Constructing perfect cubic Ag-Cu alloyed nanoclusters through selective elimination of phosphine ligands.
Tang, Li; Han, Qikai; Wang, Bin; Yang, Zhonghua; Song, Chunyuan; Feng, Guanyu; Wang, Shuxin; Physical chemistry chemical physics : PCCP 26 (2023) 62–66; doi:10.1039/d3cp04224c

data_7247854
_publ_section_title
;
 Constructing perfect cubic Ag-Cu alloyed nanoclusters through selective
 elimination of phosphine ligands.
;
_journal_issue                   1
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              62
_journal_page_last               66
_journal_paper_doi               10.1039/d3cp04224c
_journal_volume                  26
_journal_year                    2023
_chemical_formula_moiety
'C197 H229 Ag55 Cu8 I12 S24, C24 H20 P, 1[C6H14], 0.88[C6H14], 2.64[CH2Cl2]'
_chemical_formula_sum            'C216 H236 Ag55 Cu8 I12 P S24'
_chemical_formula_weight         11596.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-11-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-28 deposited with the CCDC.	2023-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 125.295(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   37.341(5)
_cell_length_b                   24.083(3)
_cell_length_c                   22.341(3)
_cell_measurement_reflns_used    7792
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.297
_cell_measurement_theta_min      2.220
_cell_volume                     16398(4)
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker D8'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0635
_diffrn_reflns_av_unetI/netI     0.0935
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            35734
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.389
_diffrn_reflns_theta_min         2.042
_exptl_absorpt_coefficient_mu    5.023
_exptl_absorpt_correction_T_max  0.0170
_exptl_absorpt_correction_T_min  0.0024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1399 before and 0.0744 after correction.
The Ratio of minimum to maximum transmission is 0.4643.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.349
_exptl_crystal_description       block
_exptl_crystal_F_000             10768
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.130
_refine_diff_density_min         -0.785
_refine_diff_density_rms         0.194
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.925
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1162
_refine_ls_number_reflns         16890
_refine_ls_number_restraints     3224
_refine_ls_restrained_S_all      0.872
_refine_ls_R_factor_all          0.1541
_refine_ls_R_factor_gt           0.0710
_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^)+(0.1276P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1992
_refine_ls_wR_factor_ref         0.2576
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6916
_reflns_number_total             16890
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cp04224c2.cif
_cod_data_source_block           wsx0606a_0m
_cod_depositor_comments          'Adding full bibliography for 7247854.cif.'
_cod_database_code               7247854
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.720
_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
 C31-C89
 1.45 with sigma of 0.01
 C111-C25
 1.45 with sigma of 0.01
 C92-C53
 1.45 with sigma of 0.01
