Hetero-biicosahedral [Au<sub>24</sub>Pd(PPh<sub>3</sub>)<sub>10</sub>(SC<sub>2</sub>H<sub>4</sub>Ph)<sub>5</sub>Cl<sub>2</sub>]<sup>+</sup> nanocluster: selective synthesis and optical and electrochemical properties.
Nair, Lakshmi V.; Hossain, Sakiat; Takagi, Shunjiro; Imai, Yukari; Hu, Guoxiang; Wakayama, Shota; Kumar, Bharat; Kurashige, Wataru; Jiang, De-En; Negishi, Yuichi; Nanoscale 10 (2018) 18969–18979; doi:10.1039/c8nr04078h

data_1552918
_publ_section_title
;
 Hetero-biicosahedral
 [Au<sub>24</sub>Pd(PPh<sub>3</sub>)<sub>10</sub>(SC<sub>2</sub>H<sub>4</sub>Ph)<sub>5</sub>Cl<sub>2</sub>]<sup>+</sup>
 nanocluster: selective synthesis and optical and electrochemical
 properties.
;
_journal_issue                   40
_journal_name_full               Nanoscale
_journal_page_first              18969
_journal_page_last               18979
_journal_paper_doi               10.1039/c8nr04078h
_journal_volume                  10
_journal_year                    2018
_chemical_formula_moiety
'C220 H195 Au25 Cl2 P10 S5, 1.27(F6 Sb), 0.38(F5 Sb), 0.26(F4 Sb1), F0.09 Sb0.12'
_chemical_formula_sum            'C220 H195 Au25 Cl2 F10.62 P10 S5 Sb2.02'
_chemical_formula_weight         8751.88
_chemical_name_systematic        Au25Biicosahedral
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-18 deposited with the CCDC.
2018-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1204(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.44900(14)
_cell_length_b                   35.9379(2)
_cell_length_c                   31.80647(19)
_cell_measurement_reflns_used    114721
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      73.1500
_cell_measurement_theta_min      2.5720
_cell_volume                     23369.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_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    SIR-92
_diffrn_ambient_temperature      113(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     63.00  89.00   0.50    2.37    --    0.00  38.00 -30.00   52
  2  \w     28.00  54.00   0.50    2.37    --    0.00  38.00 -30.00   52
  3  \w     -3.00  24.00   0.50    2.37    --    0.00 -57.00-120.00   54
  4  \w    -23.00  78.00   0.50    2.37    --    0.00  38.00 -60.00  202
  5  \w    -89.00 -40.00   0.50    2.37    --    0.00 -57.00-120.00   98
  6  \w    -27.00  86.00   0.50    2.37    --    0.00  38.00 150.00  226
  7  \w     65.00  91.00   0.50   20.00    --   98.20  77.00 150.00   52
  8  \w      9.00 127.00   0.50   20.00    --   98.20 -61.00 120.00  236
  9  \w    100.00 165.00   0.50   20.00    --   98.20  15.00  60.00  130
 10  \w     11.00 127.00   0.50   20.00    --   98.20 -61.00 -30.00  232
 11  \w     76.00 127.00   0.50   20.00    --   98.20  45.00-180.00  102
 12  \w     64.00  90.00   0.50   20.00    --   98.20  77.00 120.00   52
 13  \w     69.00 157.00   0.50   20.00    --   98.20  30.00 -90.00  176
 14  \w     87.00 112.00   0.50   20.00    --   98.20 -82.00  30.00   50
 15  \w     45.00  82.00   0.50   20.00    --   98.20 -30.00   0.00   74
 16  \w     72.00 176.00   0.50   20.00    --   98.20  45.00 -30.00  208
 17  \w    110.00 182.00   0.50   20.00    --   98.20  45.00 150.00  144
 18  \w     72.00  99.00   0.50   20.00    --   98.20  45.00 150.00   54
 19  \w     22.00  48.00   0.50   20.00    --   98.20 -82.00  90.00   52
 20  \w     74.00 100.00   0.50   20.00    --   98.20 -82.00  90.00   52
 21  \w     25.00 148.00   0.50   20.00    --   98.20 -15.00 150.00  246
 22  \w     82.00 108.00   0.50   20.00    --   98.20 -45.00  60.00   52
 23  \w     19.00 131.00   0.50   20.00    --   98.20 -82.00 -30.00  224
 24  \w     49.00  89.00   0.50   20.00    --   98.20  15.00  60.00   80
 25  \w     75.00 101.00   0.50   20.00    --   98.20  82.00 120.00   52
 26  \w      9.00 132.00   0.50   20.00    --   98.20 -82.00 120.00  246
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0437827000
_diffrn_orient_matrix_UB_12      -0.0262133000
_diffrn_orient_matrix_UB_13      0.0265445000
