Alloying and dealloying of Au<sub>18</sub>Cu<sub>32</sub> nanoclusters at precise locations <i>via</i> controlling the electronegativity of substituent groups on thiol ligands.
Tang, Li; Wang, Bin; Wang, Ru; Wang, Shuxin; Nanoscale 15 (2023) 1602–1608; doi:10.1039/d2nr05401a

data_1568237
_publ_section_title
;
 Alloying and dealloying of Au<sub>18</sub>Cu<sub>32</sub> nanoclusters at
 precise locations <i>via</i> controlling the electronegativity of
 substituent groups on thiol ligands.
;
_journal_issue                   4
_journal_name_full               Nanoscale
_journal_page_first              1602
_journal_page_last               1608
_journal_paper_doi               10.1039/d2nr05401a
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety         'C252 H252 Au20.31 Cu29.69 O36 S36'
_chemical_formula_sum            'C252 H252 Au20.31 Cu29.69 O36 S36'
_chemical_formula_weight         10897.57
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-02 deposited with the CCDC.	2022-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                111.776(2)
_cell_angle_beta                 118.542(2)
_cell_angle_gamma                96.201(2)
_cell_formula_units_Z            1
_cell_length_a                   21.3034(6)
_cell_length_b                   21.5883(7)
_cell_length_c                   21.9884(7)
_cell_measurement_reflns_used    3760
_cell_measurement_temperature    170
_cell_measurement_theta_max      72.56
_cell_measurement_theta_min      3.46
_cell_volume                     7728.8(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device_type  STOE
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0686
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            98463
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         70.232
_diffrn_reflns_theta_min         3.625
_exptl_absorpt_coefficient_mu    22.433
_exptl_absorpt_correction_T_max  0.3049
_exptl_absorpt_correction_T_min  0.0535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270. Afterwards scaling of
reflection intensities was performed within STOE LANA. J. Koziskova, F. Hahn,
J. Richter, J. Kozisek, Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136-140.
;
_exptl_crystal_colour            'dark black'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.341
_exptl_crystal_description       block
_exptl_crystal_F_000             5094
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         8.488
_refine_diff_density_min         -2.373
_refine_diff_density_rms         0.335
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1474
_refine_ls_number_reflns         28030
_refine_ls_number_restraints     2941
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1201
_refine_ls_R_factor_gt           0.0900
_refine_ls_shift/su_max          0.091
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1672P)^2^+60.5808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2464