 C58-C17
 1.45 with sigma of 0.01
 C86-C70 = C88-C79
 1.45 with sigma of 0.01
 C39-C81
 1.45 with sigma of 0.01
 C112-C66 = C113-C43
 1.45 with sigma of 0.01
 S00S-C55
 1.75 with sigma of 0.01
 C64-C67
 1.45 with sigma of 0.01
 C40-C114 = C41-C24
 1.45 with sigma of 0.01
 C77-C74
 1.45 with sigma of 0.01
 C90-C20 = C19-C21 = C21-C3
 1.37 with sigma of 0.02
 C90-C3
 1.38 with sigma of 0.02
 C20-C26 = C26-C19
 1.36 with sigma of 0.02
 C27-C45
 1.45 with sigma of 0.01
 C68-C95
 1.45 with sigma of 0.01
 S6-C16
 1.8 with sigma of 0.01
 C35-C54 = C28-C37
 1.45 with sigma of 0.01
 S1-C62
 1.8 with sigma of 0.02
 S2-C61
 1.8 with sigma of 0.01
 C63-C75
 1.45 with sigma of 0.01
 C14-C76
 1.45 with sigma of 0.01
 C2-C83 = C83-C1
 1.36 with sigma of 0.02
 C36-C2 = C1-C93 = C93-C98
 1.37 with sigma of 0.02
 C36-C98
 1.38 with sigma of 0.02
 C40_$1-C114_$1
 1.45 with sigma of 0.01
 C90-C26 = C26-C21 = C19-C3
 2.37 with sigma of 0.04
 C90-C21
 2.38 with sigma of 0.04
 C20-C19
 2.36 with sigma of 0.04
 C2-C1
 2.36 with sigma of 0.04
 C36-C83 = C83-C93 = C1-C98
 2.37 with sigma of 0.04
 C36-C93
 2.38 with sigma of 0.04
 C109-S00U \\sim S00U-C92
 with sigma of 0.02
 C110-C111 \\sim C111-C33
 with sigma of 0.02
 C33-C53 \\sim C53-C65
 with sigma of 0.02
 C99-C31 \\sim C31-C69
 with sigma of 0.02
 C46-C58 \\sim C58-C15
 with sigma of 0.02
 C107-C57 \\sim C57-C23
 with sigma of 0.02
 C23-C59 \\sim C59-C22
 with sigma of 0.02
 C73-S00U \\sim S00U-C67
 with sigma of 0.02
 C108-C86 \\sim C86-C72
 with sigma of 0.02
 C72-C79 \\sim C79-C85
 with sigma of 0.02
 C78-C77 \\sim C77-C60
 with sigma of 0.02
 C15-C81 \\sim C81-C52
 with sigma of 0.02
 C104-C113 \\sim C113-C50
 with sigma of 0.02
 C50-C112 \\sim C112-C87
 with sigma of 0.02
 C18-S00S \\sim S00S-C41
 with sigma of 0.02
 C62-C64 \\sim C64-C60
 with sigma of 0.02
 C103-C40 \\sim C40-C102
 with sigma of 0.02
 C102-C24 \\sim C24-C55
 with sigma of 0.02
 C60-C77 \\sim C77-C78
 with sigma of 0.02
 C90-C20 \\sim C20-C26 \\sim C26-C19 \\sim C19-C21 \\sim C21-C3 \\sim C3-C90
 with sigma of 0.02
 C90-C21 \\sim C90-C26 \\sim C21-C26 \\sim C19-C20 \\sim C19-C3 \\sim C3-C20
 with sigma of 0.04
 C26-P \\sim P-C21
 with sigma of 0.02
 C94-C27 \\sim C27-C56
 with sigma of 0.02
 C94-C95 \\sim C95-C38
 with sigma of 0.02
 C54-S6 \\sim S6-C97
 with sigma of 0.02
 C4-C28 \\sim C28-C6
 with sigma of 0.02
 C4-C35 \\sim C35-C16
 with sigma of 0.02
 C67-S1 \\sim S1-C73
 with sigma of 0.02
 C61-C75 \\sim C75-C105
 with sigma of 0.02
 C14-C100 \\sim C100-C105
 with sigma of 0.02
 C36-C93 \\sim C36-C83 \\sim C93-C83 \\sim C1-C2 \\sim C1-C98 \\sim C98-C2
 with sigma of 0.04
 C83-P \\sim P-C93
 with sigma of 0.02
 C36-C2 \\sim C2-C83 \\sim C83-C1 \\sim C1-C93 \\sim C93-C98 \\sim C98-C36
 with sigma of 0.02
3. Restrained planarity
 C25, C33, C65, C92, C109, C110, C111
 with sigma of 0.1
 S00P, C15, C17, C39, C46, C48, C52
 with sigma of 0.1
 C31, C51, C69, C80, C84, C89, C96, C99
 with sigma of 0.1
 C70, C72, C79, C82, C85, C86, C88, C108
 with sigma of 0.1
 C25, C33, C53, C65, C92, C109, C110, C111
 with sigma of 0.1
 C15, C17, C39, C52, C81
 with sigma of 0.1
 C43, C50, C66, C87, C104, C106, C112, C113
 with sigma of 0.1
 C18, C41, C55, C102, C103, C114, S00S
 with sigma of 0.1
 C60, C62, C67, C73, C74, C77, C78
 with sigma of 0.1
 C60, C62, C64, C67
 with sigma of 0.1
