Structural Evolution of Atomically Precise Thiolated Bimetallic [Au12+nCu32(SR)30+n](4-) (n = 0, 2, 4, 6) Nanoclusters.
Yang, Huayan; Wang, Yu; Yan, Juanzhu; Chen, Xi; Zhang, Xin; Häkkinen, Hannu; Zheng, Nanfeng; Journal of the American Chemical Society 136 (2014) 7197–7200; doi:10.1021/ja501811j

data_4121795
_publ_section_title
;
 Structural Evolution of Atomically Precise Thiolated Bimetallic
 [Au12+nCu32(SR)30+n](4-) (n = 0, 2, 4, 6) Nanoclusters.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7197
_journal_page_last               7200
_journal_paper_doi               10.1021/ja501811j
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C252 H142 Au18 Cu32 F108 S36, 4(C16 H36 N)'
_chemical_formula_sum            'C332 H314 Au18 Cl7 Cu32 F108 N4 S36'
_chemical_formula_weight         13392.86
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-01-09
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.456(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   21.8379(8)
_cell_length_b                   21.0323(11)
_cell_length_c                   43.031(2)
_cell_measurement_reflns_used    14997
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      65.3270
_cell_measurement_theta_min      4.1190
_cell_volume                     19597.1(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XH, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.3415
_diffrn_measured_fraction_theta_full 0.9428
_diffrn_measured_fraction_theta_max 0.9862
_diffrn_measurement_details
;
  1 omega -127.00  -35.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7424 -178.0000   30.0000 92

  2 omega -117.00  -13.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.7424  -77.0000   30.0000 104

  3 omega   35.00   91.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000  -60.0000 56

  4 omega   33.00  139.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -77.0000 -150.0000 106

  5 omega   79.00  153.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940   30.0000  150.0000 74

  6 omega   33.00  105.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940 -125.0000 -150.0000 72

