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_4128346
_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 Hg1 S18'
_chemical_formula_sum            'C72 H162 Au24 Hg S18'
_chemical_formula_weight         6532.87
_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                107.6140(10)
_cell_angle_beta                 91.3950(10)
_cell_angle_gamma                117.1740(10)
_cell_formula_units_Z            2
_cell_length_a                   16.2584(2)
_cell_length_b                   17.3297(3)
_cell_length_c                   25.0056(4)
_cell_measurement_reflns_used    59504
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      76.6220
_cell_measurement_theta_min      3.0570
_cell_volume                     5863.12(17)
_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      120.01(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 0.999
_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      2.00  34.00   1.00    2.00    --   38.00  87.00 -74.64   32
  2  \w   -116.00 -17.00   1.00    2.00    --  -41.65 -37.00-150.00   99
  3  \w   -114.00 -14.00   1.00    2.00    --  -41.65 -57.00 -30.00  100
  4  \w   -114.00 -14.00   1.00    2.00    --  -41.65 -57.00  90.00  100
  5  \w   -116.00 -17.00   1.00    2.00    --  -41.65 -37.00 120.00   99
  6  \w    -96.00  -2.00   1.00    2.00    --  -41.65 125.00 -60.00   94
  7  \w     23.00  98.00   1.00    2.00    --   41.65-125.00-120.00   75
  8  \w     16.00  45.00   1.00    2.00    --   50.00  82.00-149.37   29
  9  \w     16.00  45.00   1.00    2.00    --   50.00  82.00  55.54   29
 10  \w     16.00  45.00   1.00    2.00    --   50.00  81.00 -28.90   29
 11  \w     16.00  45.00   1.00    2.00    --   50.00  82.00 128.16   29
 12  \w     29.00 138.00   1.00    2.00    --   62.00  77.00-156.83  109
 13  \w     29.00 138.00   1.00    2.00    --   62.00  77.00-114.57  109
 14  \w     33.00 142.00   1.00    2.00    --   66.00  77.00 -35.04  109
 15  \w     34.00  60.00   1.00    2.00    --   66.00  76.00  19.36   26
 16  \w    100.00 135.00   1.00    2.00    --   66.00  76.00  19.36   35
 17  \w     37.00  63.00   1.00    2.00    --   70.00  77.00  -9.52   26
 18  \w     38.00  65.00   1.00    2.00    --   70.00  76.00 130.79   27
 19  \w     37.00  63.00   1.00    2.00    --   70.00  77.00-102.27   26
 20  \w     37.00  63.00   1.00    2.00    --   70.00  77.00  89.40   26
 21  \w    118.00 146.00   1.00    2.00    --   70.00  77.00  89.40   28
 22  \w     43.00  68.00   1.00    2.00    --   74.00  76.00  98.78   25
 23  \w     41.00  67.00   1.00    2.00    --   74.00  77.00 -74.86   26
 24  \w     41.00  67.00   1.00    2.00    --   74.00  77.00 160.41   26
 25  \w     41.00  67.00   1.00    2.00    --   74.00  77.00  40.61   26
 26  \w     42.00  68.00   1.00    2.00    --   74.00  76.00-131.81   26
 27  \w     49.00 150.00   1.00   10.00    --   78.00  68.00  62.23  101
 28  \w     47.00  72.00   1.00   10.00    --   78.00  75.00-175.89   25
 29  \w    100.00 158.00   1.00   10.00    --   82.00  76.00-115.06   58
 30  \w     50.00  76.00   1.00   10.00    --   82.00  76.00-115.06   26
 31  \w     52.00  78.00   1.00   10.00    --   82.00  68.00 -56.27   26
 32  \w     51.00  77.00   1.00   10.00    --   82.00  73.00  88.88   26
 33  \w     54.00  80.00   1.00   10.00    --   86.00  76.00 -12.79   26
 34  \w     57.00  83.00   1.00   10.00    --   90.00  77.00 -42.50   26
 35  \w     57.00  94.00   1.00   10.00    --   90.00  77.00 154.86   37
 36  \w     58.00  84.00   1.00   10.00    --   90.00  74.00 -59.86   26
 37  \w     63.00  89.00   1.00   10.00    --   94.00  70.00 111.12   26
 38  \w     67.00  97.00   1.00   10.00    --   98.00  72.00 133.90   30
 39  \w    109.00 165.00   1.00   10.00    --   98.00  73.00-162.86   56
 40  \w     66.00  96.00   1.00   10.00    --   98.00  73.00-162.86   30
 41  \w     66.00  95.00   1.00   10.00    --   98.00  75.00 166.53   29
 42  \w    122.00 164.00   1.00   10.00    --  102.00  63.00 -95.61   42
 43  \w     73.00  99.00   1.00   10.00    --  102.00  63.00 -95.61   26
 44  \w     70.00  96.00   1.00   10.00    --  102.00  73.00   2.49   26
