Ligand-Stabilized Au13Cux (x= 2, 4, 8) Bimetallic Nanoclusters: Ligand Engineering to Control the Exposure of Metal Sites
Huayan Yang; Yu Wang; Jing Lei; Lei Shi; Xiaohu Wu; Ville Mäkinen; Shuichao Lin; Zichao Tang; Jian He; Hannu Häkkinen; Lansun Zheng; Nanfeng Zheng; Journal of the American Chemical Society 135 (2013) 9568–9571; doi:10.1021/ja402249s

data_4120007
_publ_contact_author_address
;
State Key Laboratory of Physical Chemistry of Solid Surfaces 
and Department of Chemistry
Xiamen University
422 Siming South Road
Xiamen, Fujian 361005
P. R. China
http://210.34.14.15/kydw_ktz/nfzheng/index.html
;
_publ_contact_author_email       nfzheng@xmu.edu.cn
_publ_contact_author_fax         +86-592-2183047
_publ_contact_author_name        'Nanfeng Zheng'
_publ_contact_author_phone       +86-592-2186821
_publ_section_title
;
 Ligand-Stabilized Au13Cux (x= 2, 4, 8) Bimetallic Nanoclusters: Ligand
 Engineering to Control the Exposure of Metal Sites
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9568
_journal_page_last               9571
_journal_paper_doi               10.1021/ja402249s
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C138 H114 Au13 Cu2 N6 P6 S6, Cl, 3(O)'
_chemical_formula_sum            'C138 H114 Au13 Cl Cu2 N6 O3 P6 S6'
_chemical_formula_weight         5005.63
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   constr
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-04-25
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:20:19, GUI svn.r4385)
;
_cell_angle_alpha                90.860(3)
_cell_angle_beta                 101.783(4)
_cell_angle_gamma                93.627(4)
_cell_formula_units_Z            2
_cell_length_a                   16.1130(9)
_cell_length_b                   18.3910(8)
_cell_length_c                   24.9731(10)
_cell_measurement_reflns_used    9741
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.4139
_cell_measurement_theta_min      3.5713
_cell_volume                     7227.0(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_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
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector_area_resol_mean 10.3415
_diffrn_measured_fraction_theta_full 0.9993
_diffrn_measured_fraction_theta_max 0.9977
_diffrn_measurement_details
;
  1 omega  -77.00  -11.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9299  -57.0000    0.0000 66

  2 omega  -94.00   -2.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9299  125.0000 -150.0000 92

  3 omega -119.00  -10.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.9299  -77.0000  120.0000 109

  4 omega   25.00   52.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       40.9299 -125.0000 -120.0000 27

  5 omega  -26.00    1.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000   30.0000    0.0000 27

  6 omega  -43.00  -10.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000   30.0000   30.0000 33

  7 omega -135.00  -66.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000  -61.0000   30.0000 69

  8 omega   30.00   65.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000  -90.0000 35

  9 omega   37.00   95.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -94.0000   30.0000 58

 10 omega   44.00  109.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -94.0000  -30.0000 65

 11 omega   30.00   87.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000   30.0000 57

 12 omega   84.00  178.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940   30.0000 -150.0000 94

 13 omega   49.00   85.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000  -30.0000 36

 14 omega   42.00   79.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940 -125.0000 -180.0000 37

 15 omega   30.00   65.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000 -180.0000 35

 16 omega   78.00  178.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940   30.0000  -60.0000 100

 17 omega   96.00  121.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940 -125.0000 -180.0000 25

 18 omega   61.00   88.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000  120.0000 27

 19 omega   24.00   98.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -94.0000 -180.0000 74

 20 omega   31.00   77.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -30.0000  -60.0000 46

 21 omega   42.00  105.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -94.0000   90.0000 63

 22 omega   57.00   96.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -45.0000 -150.0000 39

