Atom-precise Modification of Silver(I) Thiolate Cluster by Shell Ligand Substitution: A New Approach to Generation of Cluster Functionality and Chirality.
Li, Si; Du, Xiang-Sha; Li, Bing; Wang, Jia-Yin; Li, Guo-Ping; Gao, Guang-Gang; Zang, Shuang-Quan; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b12136

data_4126966
_publ_section_title
;
 Atom-precise Modification of Silver(I) Thiolate Cluster by Shell Ligand
 Substitution: A New Approach to Generation of Cluster Functionality and
 Chirality.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b12136
_journal_year                    2017
_chemical_formula_moiety
'C137 H174 Ag20 Fe8 N4 O19 S10, 2(H2 O), 0.5(C4 H6 N2)'
_chemical_formula_sum            'C139 H181 Ag20 Fe8 N5 O21 S10'
_chemical_formula_weight         5182.68
_chemical_name_systematic
;
 ?
;
_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   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2017-09-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                77.024(2)
_cell_angle_beta                 87.2409(19)
_cell_angle_gamma                89.331(2)
_cell_formula_units_Z            1
_cell_length_a                   15.2883(4)
_cell_length_b                   16.3501(4)
_cell_length_c                   16.6836(4)
_cell_measurement_reflns_used    29577
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.5280
_cell_measurement_theta_min      3.8570
_cell_volume                     4059.11(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.994
_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  33.00   0.50    0.50    --   45.50 -57.00 120.00  150
  2  \w     36.00  82.00   0.50    0.50    --   45.50 -57.00 120.00   92
  3  \w     76.00 102.00   0.50    0.83    --  100.10 -82.00   0.00   52
  4  \w     89.00 132.00   0.50    0.83    --  100.10 -82.00 -30.00   86
  5  \w     98.00 124.00   0.50    0.83    --  100.10 -82.00-120.00   52
  6  \w    107.00 134.00   0.50    0.83    --  100.10 -82.00-150.00   54
  7  \w     77.00 104.00   0.50    0.83    --  100.10 -82.00-150.00   54
  8  \w     76.00 102.00   0.50    0.83    --  100.10 -61.00-150.00   52
  9  \w     61.00  89.00   0.50    0.50    --   45.50 -37.00 -60.00   56
 10  \w    -15.00  88.00   0.50    0.50    --   45.50 -82.00 -30.00  206
 11  \w     44.00  71.00   0.50    0.83    --  100.10 -82.00-150.00   54
 12  \w     54.00  96.00   0.50    0.83    --  100.10 -82.00-180.00   84
 13  \w     28.00  55.00   0.50    0.83    --  100.10 -61.00-150.00   54
 14  \w     15.00 143.00   0.50    0.83    --  100.10 -82.00 -90.00  256
 15  \w     91.00 117.00   0.50    0.83    --  100.10 -82.00  90.00   52
 16  \w     82.00 134.00   0.50    0.83    --  100.10 -82.00  23.47  104
 17  \w     55.00 189.00   0.50    0.83    --  100.10  15.00  30.00  268
 18  \w    105.00 134.00   0.50    0.50    --   45.50  82.00  30.00   58
 19  \w     88.00 130.00   0.50    0.50    --   45.50  82.00-120.00   84
 20  \w     89.00 125.00   0.50    0.83    --  100.10  82.00-120.00   72
 21  \w     13.00 142.00   0.50    0.83    --  100.10 -45.00  60.00  258
 22  \w     43.00  86.00   0.50    0.83    --  100.10 -82.00  60.00   86
 23  \w     40.00 144.00   0.50    0.83    --  100.10 -82.00 120.00  208
 24  \w     11.00 157.00   0.50    0.83    --  100.10 -30.00 -90.00  292
 25  \w     15.00  42.00   0.50    0.83    --  100.10  15.00  30.00   54
 26  \w     12.00 145.00   0.50    0.83    --  100.10 -30.00  60.00  266
 27  \w     11.00 141.00   0.50    0.83    --  100.10 -82.00 -60.00  260
 28  \w    -15.00  30.00   0.50    0.50    --   45.50 -82.00  60.00   90
 29  \w    -28.00  71.00   0.50    0.50    --   45.50 -82.00-150.00  198
 30  \w    -43.00  41.00   0.50    0.50    --   45.50 -37.00 -60.00  168
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0172113000
_diffrn_orient_matrix_UB_12      -0.0951779000
_diffrn_orient_matrix_UB_13      0.0254914000
_diffrn_orient_matrix_UB_21      -0.0640416000