_diffrn_orient_matrix_UB_21      0.0114265000
_diffrn_orient_matrix_UB_22      0.0312400000
_diffrn_orient_matrix_UB_23      0.0324595000
_diffrn_orient_matrix_UB_31      -0.0602992000
_diffrn_orient_matrix_UB_32      -0.0131636000
_diffrn_orient_matrix_UB_33      0.0242469000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0612
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            250020
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.638
_diffrn_reflns_theta_min         2.486
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    32.178
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.15280
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.487
_exptl_crystal_description       block
_exptl_crystal_F_000             15811
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.578
_refine_diff_density_min         -2.587
_refine_diff_density_rms         0.258
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2504
_refine_ls_number_reflns         46597
_refine_ls_number_restraints     2848
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0670P)^2^+160.2890P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1195
_reflns_Friedel_coverage         0.000
_reflns_number_gt                40024
_reflns_number_total             46597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8nr04078h3.cif
_cod_data_source_block           au25biicosahedral
_cod_original_cell_volume        23369.9(3)
_cod_database_code               1552918
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Au25P10C220H195S5Cl2Sb2F12
_reflns_odcompleteness_completeness 99.99
_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
2. Restrained distances
 Sb2-F11 \\sim Sb2-F8 \\sim Sb2-F7 \\sim Sb2-F12 \\sim Sb2-F10 \\sim Sb2-F9
 with sigma of 0.02
 F11-F8 \\sim F11-F7 \\sim F11-F12 \\sim F11-F10 \\sim F8-F7 \\sim F8-F10 \\sim
F8-F9 \\sim F7-F12 \\sim F7-F9
 \\sim F12-F10 \\sim F12-F9 \\sim F10-F9
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim 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 C24 \\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 C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97
\\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104
\\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111
\\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118
\\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125
\\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132
\\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139
\\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146
\\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C151 \\sim C152 \\sim C153
\\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim C158 \\sim C159 \\sim C160
\\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166 \\sim C167
\\sim C168 \\sim C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim C174
\\sim C175 \\sim C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180 \\sim C181
\\sim C182 \\sim C183 \\sim C184 \\sim C185 \\sim C186 \\sim C187 \\sim C188
\\sim C189 \\sim C190 \\sim C191 \\sim C192 \\sim C193 \\sim C194 \\sim C195
\\sim C196 \\sim C197 \\sim C198 \\sim C199 \\sim C200 \\sim C201 \\sim C202
\\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207 \\sim C208 \\sim C209
\\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim C215 \\sim C216
\\sim C217 \\sim C218 \\sim C219 \\sim C220: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04
Sb2 \\sim F11 \\sim F8 \\sim F7 \\sim F12 \\sim F10 \\sim F9: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Sb5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.002
Uanis(Sb4) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.002
Uanis(F125) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.002
Uanis(C113) = Uanis(C116)
4. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17,
 C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
  C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48,