 C24, C40, C41, C102, C114
 with sigma of 0.1
 C60, C74, C77, C78
 with sigma of 0.1
 C3, C19, C20, C21, C26, C90
 with sigma of 0.1
 P, C3, C19, C20, C21, C26, C90
 with sigma of 0.1
 C27, C38, C45, C56, C68, C71, C94
 with sigma of 0.1
 C4, C6, C16, C28, C35, C37, C54, C97
 with sigma of 0.1
 C14, C42, C61, C63, C75, C76, C100, C105
 with sigma of 0.1
 S2, C14, C42, C61, C63, C75, C76, C100, C105
 with sigma of 0.1
 C1, C2, C36, C83, C93, C98
 with sigma of 0.1
 P, C1, C2, C36, C83, C93, C98
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C3 \\sim C19 \\sim C20 \\sim C21 \\sim C26 \\sim C90: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C60 \\sim C62 \\sim C64 \\sim C67 \\sim C73 \\sim C74 \\sim C77 \\sim C78 \\sim
S00U \\sim C25 \\sim C33 \\sim C53 \\sim C65 \\sim C92 \\sim C109 \\sim C110
\\sim C111: within 3.8A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 3.8A
C18 \\sim C24 \\sim C40 \\sim C41 \\sim C55 \\sim C102 \\sim C103 \\sim C114
\\sim S00S: within 3.8A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 3.8A
C31 \\sim C51 \\sim C69 \\sim C80 \\sim C84 \\sim C89 \\sim C96 \\sim C99:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C27 \\sim C38 \\sim C45 \\sim C56 \\sim C68 \\sim C71 \\sim C94 \\sim C95:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C70 \\sim C72 \\sim C79 \\sim C82 \\sim C85 \\sim C86 \\sim C88 \\sim C108:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C4 \\sim C6 \\sim C16 \\sim C28 \\sim C35 \\sim C37 \\sim C54 \\sim C97: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S2 \\sim C14 \\sim C42 \\sim C61 \\sim C63 \\sim C75 \\sim C76 \\sim C100 \\sim
C105: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C1 \\sim C2 \\sim C36 \\sim C83 \\sim C93 \\sim C98: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
P \\sim C1 \\sim C2 \\sim C3 \\sim C5 \\sim C7 \\sim C8 \\sim C9 \\sim C10
\\sim C11 \\sim C12 \\sim C13 \\sim C19 \\sim C20 \\sim C21 \\sim C26 \\sim C30
\\sim C36 \\sim C47 \\sim C83 \\sim C90 \\sim C91 \\sim C93 \\sim C98 \\sim
C101: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
C43 \\sim C50 \\sim C66 \\sim C87 \\sim C104 \\sim C106 \\sim C112 \\sim C113:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C8 \\sim C30: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
P \\sim C8 \\sim C9 \\sim C10 \\sim C12 \\sim C30 \\sim C91: 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 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: Cu3(0.5) Cu2(0.5) S1(0.5) S2(0.5) S6(0.5) S20(0.5) P(0.25)
 C1(0.25) C2(0.25) H2(0.25) C3(0.25) H3(0.25) C9(0.25) C91(0.25) H91(0.25)
 C10(0.25) H10(0.25) C12(0.25) H12(0.25) C8(0.25) H8(0.25) C30(0.25) H30(0.25)
 C11(0.25) H11(0.25) C5(0.25) H5(0.25) C47(0.25) C101(0.25) H101(0.25)
 C13(0.25) H13(0.25) C7(0.25) H7(0.25) C14(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
 C16(0.5) C97(0.5) H97(0.5) C6(0.5) H6(0.5) C37(0.5) C4(0.5) H4(0.5) C54(0.5)
 C19(0.25) C20(0.25) H20(0.25) C21(0.25) H21(0.25) C23(0.5) H23(0.5) C32(0.5)
 C107(0.5) C34(0.5) H34(0.5) C22(0.5) H22(0.5) C44(0.5) C24(0.5) H24A(0.5)
 H24B(0.5) H24C(0.5) C26(0.25) H26(0.25) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5)
 C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5) C36(0.25) H36(0.25) C40(0.5) H40A(0.5)
 H40B(0.5) H40C(0.5) C57(0.5) H57A(0.5) H57B(0.5) H57C(0.5) C59(0.5) H59A(0.5)