  7 omega   30.00   91.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000    0.0000 61
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0423241000
_diffrn_orient_matrix_UB_12      -0.0186252000
_diffrn_orient_matrix_UB_13      -0.0300385000
_diffrn_orient_matrix_UB_21      0.0150062000
_diffrn_orient_matrix_UB_22      -0.0706517000
_diffrn_orient_matrix_UB_23      0.0065595000
_diffrn_orient_matrix_UB_31      -0.0552807000
_diffrn_orient_matrix_UB_32      -0.0048368000
_diffrn_orient_matrix_UB_33      0.0188580000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0635
_diffrn_reflns_av_unetI/netI     0.0763
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            54998
_diffrn_reflns_theta_full        61.17
_diffrn_reflns_theta_max         61.17
_diffrn_reflns_theta_min         3.43
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.211
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19506
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    2.270
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plane
_exptl_crystal_F_000             12702
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_platon_squeeze_details
;
SQUEEZE removed 8 disordered dichloromethane molecules per formula unit.
;
_refine_diff_density_max         5.866
_refine_diff_density_min         -5.272
_refine_diff_density_rms         0.320
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1971
_refine_ls_number_reflns         29916
_refine_ls_number_restraints     392
_refine_ls_restrained_S_all      1.267
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0889
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1421P)^2^+307.0838P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2447
_refine_ls_wR_factor_ref         0.2637
_reflns_number_gt                21313
_reflns_number_total             29916
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja501811j_si_005.cif
_cod_data_source_block           Au12Cu32@Au6
_cod_depositor_comments
'Adding full bibliography for 4121793--4121797.cif.'
_cod_original_cell_volume        19596.9(16)
_cod_database_code               4121795
_reflns_odcompleteness_completeness 94.28
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 F44-C105 = F43-C105 = F45-C105
 1.3 with sigma of 0.02
 F43-F45
 2.4 with sigma of 0.02
 F45-F44
 2.4 with sigma of 0.02
 F44-F43
 2.4 with sigma of 0.02
 C135-C131
 2.5 with sigma of 0.02
 C135-C139
 1.5 with sigma of 0.02
 C139-C135
 2.5 with sigma of 0.02
 C139-C127
 2.5 with sigma of 0.02
 C127-C131
 2.5 with sigma of 0.02
 N1-C136
 2.5 with sigma of 0.02
 C135-C137
 2.5 with sigma of 0.02
 C136-C138
 2.5 with sigma of 0.02
 N1-C132
 2.5 with sigma of 0.02
 C131-C133
 2.5 with sigma of 0.02
 C132-C134
 2.5 with sigma of 0.02
 N1-C128
 2.5 with sigma of 0.02
 C127-C129
 2.5 with sigma of 0.02
 C128-C130
 2.5 with sigma of 0.02
 C139-C141
 2.5 with sigma of 0.02
 C155-C157 = N2-C155 = C158-C157 = C159-C158 = N2-C147 = C148-C147 = C149-C148
 = C149-C150 = N2-C143 = C144-C143 = C145-C144 = C146-C145 = N2-C151 = C151-
 C152 = C153-C152 = C153-C154
 1.5 with sigma of 0.02
 C155-C147
 2.5 with sigma of 0.02
 C147-C143
 2.5 with sigma of 0.02
 C143-C151
 2.5 with sigma of 0.02
 C151-C155
 2.5 with sigma of 0.02
 C148-N2
 2.5 with sigma of 0.02
 C147-C149
 2.5 with sigma of 0.02
 C148-C150
 2.5 with sigma of 0.02
 N2-C144
 2.5 with sigma of 0.02
 C143-C145
 2.5 with sigma of 0.02
 C144-C146
 2.5 with sigma of 0.02
 N2-C152
 2.5 with sigma of 0.02
 C151-C153
 2.5 with sigma of 0.02
 C152-C154
 2.5 with sigma of 0.02
 N2-C157
 2.5 with sigma of 0.02
 C155-C158
 2.5 with sigma of 0.02
 C157-C159
 2.5 with sigma of 0.02
 F39-C91
 1.3 with sigma of 0.02
 F41-C98 = F42-C98 = F40-C98
 1.3 with sigma of 0.02
 F42-F41
 2.4 with sigma of 0.02
 F42-F40
 2.4 with sigma of 0.02
 F40-F41
 2.4 with sigma of 0.02
 F39-C91 = F38-C91 = F37-C91
 1.3 with sigma of 0.02
 F38-F37
 2.4 with sigma of 0.02
 F39-F37
 2.4 with sigma of 0.02
 F39-F38
 2.4 with sigma of 0.02
 N1-C135 = N1-C139 = N1-C131 = N1-C127
 1.5 with sigma of 0.02
 C127-C135
 2.45 with sigma of 0.02
 C135-C131
 2.45 with sigma of 0.02
 C131-C139
 2.45 with sigma of 0.02
 C139-C127
 2.45 with sigma of 0.02
 N1-C131 = N1-C139 = N1-C127 = N1-C135 = C131-C132 = C133-C132 = C134-C133 =
 C136-C135 = C136-C137 = C138-C137 = C140-C139 = C140-C141 = C142-C141 = C127-
 C128 = C129-C128 = C129-C130
 1.5 with sigma of 0.02
 N1-C140
 2.5 with sigma of 0.02
 C140-C142
 2.5 with sigma of 0.02
 C140-C139 = C140-C141 = N1-C131 = N1-C139 = N1-C127 = N1-C135 = C136-C135
 1.5 with sigma of 0.02
 N1-C135 = N1-C127 = N1-C139 = N1-C131
 2.45 with sigma of 0.02
 N1-C131 = N1-C135 = N1-C127 = N1-C139
 1.45 with sigma of 0.02
 C127-C135
 2.45 with sigma of 0.02
 C127-C139
 2.45 with sigma of 0.02
 C131-C135
 2.45 with sigma of 0.02
 C84-C81
 1.5 with sigma of 0.02
3. Rigid bond restraints
 S3, C68
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S15, C99
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S12, C78
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C64, C65
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C8, C13
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C27, C26
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C85, C86
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C100, C99
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C97, C92