 C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64,
  C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, C79,
 C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90, C91, C92, C93, C94, C95,
  C96, C97, C98, C99, C100, C101, C102, C103, C104, C105, C106, C107, C108,
 C109, C110, C111, C112, C113, C114, C115, C116, C117, C118, C119, C120, C121,
 C122, C123, C124, C125, C126, C127, C128, C129, C130, C131, C132, C133, C134,
 C135, C136, C137, C138, C139, C140, C141, C142, C143, C144, C145, C146, C147,
 C148, C149, C150, C151, C152, C153, C154, C155, C156, C157, C158, C159, C160,
 C161, C162, C163, C164, C165, C166, C167, C168, C169, C170, C171, C172, C173,
 C174, C175, C176, C177, C178, C179, C180, C181, C182, C183, C184, C185, C186,
 C187, C188, C189, C190, C191, C192, C193, C194, C195, C196, C197, C198, C199,
 C200, C201, C202, C203, C204, C205, C206, C207, C208, C209, C210, C211, C212,
 C213, C214, C215, C216, C217, C218, C219, C220
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Sb2, F11, F8, F7, F12, F10, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(Sb2)+Sof(F11)+Sof(F8)+Sof(F7)+Sof(F12)+Sof(F10)+Sof(F9)]+1*[Sof(Sb3)+
 Sof(F18)+Sof(F14)+Sof(F17)+Sof(F15)+Sof(F13)]+1*[Sof(Sb4)+Sof(F104)+Sof(F121)+
 Sof(F178)+Sof(F290)]+1*[Sof(Sb5)+Sof(F125)]=1 with esd of 0.001
 Sof(Sb2)=Sof(F11)=Sof(F8)=Sof(F7)=Sof(F12)=Sof(F10)=Sof(F9)=FVAR(1)
 Sof(Sb3)=Sof(F18)=Sof(F14)=Sof(F17)=Sof(F15)=Sof(F13)=FVAR(2)
 Sof(Sb4)=Sof(F104)=Sof(F121)=Sof(F178)=Sof(F290)=FVAR(3)
 Sof(F125)=FVAR(4)
 Sof(Sb5)=1.25*FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C9(H9A,H9B), C28(H28A,H28B), C78(H78A,H78B), C80(H80A,H80B),
 C81(H81A,H81B), C117(H11A,H11B), C143(H14A,H14B), C153(H15A,H15B), C154(H15C,
 H15D)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C15(H15), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32), C33(H33),
  C36(H36), C37(H37), C38(H38), C39(H39), C97(H97), C187(H187), C209(H209),
 C136(H136), C34(H34), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
 C48(H48), C49(H49), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57), C58(H58),
  C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
 C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73), C76(H76),
  C77(H77), C79(H79), C82(H82), C83(H83), C84(H84), C86(H86), C87(H87),
 C88(H88), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C95(H95),
  C96(H96), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102), C104(H104),
 C105(H105), C106(H106), C107(H107), C110(H110), C112(H112), C113(H113),
 C114(H114), C115(H115), C116(H116), C118(H118), C119(H119), C120(H120),
 C121(H121), C122(H122), C123(H123), C124(H124), C126(H126), C127(H127),
 C128(H128), C129(H129), C130(H130), C131(H131), C132(H132), C133(H133),
 C135(H135), C137(H137), C138(H138), C139(H139), C140(H140), C141(H141),
 C142(H142), C144(H144), C145(H145), C148(H148), C149(H149), C150(H150),
 C151(H151), C152(H152), C155(H155), C156(H156), C157(H157), C158(H158),
 C160(H160), C161(H161), C162(H162), C163(H163), C164(H164), C165(H165),
 C166(H166), C167(H167), C168(H168), C169(H169), C170(H170), C171(H171),
 C173(H173), C174(H174), C175(H175), C176(H176), C177(H177), C178(H178),
 C179(H179), C180(H180), C181(H181), C182(H182), C183(H183), C184(H184),
 C185(H185), C186(H186), C188(H188), C189(H189), C190(H190), C191(H191),
 C192(H192), C193(H193), C194(H194), C195(H195), C196(H196), C197(H197),
 C198(H198), C199(H199), C200(H200), C201(H201), C202(H202), C203(H203),
 C204(H204), C205(H205), C206(H206), C207(H207), C208(H208), C210(H210),
 C211(H211), C212(H212), C213(H213), C214(H214), C215(H215), C216(H216),
 C217(H217), C218(H218), C219(H219), C220(H220)
6.c Fitted hexagon refined as free rotating group:
 C41(C97,C187,C209,C136,C34), C111(C112,C113,C114,C115,C116), C125(C126,C127,
 C128,C129,C130), C159(C160,C161,C162,C163,C164)
;
_shelx_res_checksum              7442
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.434
_oxdiff_exptl_absorpt_empirical_full_min 0.571