Metal Doping of Au<sub>25</sub>(SR)<sub>18</sub><sup>-</sup> Clusters: Insights and Hindsights.
Fei, Wenwen; Antonello, Sabrina; Dainese, Tiziano; Dolmella, Alessandro; Lahtinen, Manu; Rissanen, Kari; Venzo, Alfonso; Maran, Flavio; Journal of the American Chemical Society 141 (2019) 16033–16045; doi:10.1021/jacs.9b08228

data_4128347
_publ_section_title
;
 Metal Doping of Au<sub>25</sub>(SR)<sub>18</sub><sup>-</sup> Clusters:
 Insights and Hindsights.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16033
_journal_page_last               16045
_journal_paper_doi               10.1021/jacs.9b08228
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C72 H162 Au24 Cd1 S18'
_chemical_formula_sum            'C72 H162 Au24 Cd S18'
_chemical_formula_weight         6444.68
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                107.5790(10)
_cell_angle_beta                 91.4000(10)
_cell_angle_gamma                117.2510(10)
_cell_formula_units_Z            2
_cell_length_a                   16.2535(2)
_cell_length_b                   17.3097(2)
_cell_length_c                   25.0233(3)
_cell_measurement_reflns_used    51761
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.4980
_cell_measurement_theta_min      2.9120
_cell_volume                     5855.46(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1977
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -66.00  33.00   1.00    2.00    --  -41.65  37.00 -90.00   99
  2  \w    -70.00  31.00   1.00    2.00    --  -41.65  57.00  30.00  101
  3  \w   -114.00 -14.00   1.00    2.00    --  -41.65 -57.00-120.00  100
  4  \w      6.00  35.00   1.00    2.00    --   41.65  86.00 131.29   29
  5  \w      1.00  83.00   1.00    2.00    --   41.65 -99.00  30.00   82
  6  \w      1.00  83.00   1.00    2.00    --   41.65 -99.00 -30.00   82
  7  \w    -33.00  66.00   1.00    2.00    --   41.65 -37.00  90.00   99
  8  \w     23.00  98.00   1.00    2.00    --   41.65-125.00-150.00   75
  9  \w    100.00 178.00   1.00    7.50    --  112.00 111.00 -30.00   78
 10  \w     40.00 141.00   1.00    7.50    --  112.00 -61.00  30.00  101
 11  \w     79.00 178.00   1.00    7.50    --  112.00  77.00-150.00   99
 12  \w     37.00  82.00   1.00    7.50    --  112.00-111.00 -90.00   45
 13  \w     88.00 115.00   1.00    7.50    --  112.00  45.00 -30.00   27
 14  \w     72.00 108.00   1.00    7.50    --  112.00 -53.00-110.56   36
 15  \w     42.00  82.00   1.00    7.50    --  112.00-111.00 -60.00   40
 16  \w     45.00  81.00   1.00    7.50    --  112.00-111.00  60.00   36
 17  \w     66.00 100.00   1.00    7.50    --  112.00 -94.00-120.00   34
 18  \w     91.00 116.00   1.00    7.50    --  112.00-111.00-150.00   25
 19  \w     88.00 115.00   1.00    7.50    --  112.00-111.00  60.00   27
 20  \w    106.00 140.00   1.00    7.50    --  112.00 -61.00 120.00   34
 21  \w    106.00 139.00   1.00    7.50    --  112.00 -77.00  60.00   33
 22  \w     84.00 112.00   1.00    7.50    --  112.00  62.00  24.83   28
 23  \w    137.00 176.00   1.00    7.50    --  112.00  62.00  24.83   39
 24  \w    115.00 144.00   1.00    7.50    --  112.00 111.00  60.00   29
 25  \w     88.00 116.00   1.00    7.50    --  112.00-111.00 -90.00   28
 26  \w     87.00 142.00   1.00    7.50    --  112.00  45.00-180.00   55
 27  \w    133.00 160.00   1.00    7.50    --  112.00  45.00 -30.00   27
 28  \w     50.00  98.00   1.00    7.50    --  112.00 -94.00  60.00   48
 29  \w     91.00 116.00   1.00    7.50    --  112.00-111.00 150.00   25
 30  \w     56.00  83.00   1.00    7.50    --  112.00-111.00 150.00   27
 31  \w     48.00  75.00   1.00    7.50    --  112.00-111.00-150.00   27
 32  \w     30.00 108.00   1.00    7.50    --  112.00 -94.00-150.00   78
 33  \w    147.00 174.00   1.00    7.50    --  112.00  77.00  90.00   27
 34  \w    139.00 174.00   1.00    7.50    --  112.00  30.00 150.00   35
 35  \w     90.00 116.00   1.00    7.50    --  112.00-111.00 -30.00   26
 36  \w     80.00 111.00   1.00    7.50    --  112.00  77.00  90.00   31
 37  \w     53.00  86.00   1.00    7.50    --  112.00 -94.00 -30.00   33
 38  \w     50.00  75.00   1.00    7.50    --  112.00-111.00-180.00   25
 39  \w     90.00 116.00   1.00    7.50    --  112.00-111.00-180.00   26
