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_4128349
_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             2019-07-02
_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                   31.2563(11)
_cell_length_b                   26.9439(5)
_cell_length_c                   18.4570(5)
_cell_measurement_reflns_used    11881
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      28.9560
_cell_measurement_theta_min      2.2840
_cell_volume                     15543.9(7)
_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 0.997
_diffrn_measured_fraction_theta_max 0.855
_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     -3.00  78.00   0.30   65.00    --   10.43  57.00 150.00  270
  2  \w    -63.00 -30.00   0.30   65.00    --   10.43 -57.00-180.00  110
;
_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      0.0015522000
_diffrn_orient_matrix_UB_12      -0.0226644000
_diffrn_orient_matrix_UB_13      -0.0011544000
_diffrn_orient_matrix_UB_21      0.0382863000
_diffrn_orient_matrix_UB_22      0.0008679000
_diffrn_orient_matrix_UB_23      0.0016879000
_diffrn_orient_matrix_UB_31      -0.0023987000
_diffrn_orient_matrix_UB_32      -0.0010586000
_diffrn_orient_matrix_UB_33      0.0262553000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0940
_diffrn_reflns_av_unetI/netI     0.1498
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.855
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            46697
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.304
_diffrn_reflns_theta_min         1.867
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    23.817
_exptl_absorpt_correction_T_max  0.811
_exptl_absorpt_correction_T_min  0.074
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    3.161
_exptl_crystal_description       plate
_exptl_crystal_F_000             13160
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.115
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.990
_refine_diff_density_min         -3.047
_refine_diff_density_rms         0.539
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     483
_refine_ls_number_reflns         18174
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.1395
_refine_ls_R_factor_gt           0.0824
_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^)+457.7104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1301
_refine_ls_wR_factor_ref         0.1504
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11364
_reflns_number_total             18174
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08228_si_004.cif
_cod_data_source_block           wf171_1_r2-abs
_cod_database_code               4128349
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C144 H162 Au24 Hg1 S18'
_shelx_estimated_absorpt_t_max   0.647
_shelx_estimated_absorpt_t_min   0.088
_reflns_odcompleteness_completeness 99.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Shared sites
{Au2, Hg2}
{Au3, Hg3}
{Au4, Hg4}
{Au5, Hg5}
{Au6, Hg6}
{Au7, Hg7}
3. Restrained distances
 S2B-C9B = S2A-C9A
 1.83 with sigma of 0.02
 S6B-C41
 1.83 with sigma of 0.02
4. Restrained planarity
 C27, C28B, C29B, C30, C31B, C32B
 with sigma of 0.1
 C27, C28A, C29A, C30, C31A, C32A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(S2A) \\sim Ueq, Uanis(S2B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S6A) \\sim Ueq, Uanis(S6B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S8) = Uanis(S9)
Uanis(C25) = Uanis(C26) = Uanis(C28B) = Uanis(C29B) = Uanis(C32A) = Uanis(C29A)
= Uanis(C31B) = Uanis(C32B) = Uanis(C30) = Uanis(C28A) = Uanis(C31A)
Uanis(C1) = Uanis(C2) = Uanis(C3) = Uanis(C4) = Uanis(C5) = Uanis(C6) =
Uanis(C7) = Uanis(C8)
Uanis(C65) = Uanis(C66) = Uanis(C67) = Uanis(C72) = Uanis(C71) = Uanis(C70) =
Uanis(C69) = Uanis(C68)
Uanis(C17) = Uanis(C18) = Uanis(C19) = Uanis(C20) = Uanis(C21) = Uanis(C22) =
Uanis(C23) = Uanis(C24)
Uanis(C33) = Uanis(C34) = Uanis(C35) = Uanis(C36) = Uanis(C37) = Uanis(C38) =
Uanis(C39) = Uanis(C40)
Uanis(C57) = Uanis(C58) = Uanis(C59) = Uanis(C64) = Uanis(C63) = Uanis(C62) =
Uanis(C61) = Uanis(C60)
Uanis(C49) = Uanis(C50) = Uanis(C51) = Uanis(C56) = Uanis(C55) = Uanis(C54) =
Uanis(C53) = Uanis(C52)
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(Au8B) = Uanis(Au8A)
Uanis(C9B) = Uanis(C10B) = Uanis(C11B) = Uanis(C16B) = Uanis(C15B) =
Uanis(C14B) = Uanis(C13B) = Uanis(C12B)
Uanis(C9B) = Uanis(C9A)
Uanis(C10B) = Uanis(C10A)
Uanis(C14B) = Uanis(C11B) = Uanis(C11A)
Uanis(C12B) = Uanis(C12A)
Uanis(C13B) = Uanis(C13A)
Uanis(C14B) = Uanis(C14A)
Uanis(C15B) = Uanis(C15A)
Uanis(C16B) = Uanis(C16A)
Uanis(S2A) = Uanis(S2B)
Uanis(S6A) = Uanis(S6B)
Uanis(C42) = Uanis(C43) = Uanis(C48) = Uanis(C47) = Uanis(C46) = Uanis(C45) =
Uanis(C44)
6. Others
 Sof(Au8B)=1-FVAR(1)
 Sof(Au8A)=FVAR(1)
 Sof(S2B)=Sof(S6A)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C10B)=Sof(H10C)=Sof(H10D)=
 Sof(C16B)=Sof(H16B)=Sof(C11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=
 Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(H41C)=Sof(H41D)=1-FVAR(2)
 Sof(S2A)=Sof(S6B)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(H10B)=
 Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(H41A)=Sof(H41B)=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) C28A(0.5) H28A(0.5) C29A(0.5) H29A(0.5) H30(0.5) H30A(0.5)
 C31A(0.5) H31A(0.5) C32A(0.5) H32A(0.5) C28B(0.5) H28B(0.5) C29B(0.5)
 H29B(0.5) C31B(0.5) H31B(0.5) C32B(0.5) H32B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C9A(H9AA,H9AB), C9B(H9BA,H9BB), C10A(H10A,H10B),
 C10B(H10C,H10D), C17(H17A,H17B), C18(H18A,H18B), C25(H25A,H25B), C26(H26A,
 H26B), C33(H33A,H33B), C34(H34A,H34B), C42(H42A,H42B), C49(H49A,H49B),
 C50(H50A,H50B), C57(H57A,H57B), C58(H58A,H58B), C65(H65A,H65B), C66(H66A,H66B),
  C41(H41C,H41D), C41(H41A,H41B)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C12A(H12A), C13A(H13A), C14A(H14A),
 C15A(H15A), C16A(H16A), C16B(H16B), C12B(H12B), C13B(H13B), C14B(H14B),
 C15B(H15B), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C28A(H28A),
 C29A(H29A), C30(H30), C30(H30A), C31A(H31A), C32A(H32A), C28B(H28B),
 C29B(H29B), C31B(H31B), C32B(H32B), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52), C53(H53),
  C54(H54), C55(H55), C56(H56), 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:
 C11A(C12A,C13A,C14A,C15A,C16A), C16B(C11B,C12B,C13B,C14B,C15B), C27(C28A,C29A,
 C30,C31A,C32A)
;
_shelx_res_checksum              7804
_shelx_hkl_checksum              23454
_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 1.459
_oxdiff_exptl_absorpt_empirical_full_min 0.592