 23 omega   44.00  109.00   1.0000   25.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1940  -94.0000 -120.0000 65
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0512365000
_diffrn_orient_matrix_UB_12      0.0201955000
_diffrn_orient_matrix_UB_13      -0.0562456000
_diffrn_orient_matrix_UB_21      0.0801731000
_diffrn_orient_matrix_UB_22      0.0402139000
_diffrn_orient_matrix_UB_23      -0.0128162000
_diffrn_orient_matrix_UB_31      0.0230258000
_diffrn_orient_matrix_UB_32      -0.0708933000
_diffrn_orient_matrix_UB_33      -0.0254272000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0929
_diffrn_reflns_av_unetI/netI     0.1190
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            44067
_diffrn_reflns_theta_full        58.93
_diffrn_reflns_theta_max         58.93
_diffrn_reflns_theta_min         3.57
_diffrn_source                   'SuperNova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    26.413
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29964
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    2.300
_exptl_crystal_description       block
_exptl_crystal_F_000             4592
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         4.832
_refine_diff_density_min         -4.306
_refine_diff_density_rms         0.401
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1354
_refine_ls_number_reflns         20742
_refine_ls_number_restraints     437
_refine_ls_restrained_S_all      1.002
_refine_ls_R_factor_all          0.1305
_refine_ls_R_factor_gt           0.0868
_refine_ls_shift/su_max          0.030
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1459P)^2^+81.2135P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2293
_refine_ls_wR_factor_ref         0.2740
_reflns_number_gt                12799
_reflns_number_total             20742
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja402249s_si_003.cif
_cod_data_source_block           XMC4
_cod_database_code               4120007
_chemical_oxdiff_formula         'Au Cu S P Cl C N O H'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H118 of C118, H65 of C65, H64 of C64, H62 of C62, H77 of C77, H89 of C89,
  H5 of C5, H28 of C28, H56 of C56, H63 of C63, H132 of C132, H48 of C48, H75
  of C75, H52 of C52, H100 of C100, H86 of C86, H99 of C99, H42 of C42, H111 of
  C111, H122 of C122, H46 of C46, H81 of C81, H4 of C4, H51 of C51, H47 of C47,
  H113 of C113, H39 of C39, H116 of C116, H36 of C36, H90 of C90, H60 of C60,
  H82 of C82, H41 of C41, H129 of C129, H114 of C114, H130 of C130, H96 of C96,
  H68 of C68, H21 of C21, H66 of C66, H102 of C102, H23 of C23, H95 of C95, H7
  of C7, H18 of C18, H110 of C110, H32 of C32, H59 of C59, H138 of C138, H78 of
  C78, H84 of C84, H13 of C13, H14 of C14, H107 of C107, H117 of C117, H120 of
  C120, H3 of C3, H54 of C54, H98 of C98, H119 of C119, H76 of C76, H11 of C11,
  H128 of C128, H70 of C70, H38 of C38, H58 of C58, H93 of C93, H124 of C124,
  H126 of C126, H133 of C133, H94 of C94, H24 of C24, H19 of C19, H12 of C12,
  H136 of C136, H112 of C112, H26 of C26, H88 of C88, H87 of C87, H105 of C105,
  H9 of C9, H22 of C22, H44 of C44, H108 of C108, H6 of C6, H2 of C2, H71 of
  C71, H135 of C135, H45 of C45, H40 of C40, H106 of C106, H57 of C57, H72 of
  C72, H17 of C17, H80 of C80, H131 of C131, H33 of C33, H92 of C92, H123 of
  C123, H137 of C137, H74 of C74, H8 of C8, H125 of C125, H29 of C29, H35 of
  C35, H27 of C27, H69 of C69, H104 of C104, H53 of C53, H50 of C50, H83 of C83,
   H101 of C101, H20 of C20, H34 of C34
2. Rigid bond restraints
 C7, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C13, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C14, C15
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C88, C89