 H59B(0.5) H59C(0.5) C60(0.5) H60(0.5) C67(0.5) C62(0.5) C73(0.5) H73(0.5)
 C78(0.5) H78(0.5) C74(0.5) C64(0.5) H64A(0.5) H64B(0.5) H64C(0.5) C75(0.5)
 H75A(0.5) H75B(0.5) H75C(0.5) C76(0.5) C100(0.5) H100(0.5) C42(0.5) H42(0.5)
 C61(0.5) C63(0.5) C105(0.5) H105(0.5) C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5)
 C83(0.25) H83(0.25) C90(0.25) H90(0.25) C93(0.25) H93(0.25) C98(0.25)
 H98(0.25) C114(0.5) C103(0.5) H103(0.5) C18(0.5) H18(0.5) C55(0.5) C41(0.5)
 C102(0.5) H102(0.5) S00P(0.5) S00S(0.5) S00T(0.5) S00U(0.5) C25(0.5) C33(0.5)
 H33(0.5) C92(0.5) C65(0.5) C109(0.5) H109(0.5) C110(0.5) H110(0.5) C27(0.5)
 H27A(0.5) H27B(0.5) H27C(0.5) C39(0.5) C15(0.5) H15(0.5) C17(0.5) C46(0.5)
 H46(0.5) C48(0.5) H48(0.5) C52(0.5) C45(0.5) C94(0.5) H94(0.5) C68(0.5)
 C38(0.5) C71(0.5) H71(0.5) C56(0.5) H56(0.5) C53(0.5) H53A(0.5) H53B(0.5)
 H53C(0.5) C58(0.5) H58A(0.5) H58B(0.5) H58C(0.5) C70(0.5) C72(0.5) H72(0.5)
 C88(0.5) C85(0.5) H85(0.5) C82(0.5) H82(0.5) C108(0.5) C79(0.5) H79A(0.5)
 H79B(0.5) H79C(0.5) C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C86(0.5) H86A(0.5)
 H86B(0.5) H86C(0.5) C95(0.5) H95A(0.5) H95B(0.5) H95C(0.5) C104(0.5) H104(0.5)
 C43(0.5) C50(0.5) H50(0.5) C66(0.5) C87(0.5) C106(0.5) H106(0.5) C111(0.5)
 H11A(0.5) H11B(0.5) H11C(0.5) C112(0.5) H11D(0.5) H11E(0.5) H11F(0.5)
 C113(0.5) H11G(0.5) H11H(0.5) H11I(0.5)
7.a Riding coordinates:
 C81(H81A,H81B,H81C), C86(H86A,H86B,H86C), C111(H11A,H11B,H11C), C112(H11D,
 H11E,H11F)
7.b Aromatic/amide H refined with riding coordinates:
 C80(H80), C99(H99), C69(H69), C2(H2), C3(H3), C91(H91), C10(H10), C12(H12),
 C8(H8), C30(H30), C11(H11), C5(H5), C101(H101), C13(H13), C7(H7), C97(H97),
 C6(H6), C4(H4), C20(H20), C21(H21), C23(H23), C34(H34), C22(H22), C26(H26),
 C36(H36), C60(H60), C73(H73), C78(H78), C100(H100), C42(H42), C105(H105),
 C83(H83), C90(H90), C93(H93), C98(H98), C103(H103), C18(H18), C102(H102),
 C33(H33), C109(H109), C110(H110), C15(H15), C46(H46), C48(H48), C94(H94),
 C71(H71), C56(H56), C72(H72), C85(H85), C82(H82), C104(H104), C50(H50),
 C106(H106)
7.c Fitted hexagon refined as free rotating group:
 C80(C96,C51,C99,C89,C69), C9(C91,C10,C12,C8,C30), C11(C5,C47,C101,C13,C7),
 C16(C97,C6,C37,C4,C54), C23(C32,C107,C34,C22,C44), C60(C67,C62,C73,C78,C74),
 C76(C100,C42,C61,C63,C105), C114(C103,C18,C55,C41,C102), C25(C33,C92,C65,C109,
 C110), C39(C15,C17,C46,C48,C52), C45(C94,C68,C38,C71,C56), C70(C72,C88,C85,C82,
 C108), C104(C43,C50,C66,C87,C106)
7.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C84(H84A,H84B,H84C), C14(H14A,H14B,H14C), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C40(H40A,H40B,H40C), C57(H57A,
 H57B,H57C), C59(H59A,H59B,H59C), C64(H64A,H64B,H64C), C75(H75A,H75B,H75C),
 C77(H77A,H77B,H77C), C27(H27A,H27B,H27C), C53(H53A,H53B,H53C), C58(H58A,H58B,
 H58C), C79(H79A,H79B,H79C), C95(H95A,H95B,H95C), C113(H11G,H11H,H11I)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 388 electrons were 
found in a volume of 1568\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
4[CH2CL2], 4.5[C6H14] per Asymmetric Unit 
which account for 400 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              91582
_shelx_fab_checksum              31917
_olex2_submission_special_instructions 'No special instructions were received'