 40  \w     74.00 101.00   1.00    7.50    --  112.00 -30.00 -90.00   27
 41  \w     32.00  89.00   1.00    7.50    --  112.00 -15.00 -30.00   57
 42  \w     66.00 100.00   1.00    7.50    --  112.00 -30.00 120.00   34
 43  \w     43.00  78.00   1.00    7.50    --  112.00 -61.00 120.00   35
 44  \w    138.00 178.00   1.00    7.50    --  112.00  30.00 120.00   40
 45  \w     69.00  99.00   1.00    7.50    --  112.00 -94.00 -90.00   30
 46  \w     55.00  82.00   1.00    7.50    --  112.00 -94.00  30.00   27
 47  \w     77.00 109.00   1.00    7.50    --  112.00 -94.00  90.00   32
 48  \w     54.00 103.00   1.00    7.50    --  112.00 -94.00 120.00   49
 49  \w     60.00 102.00   1.00    7.50    --  112.00  15.00-150.00   42
 50  \w    113.00 138.00   1.00    7.50    --  112.00  15.00-120.00   25
 51  \w    147.00 172.00   1.00    7.50    --  112.00  15.00-120.00   25
 52  \w     39.00 109.00   1.00    7.50    --  112.00 -94.00 -60.00   70
 53  \w     81.00 106.00   1.00    7.50    --  112.00 -94.00 150.00   25
 54  \w     86.00 113.00   1.00    7.50    --  112.00-111.00  90.00   27
 55  \w     50.00 103.00   1.00    7.50    --  112.00 -94.00   0.00   53
 56  \w     90.00 117.00   1.00    7.50    --  112.00  45.00  60.00   27
 57  \w     60.00  87.00   1.00    7.50    --  112.00 178.00-180.00   27
 58  \w     98.00 140.00   1.00    7.50    --  112.00 178.00-180.00   42
 59  \w     95.00 122.00   1.00    7.50    --  112.00  30.00 120.00   27
 60  \w     64.00 144.00   1.00    7.50    --  112.00 -25.00-128.79   80
 61  \w     64.00 130.00   1.00    7.50    --  112.00  15.00 -30.00   66
 62  \w     36.00 120.00   1.00    7.50    --  112.00 -24.00  39.07   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0312539000
_diffrn_orient_matrix_UB_12      0.0267122000
_diffrn_orient_matrix_UB_13      0.0572292000
_diffrn_orient_matrix_UB_21      -0.0518333000
_diffrn_orient_matrix_UB_22      0.0404256000
_diffrn_orient_matrix_UB_23      -0.0250982000
_diffrn_orient_matrix_UB_31      -0.0902152000
_diffrn_orient_matrix_UB_32      -0.0953715000
_diffrn_orient_matrix_UB_33      -0.0206220000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0570
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            98087
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.990
_diffrn_reflns_theta_min         2.983
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    59.539
_exptl_absorpt_correction_T_max  0.196
_exptl_absorpt_correction_T_min  0.014
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    3.655
_exptl_crystal_description       plate
_exptl_crystal_F_000             5652
_exptl_crystal_size_max          0.195
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.061
_refine_diff_density_max         4.593
_refine_diff_density_min         -3.211
_refine_diff_density_rms         0.386
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1043
_refine_ls_number_reflns         23013
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0481
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0882P)^2^+34.2951P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1275
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21056
_reflns_number_total             23013
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08228_si_005.cif
_cod_data_source_block           wf127_1_r2-abs_8-icosahderal
_cod_original_cell_volume        5855.45(13)
_cod_database_code               4128347
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72 H162 Au24 Cd1 S18'
_reflns_odcompleteness_completeness 98.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Au4, Cd4}
{Au6, Cd6}
{Au5, Cd5}
{Au7, Cd7}
{Au21, Cd21}
{Au24, Cd24}
{Au22, Cd22}
{Au25, Cd25}
{Au23, Cd23}
{Au3, Cd3}
{Au2, Cd2}
{Au20, Cd20}
3. Restrained distances
 C9-C10B = C11B-C10B = C12B-C11B
 1.53 with sigma of 0.02
 C9-C10A = C11A-C10A = C12A-C11A
 1.53 with sigma of 0.02
 C15-C14
 1.53 with sigma of 0.02
 C18A-C17 = C19A-C18A = C20A-C19A
 1.53 with sigma of 0.02
 C18B-C17 = C20B-C19B = C19B-C18B
 1.53 with sigma of 0.02
 C58B-C59B = C60B-C59B = C60A-C59A = C59A-C58A
 1.53 with sigma of 0.02
 C61-C62B = C63B-C62B = C64B-C63B = C62A-C61 = C63A-C62A = C64A-C63A
