), C56(H56), C57(H57),
 C64(H64), C73(H73), C74(H74), C77(H77), C81(H81), C94(H94), C99(H99),
 C103(H103), C105(H105), C108(H108), C122(H122), C135(H135), C140(H140),
 C161(H161), C163(H163), C167(H167), C175(H175), C185(H185), C11(H11),
 C1CA(H1CA), C0AA(H0AA), C89(H89), C0CA(H0CA), C2CA(H2CA), C116(H116),
 C3CA(H3CA), C0DA(H0DA), C2DA(H2DA), C3DA(H3DA), C4DA(H4DA), C5DA(H5DA),
 C8FA(H8FA), C9FA(H9FA), C7GA(H7GA), C8GA(H8GA), C0GA(H0GA), C6GA(H6GA),
 C9GA(H9GA), C37(H37), C1GA(H1GA), C2HA(H2HA), C7EA(H7EA), C61(H61), C8EA(H8EA),
  C5(H5), C6(H6)
6.e Fitted hexagon refined as free rotating group:
 C3(C7EA,C61,C8EA,C5,C6)
6.f Idealised Me refined as rotating group:
 C84(H84A,H84B,H84C), C52(H52A,H52B,H52C), C23(H23A,H23B,H23C), C1HA(H1HA,H1HB,
 H1HC)
;
_shelx_res_checksum              54680
_shelx_fab_checksum              77238
_olex2_submission_special_instructions 'No special instructions were received'