In Situ Two-Phase Ligand Exchange: A New Method for the Synthesis of Alloy Nanoclusters with Precise Atomic Structures.
Yang, Sha; Chai, Jinsong; Song, Yongbo; Fan, Jiqiang; Chen, Tao; Wang, Shuxin; Yu, Haizhu; Li, Xiaowu; Zhu, Manzhou; Journal of the American Chemical Society 139 (2017) 5668–5671; doi:10.1021/jacs.7b00668

data_4126122
_publ_section_title
;
 In Situ Two-Phase Ligand Exchange: A New Method for the Synthesis of
 Alloy Nanoclusters with Precise Atomic Structures.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5668
_journal_page_last               5671
_journal_paper_doi               10.1021/jacs.7b00668
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C60 H135 Ag4.93 Au16.07 S15'
_chemical_formula_sum            'C60 H135 Ag5.2 Au15.81 S15'
_chemical_formula_weight         5011.01
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_symmetry_space_group_name_Hall  '-P 2yc'
_symmetry_space_group_name_H-M   'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.1239(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.1635(17)
_cell_length_b                   15.0108(10)
_cell_length_c                   29.0512(19)
_cell_measurement_reflns_used    6336
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      21.09
_cell_measurement_theta_min      2.20
_cell_volume                     11265.1(13)
_computing_cell_refinement       'SAINT V8.35A (?, 2016)'
_computing_data_reduction        'SAINT V8.35A (?, 2016)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.1148
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            82684
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.353
_diffrn_reflns_theta_min         0.788
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    21.673
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4100
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1305 before and 0.0595 after correction.
The Ratio of minimum to maximum transmission is 0.5502.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    2.955
_exptl_crystal_description       block
_exptl_crystal_F_000             8911
_refine_diff_density_max         1.709
_refine_diff_density_min         -2.188
_refine_diff_density_rms         0.306
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     919
_refine_ls_number_reflns         20615
_refine_ls_number_restraints     573
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.1415
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.051
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0631P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1267
_refine_ls_wR_factor_ref         0.1560
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10521
_reflns_number_total             20615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00668_si_003.cif
_cod_data_source_block           20160403c_0m
_cod_original_formula_sum        'C60 H135 Ag5.20 Au15.81 S15'
_cod_database_code               4126122
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   21.09
_shelx_estimated_absorpt_t_min   2.28
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Au14, Ag14}
{Au13, Ag13}
{Au5, Ag5}
{Au8, Ag8}
{Au9, Ag9}
{Au11, Ag11}
{Au19, Ag19}
{Au2, Ag2}
{Au16, Ag16}
3. Restrained distances
 C60-C68
 1.51 with sigma of 0.02
 C60-C77
 1.51 with sigma of 0.02
 C60-C10
 1.51 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
S5 \\sim C60 \\sim C68 \\sim C10 \\sim C77: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
S5 \\sim C60 \\sim C10 \\sim C77 \\sim C68: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C25 \\sim C26 \\sim C27 \\sim
C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim
C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim
C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C60 \\sim
C61 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C68 \\sim C70 \\sim C72 \\sim
C77 \\sim C78 \\sim C97 \\sim C10: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Au14) = Uanis(Ag14)
Uanis(Au13) = Uanis(Ag13)
Uanis(Au5) = Uanis(Ag5)
Uanis(Au8) = Uanis(Ag8)
Uanis(Au9) = Uanis(Ag9)
Uanis(Au11) = Uanis(Ag11)
Uanis(Au19) = Uanis(Ag19)
Uanis(Au2) = Uanis(Ag2)
Uanis(Au16) = Uanis(Ag16)
5. Others
 Sof(Ag14)=1-FVAR(1)
 Sof(Au14)=FVAR(1)
 Sof(Ag13)=1-FVAR(2)
 Sof(Au13)=FVAR(2)
 Sof(Ag5)=1-FVAR(3)
 Sof(Au5)=FVAR(3)
 Sof(Ag8)=1-FVAR(4)
 Sof(Au8)=FVAR(4)
 Sof(Ag9)=1-FVAR(5)
 Sof(Au9)=FVAR(5)
 Sof(Ag11)=1-FVAR(6)
 Sof(Au11)=FVAR(6)
 Sof(Ag19)=1-FVAR(7)
 Sof(Au19)=FVAR(7)
 Sof(Ag2)=1-FVAR(8)
 Sof(Au2)=FVAR(8)
 Sof(Ag16)=1-FVAR(9)
 Sof(Au16)=FVAR(9)
6.a Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C25(H25A,
 H25B,H25C), C26(H26A,H26B,H26C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,
 H54B,H54C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C),
 C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C72(H72A,
 H72B,H72C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C97(H97A,H97B,H97C),
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              97608
_shelx_hkl_checksum              55654
_shelx_fab_checksum              30436
_olex2_submission_special_instructions 'No special instructions were received'