 1.53 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C10B) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq,
Uanis(C11B) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C12A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18A) \\sim Ueq, Uanis(C18B) \\sim Ueq, Uanis(C19B) \\sim Ueq,
Uanis(C19A) \\sim Ueq, Uanis(C20B) \\sim Ueq, Uanis(C20A) \\sim Ueq: with sigma
of 0.05 and sigma for terminal atoms of 0.1
Uanis(C64A) \\sim Ueq, Uanis(C64B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C10B) = Uanis(C10A) = Uanis(C11B) = Uanis(C11A) = Uanis(C12B) =
Uanis(C12A)
Uanis(C18B) = Uanis(C18A) = Uanis(C19A) = Uanis(C19B) = Uanis(C20B) =
Uanis(C20A)
Uanis(C58A) = Uanis(C58B) = Uanis(C59B) = Uanis(C59A)
Uanis(C60B) = Uanis(C60A)
Uanis(C62B) = Uanis(C62A) = Uanis(C63A) = Uanis(C63B)
Uanis(C64A) = Uanis(C64B)
Uanis(Au4) = Uanis(Cd4)
Uanis(Cd6) = Uanis(Au6)
Uanis(Au6) = Uanis(Cd6)
Uanis(Au5) = Uanis(Cd5)
Uanis(Au7) = Uanis(Cd7)
Uanis(Cd21) = Uanis(Au21)
Uanis(Au24) = Uanis(Cd24)
Uanis(Cd22) = Uanis(Au22)
Uanis(Au25) = Uanis(Cd25)
Uanis(Au23) = Uanis(Cd23)
Uanis(Au3) = Uanis(Cd3)
Uanis(Au2) = Uanis(Cd2)
Uanis(Au20) = Uanis(Cd20)
5. Others
 Sof(H9BC)=Sof(H9BD)=Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C11B)=Sof(H11C)=
 Sof(H11D)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(C11A)=Sof(H11A)=
 Sof(H11B)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Sof(H17C)=Sof(H17D)=Sof(C18B)=Sof(H18C)=Sof(H18D)=Sof(C19B)=Sof(H19C)=
 Sof(H19D)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(H17A)=Sof(H17B)=Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(C19A)=Sof(H19A)=
 Sof(H19B)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
 Sof(H57A)=Sof(H57B)=Sof(C58A)=Sof(H58A)=Sof(H58B)=Sof(C59A)=Sof(H59A)=
 Sof(H59B)=Sof(C60A)=Sof(H60A)=Sof(H60B)=Sof(H60C)=1-FVAR(3)
 Sof(H57C)=Sof(H57D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=Sof(C59B)=Sof(H59C)=
 Sof(H59D)=Sof(C60B)=Sof(H60D)=Sof(H60E)=Sof(H60F)=FVAR(3)
 Sof(H61C)=Sof(H61D)=Sof(C62B)=Sof(H62C)=Sof(H62D)=Sof(C63B)=Sof(H63C)=
 Sof(H63D)=Sof(C64B)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(4)
 Sof(H61A)=Sof(H61B)=Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(C63A)=Sof(H63A)=
 Sof(H63B)=Sof(C64A)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(4)
 Fixed Sof: Au2(0.9167) Au3(0.9167) Au4(0.9167) Au5(0.9167) Au6(0.9167)
 Au7(0.9167) Au20(0.9167) Au21(0.9167) Au22(0.9167) Au23(0.9167) Au24(0.9167)
 Au25(0.9167) Cd2(0.0833) Cd3(0.0833) Cd4(0.0833) Cd5(0.0833) Cd6(0.0833)
 Cd7(0.0833) Cd20(0.0833) Cd21(0.0833) Cd22(0.0833) Cd23(0.0833) Cd24(0.0833)
 Cd25(0.0833)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C9(H9BC,H9BD), C9(H9AA,H9AB), C10A(H10A,H10B), C10B(H10C,H10D), C11A(H11A,
 H11B), C11B(H11C,H11D), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C17(H17C,H17D), C17(H17A,H17B), C18A(H18A,H18B), C18B(H18C,H18D), C19A(H19A,
 H19B), C19B(H19C,H19D), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B),
  C31(H31A,H31B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C37(H37A,
 H37B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,H41B), C42(H42A,H42B),
 C43(H43A,H43B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C49(H49A,H49B),
  C50(H50A,H50B), C51(H51A,H51B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,
 H55B), C57(H57A,H57B), C57(H57C,H57D), C58A(H58A,H58B), C58B(H58C,H58D),
 C59A(H59A,H59B), C59B(H59C,H59D), C61(H61A,H61B), C61(H61C,H61D), C62A(H62A,
 H62B), C62B(H62C,H62D), C63A(H63A,H63B), C63B(H63C,H63D), C65(H65A,H65B),
 C66(H66A,H66B), C67(H67A,H67B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B)
6.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F),
 C16(H16A,H16B,H16C), C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C36(H36A,H36B,H36C), C40(H40A,
 H40B,H40C), C44(H44A,H44B,H44C), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C),
 C56(H56A,H56B,H56C), C60A(H60A,H60B,H60C), C60B(H60D,H60E,H60F), C64A(H64A,
 H64B,H64C), C64B(H64D,H64E,H64F), C68(H68A,H68B,H68C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              4424
_shelx_hkl_checksum              95673
_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 1.562
_oxdiff_exptl_absorpt_empirical_full_min 0.706