_refine_ls_wR_factor_ref         0.2691
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18944
_reflns_number_total             28030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nr05401a2.cif
_cod_data_source_block           qust02
_cod_depositor_comments
'Adding full bibliography for 1568236--1568237.cif.'
_cod_original_cell_volume        7728.8(4)
_cod_database_code               1568237
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.663
_shelx_estimated_absorpt_t_min   0.192
_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
{Cu12, Au12}
{Cu16, Au16}
{Cu13, Au13}
{Cu15, Au15}
{Cu11, Au11}
{Cu14, Au14}
3. Restrained distances
 O1AA-C8EA
 1.45 with sigma of 0.01
 O1AA-C5CA
 1.45 with sigma of 0.01
 O31-C2FA
 1.45 with sigma of 0.02
 O34-C9EA
 1.45 with sigma of 0.02
 O39-C2EA
 1.45 with sigma of 0.02
 O48-C4BA
 1.45 with sigma of 0.02
 O48-C7FA
 1.45 with sigma of 0.02
 C4BA-C7FA
 2.5 with sigma of 0.02
 C4FA-O23
 1.45 with sigma of 0.02
 C3EA-O61
 2.5 with sigma of 0.02
 O61-C5EA
 2.5 with sigma of 0.02
 O18-C1EA
 1.45 with sigma of 0.02
 O32-C0EA
 1.45 with sigma of 0.02
 H3EA-H6FC
 2.1 with sigma of 0.01
 H0DA-H9EC
 2.1 with sigma of 0.01
 H53-H54A
 2.1 with sigma of 0.01
 H2AA-H3FB
 2.1 with sigma of 0.01
 H7BA-H63
 2.1 with sigma of 0.01
 H3EA-H6FA
 2.1 with sigma of 0.01
 H0CA-H2FC
 2.1 with sigma of 0.01
 H40B-H76
 2.1 with sigma of 0.01
4. Restrained planarity
 C4AA, C5AA, C4EA, C5EA, O61, C6FA, C3EA, C8BA
 with sigma of 0.1
 C4AA, C5AA, C5EA, C4EA, O61, C3EA, C8BA, C6FA
 with sigma of 0.1
 O1AA, C8EA, C89, C5CA, C9AA, C95, C65, C55
 with sigma of 0.1
5. Rigid bond restraints
 C6FA, O61
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0
C24 \\sim C39 \\sim C7AA \\sim C7EA \\sim C64 \\sim C6AA \\sim C29 \\sim C48
\\sim C63 \\sim C47 \\sim C6EA \\sim C67 \\sim C30 \\sim C70 \\sim C97 \\sim
C61 \\sim C76 \\sim C3AA \\sim C31 \\sim C51 \\sim C2DA \\sim C93 \\sim C86
\\sim C85 \\sim C32 \\sim C38 \\sim C52 \\sim C88 \\sim C36 \\sim C33 \\sim C44
\\sim C46 \\sim C6BA \\sim C5BA \\sim C37 \\sim C49 \\sim C50 \\sim C68 \\sim
C82 \\sim C66 \\sim C84 \\sim C99 \\sim C56 \\sim C98 \\sim C5DA \\sim C4DA
\\sim C53 \\sim C3DA \\sim C60 \\sim C62 \\sim C57 \\sim C34 \\sim C35 \\sim
C59 \\sim C65 \\sim C55 \\sim C89 \\sim C5CA \\sim C9AA \\sim C95 \\sim C69
\\sim C87 \\sim C83 \\sim C80 \\sim C91 \\sim C71 \\sim C72 \\sim C43 \\sim
C1BA \\sim C2BA \\sim C92 \\sim C0BA \\sim C75 \\sim C94 \\sim C2AA \\sim C1AA
\\sim C2CA \\sim C0AA \\sim C78 \\sim C73 \\sim C58 \\sim C4BA \\sim C3BA \\sim
C45 \\sim C4AA \\sim C5AA \\sim C5EA \\sim C4EA \\sim C3EA \\sim C8BA \\sim
C8AA \\sim C81 \\sim C9DA \\sim C8DA \\sim C7DA \\sim C6DA \\sim C25 \\sim C9BA
\\sim C0CA \\sim C1CA \\sim C3CA \\sim C4CA \\sim C6CA \\sim C7CA \\sim C8CA
\\sim C9CA \\sim C0DA \\sim C1DA \\sim C1EA \\sim C2EA \\sim C0EA \\sim C40