 45  \w     80.00 169.00   1.00   10.00    --  112.00  77.00-180.00   89
 46  \w    134.00 161.00   1.00   10.00    --  112.00  69.00 -73.70   27
 47  \w     82.00 132.00   1.00   10.00    --  112.00  69.00 -73.70   50
 48  \w     84.00 115.00   1.00   10.00    --  112.00  61.00  30.00   31
 49  \w     84.00 111.00   1.00   10.00    --  112.00  61.00  60.00   27
 50  \w    147.00 172.00   1.00   10.00    --  112.00  74.00 -95.84   25
 51  \w     79.00 164.00   1.00   10.00    --  112.00  77.00 -60.00   85
 52  \w     80.00 107.00   1.00   10.00    --  112.00  74.00 -95.84   27
 53  \w     79.00 178.00   1.00   10.00    --  112.00  77.00  90.00   99
 54  \w     79.00 176.00   1.00   10.00    --  112.00  77.00 -30.00   97
 55  \w     53.00 139.00   1.00   10.00    --  112.00 -61.00-150.00   86
 56  \w    120.00 178.00   1.00   10.00    --  112.00  61.00-120.00   58
 57  \w     83.00 116.00   1.00   10.00    --  112.00  61.00-120.00   33
 58  \w     41.00 116.00   1.00   10.00    --  112.00-111.00-150.00   75
 59  \w     79.00 178.00   1.00   10.00    --  112.00  77.00   0.00   99
 60  \w     79.00 175.00   1.00   10.00    --  112.00  77.00  60.00   96
 61  \w     79.00 155.00   1.00   10.00    --  112.00  77.00 120.00   76
 62  \w    110.00 139.00   1.00   10.00    --  112.00 -61.00  30.00   29
 63  \w     43.00 108.00   1.00   10.00    --  112.00 -61.00  30.00   65
 64  \w     79.00 173.00   1.00   10.00    --  112.00  77.00  30.00   94
 65  \w    130.00 178.00   1.00   10.00    --  112.00 111.00 120.00   48
 66  \w     79.00 177.00   1.00   10.00    --  112.00  77.00-150.00   98
 67  \w     79.00 164.00   1.00   10.00    --  112.00  77.00 150.00   85
 68  \w     43.00 109.00   1.00   10.00    --  112.00 -94.00  30.00   66
 69  \w     55.00 116.00   1.00   10.00    --  112.00-111.00-120.00   61
 70  \w     61.00 104.00   1.00   10.00    --  112.00 -94.00 120.00   43
 71  \w     80.00 116.00   1.00   10.00    --  112.00-111.00 -30.00   36
;
_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      -0.0300020000
_diffrn_orient_matrix_UB_12      -0.0832203000
_diffrn_orient_matrix_UB_13      0.0199902000
_diffrn_orient_matrix_UB_21      0.1027622000
_diffrn_orient_matrix_UB_22      0.0195367000
_diffrn_orient_matrix_UB_23      0.0083914000
_diffrn_orient_matrix_UB_31      0.0178094000
_diffrn_orient_matrix_UB_32      0.0640085000
_diffrn_orient_matrix_UB_33      0.0621900000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_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            134803
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.997
_diffrn_reflns_theta_min         3.063
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    60.324
_exptl_absorpt_correction_T_max  0.260
_exptl_absorpt_correction_T_min  0.016
_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    3.700
_exptl_crystal_description       plank
_exptl_crystal_F_000             5716
_exptl_crystal_size_max          0.442
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.036
_refine_diff_density_min         -3.394
_refine_diff_density_rms         0.333
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         23033
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0396
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0646P)^2^+40.0534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1040
_refine_ls_wR_factor_ref         0.1075
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21004
_reflns_number_total             23033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08228_si_006.cif
_cod_data_source_block           wf113_1_r2-abs
_cod_original_cell_volume        5863.11(17)
_cod_database_code               4128346
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72  H162 S18 Au25 Hg1'
_chemical_oxdiff_usercomment     'black Au-cluster thin long plates'
_shelx_estimated_absorpt_t_max   0.196
_shelx_estimated_absorpt_t_min   0.015
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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, All C(H,H,H,H,H,H) groups
2. Shared sites
{Au6, Hg6}
{Au4, Hg4}
{Au3, Hg3}