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C50, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S2, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C130, C131
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 P1, C43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
S2 ~ C10 ~ Au1: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C41 ~ C40 ~ C42: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C69 ~ C68 ~ C70: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C47 ~ C46 ~ C48: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C40 ~ C39 ~ C41: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C42 ~ C41 ~ C43: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C68 ~ C69 ~ C67: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C67 ~ C68 ~ C72: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C66 ~ C65 ~ C61: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C64 ~ C65 ~ C63: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C9 ~ C8 ~ C10: 
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C32) ~ Ueq, Uanis(C86) ~ Ueq: with sigma of 0.1 and sigma 
for terminal atoms of 0.2
Uanis(C41) ~ Ueq, Uanis(C42) ~ Ueq, Uanis(C66) ~ Ueq, Uanis(C65) ~ Ueq, 
Uanis(C64) ~ Ueq, Uanis(C69) ~ Ueq, Uanis(C70) ~ Ueq, Uanis(C71) ~ Ueq, 
Uanis(C72) ~ Ueq, Uanis(C68) ~ Ueq, Uanis(C56) ~ Ueq, Uanis(C58) ~ Ueq, 
Uanis(C57) ~ Ueq, Uanis(C77) ~ Ueq, Uanis(C78) ~ Ueq, Uanis(C76) ~ Ueq, 
Uanis(C8) ~ Ueq, Uanis(C9) ~ Ueq, Uanis(C10) ~ Ueq, Uanis(C6) ~ Ueq, 
Uanis(C7) ~ Ueq, Uanis(C48) ~ Ueq, Uanis(C47) ~ Ueq, Uanis(C46) ~ Ueq, 
Uanis(C75) ~ Ueq, Uanis(C83) ~ Ueq, Uanis(C81) ~ Ueq, Uanis(C51) ~ Ueq, 
Uanis(C52) ~ Ueq, Uanis(C53) ~ Ueq, Uanis(C50) ~ Ueq, Uanis(C101) ~ Ueq, 
Uanis(C20) ~ Ueq, Uanis(C60) ~ Ueq: with sigma of 0.1 and sigma for 
terminal atoms of 0.2
Uanis(C11) ~ Ueq, Uanis(C15) ~ Ueq, Uanis(C16) ~ Ueq, Uanis(C30) ~ Ueq, 
Uanis(C80) ~ Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C16) ~ Ueq, Uanis(C86) ~ Ueq: with sigma of 0.1 and sigma for 
terminal atoms of 0.2
Uanis(C11) = Uanis(C15) = Uanis(C16) = Uanis(C86) = Uanis(C7) = Uanis(C10) 
= Uanis(C32) = Uanis(C30) = Uanis(C24) = Uanis(C61) = Uanis(C103) = Uanis(N1) 
= Uanis(C13) = Uanis(C23) = Uanis(C105) = Uanis(C110) = Uanis(C134) 
= Uanis(C127)
4.a Aromatic/amide H refined with riding coordinates:
 C110(H110), C12(H12), C102(H102), C86(H86), C87(H87), C88(H88), C89(H89),
 C90(H90), C98(H98), C96(H96), C11(H11), C93(H93), C108(H108), C112(H112),
 C133(H133), C135(H135), C136(H136), C137(H137), C138(H138), C94(H94),
 C107(H107), C92(H92), C26(H26), C126(H126), C27(H27), C122(H122), C111(H111),
 C32(H32), C101(H101), C20(H20), C54(H54), C53(H53), C52(H52), C51(H51),
 C50(H50), C29(H29), C19(H19), C120(H120), C13(H13), C128(H128), C99(H99),
 C104(H104), C119(H119), C116(H116), C113(H113), C5(H5), C129(H129), C48(H48),
 C47(H47), C46(H46), C45(H45), C44(H44), C4(H4), C95(H95), C2(H2), C114(H114),
 C130(H130), C82(H82), C132(H132), C18(H18), C131(H131), C36(H36), C14(H14),
 C123(H123), C105(H105), C100(H100), C78(H78), C77(H77), C76(H76), C75(H75),
 C74(H74), C117(H117), C3(H3), C118(H118), C84(H84), C42(H42), C41(H41),
 C40(H40), C39(H39), C38(H38), C34(H34), C83(H83), C106(H106), C17(H17),
 C33(H33), C28(H28), C124(H124), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C81(H81),
 C125(H125), C80(H80), C9(H9), C8(H8), C7(H7), C6(H6), C21(H21), C22(H22),
 C24(H24), C23(H23), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C35(H35)
4.b Fitted hexagon refined as free rotating group:
 C85(C86,C87,C88,C89,C90), C134(C133,C135,C136,C137,C138), C49(C54,C53,C52,C51,
 C50), C43(C48,C47,C46,C45,C44), C73(C78,C77,C76,C75,C74), C37(C42,C41,C40,C39,
 C38), C61(C62,C63,C64,C65,C66), C67(C68,C69,C70,C71,C72), C10(C9,C8,C7,C6,N3),
 C56(C57,C58,C59,C60,C55)
;