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_4128348
_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 Cd1 S18'
_chemical_formula_sum            'C144 H162 Au24 Cd S18'
_chemical_formula_weight         7309.40
_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                   31.3135(5)
_cell_length_b                   27.0073(3)
_cell_length_c                   18.5226(2)
_cell_measurement_reflns_used    20773
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.5820
_cell_measurement_theta_min      2.1140
_cell_volume                     15664.4(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      120.00(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 0.999
_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    -66.00  33.00   1.00   12.50    --  -41.65  37.00-150.00   99
  2  \w     51.00  97.00   1.00   12.50    --   41.65-125.00-150.00   46
  3  \w      3.00  37.00   1.00   12.50    --   41.65 -99.00 150.00   34
  4  \w    101.00 134.00   1.00   60.00    --  112.00 111.00  60.00   33
  5  \w    101.00 132.00   1.00   60.00    --  112.00 111.00  30.00   31
  6  \w    149.00 176.00   1.00   60.00    --  112.00 111.00  30.00   27
  7  \w    107.00 133.00   1.00   60.00    --  112.00 111.00   0.00   26
  8  \w     65.00 114.00   1.00   60.00    --  112.00-111.00   0.00   49
  9  \w    146.00 178.00   1.00   60.00    --  112.00 111.00  60.00   32
 10  \w    150.00 178.00   1.00   60.00    --  112.00 111.00   0.00   28
 11  \w     39.00  84.00   1.00   60.00    --  112.00 -94.00   0.00   45
 12  \w     94.00 159.00   1.00   60.00    --  112.00  77.00 150.00   65
 13  \w     94.00 139.00   1.00   60.00    --  112.00  45.00 -90.00   45
 14  \w    117.00 161.00   1.00   60.00    --  112.00 111.00 -30.00   44
 15  \w     41.00 134.00   1.00   60.00    --  112.00 -51.00 -13.95   93
;
_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      0.0147148000
_diffrn_orient_matrix_UB_12      -0.0481877000
_diffrn_orient_matrix_UB_13      0.0057285000
_diffrn_orient_matrix_UB_21      0.0452405000
_diffrn_orient_matrix_UB_22      0.0089951000
_diffrn_orient_matrix_UB_23      0.0466794000
_diffrn_orient_matrix_UB_31      -0.0681918000
_diffrn_orient_matrix_UB_32      -0.0044817000
_diffrn_orient_matrix_UB_33      0.0322595000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0738
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            61448
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.485
_diffrn_reflns_theta_min         2.160
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    44.677
_exptl_absorpt_correction_T_max  0.584
_exptl_absorpt_correction_T_min  0.082
_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    3.099
_exptl_crystal_description       plate
_exptl_crystal_F_000             13032
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.013
_refine_diff_density_max         2.307
_refine_diff_density_min         -2.266
_refine_diff_density_rms         0.411
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     763
_refine_ls_number_reflns         15745
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0652
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0670P)^2^+473.1324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1453
_refine_ls_wR_factor_ref         0.1520
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13361
_reflns_number_total             15745
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08228_si_002.cif
_cod_data_source_block           wf150_1_r2-abs
_cod_database_code               4128348
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Au24 Cd1 S18 C144 H162'
_shelx_estimated_absorpt_t_max   0.594
_shelx_estimated_absorpt_t_min   0.053
_reflns_odcompleteness_completeness 98.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_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
{Au7, Cd7}
{Au2, Cd2}
{Au3, Cd3}
{Au4, Cd4}
{Cd5, Au5}
{Cd6, Au6}
3. Restrained distances
 Au23-Cd3
 3.2 with sigma of 0.02