_diffrn_orient_matrix_UB_22      0.0075952000
_diffrn_orient_matrix_UB_23      -0.0698309000
_diffrn_orient_matrix_UB_31      0.0760270000
_diffrn_orient_matrix_UB_32      -0.0152644000
_diffrn_orient_matrix_UB_33      -0.0589312000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            47539
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.986
_diffrn_reflns_theta_min         2.721
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    26.054
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35244
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.120
_exptl_crystal_description       block
_exptl_crystal_F_000             2526
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.097
_refine_diff_density_min         -2.216
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     999
_refine_ls_number_reflns         14399
_refine_ls_number_restraints     193
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0706P)^2^+48.3518P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1444
_refine_ls_wR_factor_ref         0.1473
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13097
_reflns_number_total             14399
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12136_si_005.cif
_cod_data_source_block           20161127a1
_cod_original_cell_volume        4059.10(17)
_cod_database_code               4126966
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C H O S Ag Fe'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 99.38
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C69-C68
 1.53 with sigma of 0.01
 C70b-N2
 1.2 with sigma of 0.02
 N3-C68
 1.3 with sigma of 0.01
 C71b-C70b
 1.53 with sigma of 0.01
 H12a_$1-H67c
 2 with sigma of 0.01
 N2-C70a \\sim N2-C70b
 with sigma of 0.01
 C71a-C70a \\sim C70b-C71b
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C70a \\sim C70b \\sim C71a \\sim C71b: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C71a \\sim C71b \\sim C70a \\sim C70b \\sim N2: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C71b \\sim N2: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C71b \\sim C71a \\sim C70b \\sim C70a \\sim N2: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
Uanis(C57) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O4) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O10)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(O4)
\\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C15) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C69) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C68) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Ag9)=1-FVAR(1)
 Sof(Ag10)=FVAR(1)
 Sof(Ag9b)=1-FVAR(2)
 Sof(Ag9a)=FVAR(2)
 Sof(C71b)=Sof(H71a)=Sof(H71b)=Sof(H71c)=Sof(C70b)=1-FVAR(3)
 Sof(C70a)=Sof(C71a)=Sof(H71d)=Sof(H71e)=Sof(H71f)=FVAR(3)
 Fixed Sof: O2(0.5) O3(0.5) O1(0.5) C69(0.5) H69a(0.5) H69b(0.5) H69c(0.5)
 C68(0.5)
5.a Riding coordinates:
 C71b(H71a,H71b,H71c), C71a(H71d,H71e,H71f)
5.b Free rotating group:
 O12(H12a,H12b)
5.c Ternary CH refined with riding coordinates:
 C37(H37), C19(H19), C20(H20), C22(H22), C23(H23), C21(H21), C12(H12), C9(H9)
5.d Aromatic/amide H refined with riding coordinates:
 C29(H29), C40(H40), C28(H28), C30(H30), C27(H27), C26(H26), C34(H34),
 C31(H31), C42(H42), C39(H39), C38(H38), C43(H43), C33(H33), C7(H7), C16(H16),
 C32(H32), C15(H15), C44(H44), C41(H41), C45(H45), C17(H17), C6(H6), C4(H4),
 C18(H18), C5(H5), C8(H8), C10(H10), C11(H11)
5.e Idealised Me refined as rotating group:
 C61(H61a,H61b,H61c), C52(H52a,H52b,H52c), C47(H47a,H47b,H47c), C51(H51a,H51b,
 H51c), C53(H53a,H53b,H53c), C49(H49a,H49b,H49c), C60(H60a,H60b,H60c), C59(H59a,
 H59b,H59c), C48(H48a,H48b,H48c), C64(H64a,H64b,H64c), C65(H65a,H65b,H65c),
 C63(H63a,H63b,H63c), C67(H67a,H67b,H67c), C57(H57a,H57b,H57c), C56(H56a,H56b,
 H56c), C55(H55a,H55b,H55c), C69(H69a,H69b,H69c)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.575
_oxdiff_exptl_absorpt_empirical_full_min 0.649