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_4128350
_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         'C144 H162 Au24 Hg1 S18'
_chemical_formula_sum            'C144 H162 Au24 Hg S18'
_chemical_formula_weight         7397.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_symmetry_space_group_name_Hall  '-P 2ab 2ac'
_symmetry_space_group_name_H-M   'P c c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.2914(4)
_cell_length_b                   27.0095(3)
_cell_length_c                   18.5163(2)
_cell_measurement_reflns_used    37551
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      29.6910
_cell_measurement_theta_min      1.9770
_cell_volume                     15649.3(3)
_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 0.999
_diffrn_measured_fraction_theta_max 0.981
_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    -42.00 100.50   0.75  100.00    --   16.09  19.00-120.00  190
  2  \w    -49.00   0.50   0.75  100.00    --  -16.25  57.00 150.00   66
;
_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      -0.0139006000
_diffrn_orient_matrix_UB_12      -0.0090642000
_diffrn_orient_matrix_UB_13      -0.0272228000
_diffrn_orient_matrix_UB_21      -0.0179085000
_diffrn_orient_matrix_UB_22      0.0068450000
_diffrn_orient_matrix_UB_23      0.0212597000
_diffrn_orient_matrix_UB_31      -0.0001476000
_diffrn_orient_matrix_UB_32      0.0236784000
_diffrn_orient_matrix_UB_33      -0.0165499000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            71320
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.500
_diffrn_reflns_theta_min         1.863
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    23.657
_exptl_absorpt_correction_T_max  0.499
_exptl_absorpt_correction_T_min  0.041
_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    3.140
_exptl_crystal_description       plate
_exptl_crystal_F_000             13160
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.751
_refine_diff_density_min         -1.808
_refine_diff_density_rms         0.310
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.235
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         19473
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.235
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0119P)^2^+181.6796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0797
_refine_ls_wR_factor_ref         0.0826
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17027
_reflns_number_total             19473
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08228_si_003.cif
_cod_data_source_block           fw172_fm_190207b_r2-abs
_cod_database_code               4128350
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Au24 Hg1 S18 C144 H162'
_shelx_estimated_absorpt_t_max   0.537
_shelx_estimated_absorpt_t_min   0.053
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{Au2, Hg2}
{Au3, Hg3}
{Au4, Hg4}
{Au5, Hg5}
{Au6, Hg6}
{Au7, Hg7}
3. Restrained distances
 C35A-C34A
 1.51 with sigma of 0.02
 C34B-C33B = C35B-C34B
 1.51 with sigma of 0.02
 C28B-C27 = C32B-C27
 1.39 with sigma of 0.02
4. Restrained planarity
 C50B, C51B, C52B, C53B, C54B, C55B, C56B
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(Au2) = Uanis(Hg2)
Uanis(Au3) = Uanis(Hg3)
Uanis(Au4) = Uanis(Hg4)
Uanis(Au5) = Uanis(Hg5)
Uanis(Au6) = Uanis(Hg6)
Uanis(Au7) = Uanis(Hg7)
Uanis(C40A) = Uanis(C39A) = Uanis(C38A) = Uanis(C37A) = Uanis(C36A) =
Uanis(C35A) = Uanis(C40B) = Uanis(C39B) = Uanis(C38B) = Uanis(C37B) =
Uanis(C36B) = Uanis(C35B)
Uanis(C34A) = Uanis(C34B) = Uanis(C33A) = Uanis(C33B) = Uanis(C35A) =
Uanis(C35B)
Uanis(Au13) = Uanis(Au23)
Uanis(S7A) = Uanis(S7B)
Uanis(C49A) = Uanis(C49B)
Uanis(C54B) = Uanis(C54A)
Uanis(C50A) = Uanis(C50B)
Uanis(C51B) = Uanis(C56B) = Uanis(C55B) = Uanis(C54B) = Uanis(C53B) =
Uanis(C52B) = Uanis(C50B)
Uanis(C28A) = Uanis(C29A) = Uanis(C30A) = Uanis(C31A) = Uanis(C32A)
Uanis(C32B) = Uanis(C31B) = Uanis(C30B) = Uanis(C29B) = Uanis(C28B)
6. Others
 Sof(S5A)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=
 Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=
 Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(C35B)=Sof(C36B)=Sof(H36B)=Sof(C37B)=
 Sof(H37B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=Sof(H39B)=Sof(C40B)=Sof(H40B)=1-FVAR(1)
 Sof(S5B)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33B)=Sof(H33C)=Sof(H33D)=
 Sof(C34B)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=
 Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=FVAR(1)
 Sof(Au23)=Sof(S7B)=Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(C50B)=Sof(H50C)=
 Sof(H50D)=Sof(C51B)=Sof(H51B)=Sof(C52B)=Sof(H52B)=Sof(C53B)=Sof(H53B)=
 Sof(C54B)=Sof(H54B)=Sof(C55B)=Sof(H55B)=Sof(C56B)=1-FVAR(2)
 Sof(Au13)=Sof(S7A)=Sof(C49A)=Sof(H49A)=Sof(H49B)=Sof(C50A)=Sof(H50A)=
 Sof(H50B)=Sof(C51A)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=
 Sof(H54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=FVAR(2)
 Fixed Sof: Hg2(0.0833) Hg3(0.0833) Hg4(0.0833) Hg5(0.0833) Hg6(0.0833)
 Hg7(0.0833) Au2(0.9167) Au3(0.9167) Au4(0.9167) Au5(0.9167) Au6(0.9167)
 Au7(0.9167)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B),
 C18(H18A,H18B), C25(H25A,H25B), C26(H26A,H26B), C33A(H33A,H33B), C33B(H33C,
 H33D), C34A(H34A,H34B), C34B(H34C,H34D), C41(H41A,H41B), C42(H42A,H42B),
 C49A(H49A,H49B), C49B(H49C,H49D), C50A(H50A,H50B), C50B(H50C,H50D), C57(H57A,
 H57B), C58(H58A,H58B), C65(H65A,H65B), C66(H66A,H66B)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
 C28A(H28A), C28B(H28B), C29A(H29A), C29B(H29B), C30A(H30A), C30B(H30B),
 C31A(H31A), C31B(H31B), C32A(H32A), C32B(H32B), C36A(H36A), C37A(H37A),
 C38A(H38A), C39A(H39A), C40A(H40A), C36B(H36B), C37B(H37B), C38B(H38B),
 C39B(H39B), C40B(H40B), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
 C51B(H51B), C52B(H52B), C53B(H53B), C54B(H54B), C55B(H55B), C52A(H52A),
 C53A(H53A), C54A(H54A), C55A(H55A), C56A(H56A), C60(H60), C61(H61), C62(H62),
 C63(H63), C64(H64), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72)
7.c Fitted hexagon refined as free rotating group:
 C35A(C36A,C37A,C38A,C39A,C40A), C35B(C36B,C37B,C38B,C39B,C40B), C51B(C52B,
 C53B,C54B,C55B,C56B)
;
_shelx_res_checksum              10561
_shelx_hkl_checksum              27826
_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 1.609
_oxdiff_exptl_absorpt_empirical_full_min 0.561