\\sim C1FA \\sim C0FA \\sim C7BA \\sim C9EA \\sim C2FA \\sim C3FA \\sim C4FA
\\sim C28 \\sim C5FA \\sim C54 \\sim C6FA \\sim C41 \\sim C8EA \\sim C7FA:
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C4AA \\sim C5AA \\sim C5EA \\sim C4EA \\sim C3EA \\sim C8BA \\sim O61 \\sim
C6FA: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6FA) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Cu12) = Uanis(Au12)
Uanis(Cu16) = Uanis(Au16)
Uanis(Cu13) = Uanis(Au13)
Uanis(Cu15) = Uanis(Au15)
Uanis(Cu11) = Uanis(Au11)
Uanis(Cu14) = Uanis(Au14)
Uanis(O48) = Uanis(C7FA)
Uanis(O23) = Uanis(C4FA)
Uanis(C54) = Uanis(O36)
7. Others
 Sof(Au12)=1-FVAR(1)
 Sof(Cu12)=FVAR(1)
 Sof(Au16)=1-FVAR(2)
 Sof(Cu16)=FVAR(2)
 Sof(Au13)=1-FVAR(3)
 Sof(Cu13)=FVAR(3)
 Sof(Au15)=1-FVAR(4)
 Sof(Cu15)=FVAR(4)
 Sof(Au11)=1-FVAR(5)
 Sof(Cu11)=FVAR(5)
 Sof(Au14)=1-FVAR(6)
 Sof(Cu14)=FVAR(6)
8.a Aromatic/amide H refined with riding coordinates:
 C39(H39), C7AA(H7AA), C64(H64), C6AA(H6AA), C48(H48), C63(H63), C6EA(H6EA),
 C67(H67), C70(H70), C97(H97), C76(H76), C3AA(H3AA), C51(H51), C2DA(H2DA),
 C86(H86), C85(H85), C38(H38), C52(H52), C36(H36), C33(H33), C46(H46),
 C6BA(H6BA), C37(H37), C49(H49), C68(H68), C82(H82), C84(H84), C99(H99),
 C98(H98), C5DA(H5DA), C53(H53), C3DA(H3DA), C62(H62), C57(H57), C35(H35),
 C59(H59), C55(H55), C89(H89), C9AA(H9AA), C95(H95), C87(H87), C83(H83),
 C91(H91), C71(H71), C43(H43), C1BA(H1BA), C92(H92), C0BA(H0BA), C94(H94),
 C2AA(H2AA), C2CA(H2CA), C0AA(H0AA), C73(H73), C58(H58), C3BA(H3BA), C45(H45),
 C5AA(H5AA), C5EA(H5EA), C3EA(H3EA), C8BA(H8BA), C81(H81), C9DA(H9DA),
 C7DA(H7DA), C6DA(H6DA), C9BA(H9BA), C0CA(H0CA), C3CA(H3CA), C4CA(H4CA),
 C7CA(H7CA), C8CA(H8CA), C0DA(H0DA), C1DA(H1DA)
8.b Fitted hexagon refined as free rotating group:
 C24(C39,C7AA,C7EA,C64,C6AA), C29(C48,C63,C47,C6EA,C67), C30(C70,C97,C61,C76,
 C3AA), C31(C51,C2DA,C93,C86,C85), C32(C38,C52,C88,C36,C33), C44(C46,C6BA,C5BA,
 C37,C49), C50(C68,C82,C66,C84,C99), C56(C98,C5DA,C4DA,C53,C3DA), C60(C62,C57,
 C34,C35,C59), C65(C55,C89,C5CA,C9AA,C95), C69(C87,C83,C80,C91,C71), C72(C43,
 C1BA,C2BA,C92,C0BA), C75(C94,C2AA,C1AA,C2CA,C0AA), C78(C73,C58,C4BA,C3BA,C45),
 C4AA(C5AA,C5EA,C4EA,C3EA,C8BA), C8AA(C81,C9DA,C8DA,C7DA,C6DA), C25(C9BA,C0CA,
 C1CA,C3CA,C4CA), C6CA(C7CA,C8CA,C9CA,C0DA,C1DA)
8.c Idealised Me refined as rotating group:
 C1EA(H1EA,H1EB,H1EC), C2EA(H2EA,H2EB,H2EC), C0EA(H0EA,H0EB,H0EC), C40(H40A,
 H40B,H40C), C1FA(H1FA,H1FB,H1FC), C0FA(H0FA,H0FB,H0FC), C7BA(H7BA,H7BB,H7BC),
 C9EA(H9EA,H9EB,H9EC), C2FA(H2FA,H2FB,H2FC), C3FA(H3FA,H3FB,H3FC), C4FA(H4FA,
 H4FB,H4FC), C28(H28A,H28B,H28C), C5FA(H5FA,H5FB,H5FC), C54(H54A,H54B,H54C),
 C6FA(H6FA,H6FB,H6FC), C41(H41A,H41B,H41C), C8EA(H8EA,H8EB,H8EC), C7FA(H7FA,
 H7FB,H7FC)
;
_shelx_res_checksum              63339
_shelx_fab_checksum              21414
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'