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 N2, C155
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 N2, C143
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 N2, C151
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S3, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S15, C99
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S12, C78
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C64, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C85, C86
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C85, C86
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C85, C90
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C100, C99
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C97, C92
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, C155
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C157, C155
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S12, C99
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S13, C85
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S12, C78
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C100, C99
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C157, C158
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C85 \\sim C86 \\sim S13: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C99 \\sim C104 \\sim C100 \\sim S15: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
N2 \\sim C143 \\sim C151 \\sim C147 \\sim C155: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C85 \\sim C86 \\sim C90: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C99 \\sim C104 \\sim C100 \\sim S15: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
N2 \\sim C143 \\sim C151 \\sim C147 \\sim C155: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C136 \\sim C135 \\sim C137: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C99 \\sim C100 \\sim C104: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C103 \\sim C104 \\sim C102: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C157 \\sim C155 \\sim C158: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C140 \\sim C141: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C104 \\sim C103 \\sim C99: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C155 \\sim C157 \\sim N2: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C139 \\sim C140 \\sim N1: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C141 \\sim C142 \\sim C140: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C137 \\sim C138 \\sim C136: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F5) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F36) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(F34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F38) = Uanis(C85)
Uanis(F22) = Uanis(F22A) = Uanis(F24) = Uanis(F24A) = Uanis(F23) = Uanis(F23A)
Uanis(F33A) = Uanis(F33) = Uanis(F32A) = Uanis(F32) = Uanis(F31A) = Uanis(F31)
Uanis(C86) = Uanis(C87) = Uanis(C88) = Uanis(C89) = Uanis(F37) = Uanis(C91) = Uanis(F39) = Uanis(C79) = Uanis(C82) = Uanis(C81) = Uanis(C80) = Uanis(C84) = Uanis(C83) = Uanis(C90) = Uanis(C78) = Uanis(C144) = Uanis(C145) = Uanis(C146) = Uanis(C143) = Uanis(C154) = Uanis(C153) = Uanis(C152) = Uanis(C151) = Uanis(C155) = Uanis(C159) = Uanis(C134) = Uanis(C133) = Uanis(C132) = Uanis(C131) = Uanis(C142) = Uanis(C141) = Uanis(C139) = Uanis(N1) = Uanis(C127) = Uanis(C128) = Uanis(C129) = Uanis(C130) = Uanis(C137) = Uanis(C138) = Uanis(F41) = Uanis(C98) = Uanis(F42) = Uanis(F40) = Uanis(C99)
5. Others
 Sof(F23A)=Sof(F22A)=Sof(F24A)=1-FVAR(1)
 Sof(F24)=Sof(F23)=Sof(F22)=FVAR(1)
 Sof(F33A)=Sof(F32A)=Sof(F31A)=1-FVAR(2)
 Sof(F33)=Sof(F31)=Sof(F32)=FVAR(2)
6.a Free rotating group:
 F44(F43,F45), F36(F34,F35)
6.b Secondary CH2 refined with riding coordinates:
 C147(H14A,H14B), C148(H14C,H14D), C141(H14P,H14Q), C157(H15D,H15E), C158(H15F,
 H15G), C140(H14R,H14S), C132(H13A,H13B), C152(H15H,H15I), C155(H15J,H15K),
 C149(H14E,H14F), C143(H14G,H14H), C128(H12A,H12B), C137(H13C,H13D), C135(H13E,
 H13F), C133(H13G,H13H), C136(H13L,H13M), C153(H15L,H15M), C151(H15Q,H15R),
 C131(H13T,H13U), C127(H12C,H12D), C144(H14I,H14J), C145(H14K,H14L), C129(H12E,
 H12F), C139(H13V,H13W)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C44(H44), C9(H9), C111(H111), C23(H23), C3(H3), C45(H45), C5(H5),
 C20(H20), C76(H76), C101(H101), C100(H100), C104(H104), C103(H103), C114(H114),
  C121(H121), C47(H47), C10(H10), C27(H27), C110(H110), C16(H16), C58(H58),
 C48(H48), C107(H107), C117(H117), C65(H65), C68(H68), C59(H59), C26(H26),
 C125(H125), C69(H69), C24(H24), C122(H122), C66(H66), C115(H115), C86(H86),
 C87(H87), C89(H89), C90(H90), C124(H124), C2(H2), C17(H17), C118(H118),
 C108(H108), C62(H62), C12(H12), C51(H51), C72(H72), C13(H13), C34(H34),
 C75(H75), C19(H19), C41(H41), C55(H55), C61(H61), C52(H52), C73(H73), C54(H54),
  C40(H40), C30(H30), C33(H33), C31(H31), C37(H37), C38(H38), C93(H93),
 C97(H97), C96(H96), C94(H94), C82(H82), C80(H80), C79(H79)
6.d Fitted hexagon refined as free rotating group:
 C102(C101,C100,C99,C104,C103), C85(C86,C87,C88,C89,C90), C93(C92,C97,C96,C95,
 C94), C83(C82,C81,C80,C79,C78)
6.e Idealised Me refined as rotating group:
 C150(H15A,H15B,H15C), C130(H13I,H13J,H13K), C142(H14T,H14U,H14V), C138(H13N,
 H13O,H13P), C159(H15N,H15O,H15P), C134(H13Q,H13R,H13S), C146(H14M,H14N,H14O),
 C154(H15S,H15T,H15U)
;