 Au23-S3A = Au23-S2
 2.4 with sigma of 0.05
 S3B-C17B
 1.83 with sigma of 0.02
 C18B-C17B
 1.51 with sigma of 0.02
 C19B-C18B
 1.51 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Au2) = Uanis(Cd2)
Uanis(Cd2) = Uanis(Au2)
Uanis(Au7) = Uanis(Cd7)
Uanis(Au3) = Uanis(Cd3)
Uanis(Au4) = Uanis(Cd4)
Uanis(Cd5) = Uanis(Au5)
Uanis(Cd6) = Uanis(Au6)
Uanis(C51B) = Uanis(C52B) = Uanis(C53B) = Uanis(C54B) = Uanis(C55B) =
Uanis(C56B)
Uanis(C3B) = Uanis(C4B) = Uanis(C5B) = Uanis(C6B) = Uanis(C7B) = Uanis(C8B)
Uanis(C51A) = Uanis(C52A) = Uanis(C53A) = Uanis(C54A) = Uanis(C55A) =
Uanis(C56A)
Uanis(C3A) = Uanis(C4A) = Uanis(C5A) = Uanis(C6A) = Uanis(C7A) = Uanis(C8A)
Uanis(Au13) = Uanis(Au23)
Uanis(C17B) = Uanis(C17A)
Uanis(C22B) = Uanis(C23B)
Uanis(C19A) = Uanis(C24A) = Uanis(C23A) = Uanis(C22A) = Uanis(C21A) =
Uanis(C20A) = Uanis(C19B) = Uanis(C24B) = Uanis(C23B) = Uanis(C22B) =
Uanis(C21B) = Uanis(C20B)
Uanis(C18A) = Uanis(C18B) = Uanis(C17B) = Uanis(C17A)
5. Others
 Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(C56B)=Sof(H56B)=Sof(C55B)=Sof(H55B)=
 Sof(C54B)=Sof(H54B)=Sof(C53B)=Sof(H53B)=Sof(C52B)=Sof(H52B)=1-FVAR(1)
 Sof(H50A)=Sof(H50B)=Sof(C51A)=Sof(C56A)=Sof(H56A)=Sof(C55A)=Sof(H55A)=
 Sof(C54A)=Sof(H54A)=Sof(C53A)=Sof(H53A)=Sof(C52A)=Sof(H52A)=FVAR(1)
 Sof(H2BC)=Sof(H2BD)=Sof(C3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=
 Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=1-FVAR(2)
 Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=
 Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=FVAR(2)
 Sof(Au23)=Sof(C17B)=Sof(H17A)=Sof(H17B)=Sof(C18B)=Sof(H18A)=Sof(H18B)=
 Sof(C19B)=Sof(C24B)=Sof(H24B)=Sof(C23B)=Sof(H23B)=Sof(C22B)=Sof(H22B)=
 Sof(C21B)=Sof(H21B)=Sof(C20B)=Sof(H20B)=Sof(S3B)=1-FVAR(3)
 Sof(Au13)=Sof(S3A)=Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18C)=
 Sof(H18D)=Sof(C19A)=Sof(C24A)=Sof(H24A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=
 Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(H20A)=FVAR(3)
 Fixed Sof: Au2(0.9167) Au3(0.9167) Au4(0.9167) Au5(0.9167) Au6(0.9167)
 Au7(0.9167) Cd2(0.0833) Cd3(0.0833) Cd4(0.0833) Cd5(0.0833) Cd6(0.0833)
 Cd7(0.0833)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2AA,H2AB), C2(H2BC,H2BD), C9(H9A,H9B), C10(H10A,H10B),
 C17B(H17A,H17B), C18B(H18A,H18B), C25(H25A,H25B), C26(H26A,H26B), C33(H33A,
 H33B), C34(H34A,H34B), C41(H41A,H41B), C42(H42A,H42B), C49(H49A,H49B),
 C50(H50A,H50B), C50(H50C,H50D), C57(H57A,H57B), C58(H58A,H58B), C65(H65A,H65B),
  C66(H66A,H66B), C17A(H17C,H17D), C18A(H18C,H18D)
6.b Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C8A(H8A), C4B(H4B), C5B(H5B),
 C6B(H6B), C7B(H7B), C8B(H8B), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
  C24B(H24B), C23B(H23B), C22B(H22B), C21B(H21B), C20B(H20B), C28(H28),
 C29(H29), C30(H30), C31(H31), C32(H32), C36(H36), C37(H37), C38(H38), C39(H39),
  C40(H40), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C56A(H56A),
 C55A(H55A), C54A(H54A), C53A(H53A), C52A(H52A), C56B(H56B), C55B(H55B),
 C54B(H54B), C53B(H53B), C52B(H52B), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C24A(H24A),
 C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A)
6.c Fitted hexagon refined as free rotating group:
 C3A(C4A,C5A,C6A,C7A,C8A), C3B(C4B,C5B,C6B,C7B,C8B), C19B(C24B,C23B,C22B,C21B,
 C20B), C51A(C56A,C55A,C54A,C53A,C52A), C51B(C56B,C55B,C54B,C53B,C52B),
 C19A(C24A,C23A,C22A,C21A,C20A)
;
_shelx_res_checksum              4482
_shelx_hkl_checksum              93168
_ins_header
;
TITL WF150_1_R2-abs in Pnma 
REM Pnma (#62, found as Pnam in a-cb setting)
CELL 1.54184  18.522575  31.313513  27.007252  90.0000  90.0000  90.0000
ZERR    4.00   0.000240   0.000458   0.000333   0.0000   0.0000   0.0000
LATT  1
SYMM -x+1/2,-y, z+1/2 
SYMM -x, y+1/2,-z 
SYMM  x+1/2,-y+1/2,-z+1/2 
SFAC C H S Cd Au
UNIT 576.00 648.00 72.00 4.00 96.00
TREF
HKLF 4
END
;
_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 1.699
_oxdiff_exptl_absorpt_empirical_full_min 0.673