{Au7, Hg7}
{Au2, Hg2}
{Au5, Hg5}
{Au20, Hg20}
{Au21, Hg21}
{Au24, Hg24}
{Au23, Hg23}
{Au22, Hg22}
{Au25, Hg25}
3. Restrained distances
 C2B-C3B
 1.51 with sigma of 0.02
 C15B-C14
 1.51 with sigma of 0.02
 C59B-C60B
 1.51 with sigma of 0.02
 C3B-C4
 1.51 with sigma of 0.02
 C15A-C14
 1.51 with sigma of 0.02
 C59A-C60A
 1.51 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C64) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C28) = Uanis(C27) = Uanis(C26) = Uanis(C25)
Uanis(C39A) = Uanis(C39B)
Uanis(C40B) = Uanis(C40A)
Uanis(C56A) = Uanis(C55A) = Uanis(C54A) = Uanis(C54B) = Uanis(C55B) =
Uanis(C56B)
Uanis(C16B) = Uanis(C16A) = Uanis(C15B) = Uanis(C15A) = Uanis(C14) = Uanis(C13)
Uanis(C58A) = Uanis(C60A)
Uanis(C4) = Uanis(C3A) = Uanis(C2A) = Uanis(C1)
Uanis(C1) = Uanis(C2A) = Uanis(C2B) = Uanis(C3B) = Uanis(C3A) = Uanis(C4)
Uanis(C58B) = Uanis(C59B) = Uanis(C60B)
Uanis(Au6) = Uanis(Hg6)
Uanis(Au4) = Uanis(Hg4)
Uanis(Au3) = Uanis(Hg3)
Uanis(Au2) = Uanis(Hg2)
Uanis(Au5) = Uanis(Hg5)
Uanis(Au7) = Uanis(Hg7)
Uanis(Au21) = Uanis(Hg21)
Uanis(Au24) = Uanis(Hg24)
Uanis(Au23) = Uanis(Hg23)
Uanis(Au22) = Uanis(Hg22)
Uanis(Au25) = Uanis(Hg25)
Uanis(Au20) = Uanis(Hg20)
5. Others
 Sof(H1BC)=Sof(H1BD)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=
 Sof(H4BD)=Sof(H4BE)=Sof(H4BF)=Sof(H14C)=Sof(H14D)=Sof(C15B)=Sof(H15C)=
 Sof(H15D)=Sof(C16B)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(H37C)=Sof(H37D)=
 Sof(C38B)=Sof(H38C)=Sof(H38D)=Sof(C39B)=Sof(H39C)=Sof(H39D)=Sof(C40B)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(H53C)=Sof(H53D)=Sof(C54B)=Sof(H54C)=
 Sof(H54D)=Sof(C55B)=Sof(H55C)=Sof(H55D)=Sof(C56B)=Sof(H56D)=Sof(H56E)=
 Sof(H56F)=Sof(H57C)=Sof(H57D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=Sof(C59B)=
 Sof(H59C)=Sof(H59D)=Sof(C60B)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=
 Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(H14A)=Sof(H14B)=Sof(C15A)=Sof(H15A)=
 Sof(H15B)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(H37A)=Sof(H37B)=
 Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(C40A)=
 Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(H53A)=Sof(H53B)=Sof(C54A)=Sof(H54A)=
 Sof(H54B)=Sof(C55A)=Sof(H55A)=Sof(H55B)=Sof(C56A)=Sof(H56A)=Sof(H56B)=
 Sof(H56C)=Sof(H57A)=Sof(H57B)=Sof(C58A)=Sof(H58A)=Sof(H58B)=Sof(C59A)=
 Sof(H59A)=Sof(H59B)=Sof(C60A)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Fixed Sof: Hg2(0.0833) Hg3(0.0833) Hg4(0.0833) Hg5(0.0833) Hg6(0.0833)
 Hg7(0.0833) Hg20(0.0833) Hg21(0.0833) Hg22(0.0833) Hg23(0.0833) Hg24(0.0833)
 Hg25(0.0833) 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)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD), C2A(H2AA,H2AB), C2B(H2BA,H2BB), C3A(H3AA,H3AB),
 C3B(H3BA,H3BB), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C14(H14C,H14D),
 C15A(H15A,H15B), C15B(H15C,H15D), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), 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), C37(H37C,
 H37D), C38A(H38A,H38B), C38B(H38C,H38D), C39A(H39A,H39B), C39B(H39C,H39D),
 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), C53(H53C,H53D), C54A(H54A,H54B), C54B(H54C,H54D), C55A(H55A,H55B),
 C55B(H55C,H55D), C57(H57A,H57B), C57(H57C,H57D), C58A(H58A,H58B), C58B(H58C,
 H58D), C59A(H59A,H59B), C59B(H59C,H59D), C61(H61A,H61B), C62(H62A,H62B),
 C63(H63A,H63B), 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:
 C68(H68A,H68B,H68C)
6.c Idealised Me refined as rotating group:
 C4(H4AA,H4AB,H4AC), C4(H4BD,H4BE,H4BF), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C),
 C16A(H16A,H16B,H16C), C16B(H16D,H16E,H16F), C20(H20A,H20B,H20C), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C36(H36A,H36B,H36C),
 C40A(H40A,H40B,H40C), C40B(H40D,H40E,H40F), C44(H44A,H44B,H44C), C48(H48A,H48B,
 H48C), C52(H52A,H52B,H52C), C56A(H56A,H56B,H56C), C56B(H56D,H56E,H56F),
 C60A(H60A,H60B,H60C), C60B(H60D,H60E,H60F), C64(H64A,H64B,H64C), C72(H72A,H72B,
 H72C)
;
_shelx_res_checksum              21814
_shelx_hkl_checksum              39686
_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 1.894
_oxdiff_exptl_absorpt_empirical_full_min 0.545