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_4126965
_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
'C81 H154 Ag24 N10 O26 S10, 4(C2 H3 N), 2(H2 O), 2(N O3), O'
_chemical_formula_sum            'C89 H170 Ag24 N16 O35 S10'
_chemical_formula_weight         4933.88
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-09-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4709(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.5540(3)
_cell_length_b                   16.6389(2)
_cell_length_c                   20.6842(2)
_cell_measurement_reflns_used    13246
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.5950
_cell_measurement_theta_min      2.1730
_cell_volume                     7052.39(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.739
_diffrn_measured_fraction_theta_max 0.926
_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    -43.00  24.00   0.50    1.01    --   45.50  19.00  30.00  134
  2  \w     27.00  77.00   0.50    1.01    --   45.50  19.00  30.00  100
  3  \w     89.00 134.00   0.50    1.01    --   45.50  19.00  30.00   90
  4  \w     95.00 120.00   0.50    1.01    --   45.50  82.00 -30.00   50
  5  \w     95.00 130.00   0.50    1.01    --   45.50  82.00  90.00   70
  6  \w     90.00 173.00   0.50    2.50    --  100.10  77.00 -60.00  166
  7  \w    146.00 183.00   0.50    2.50    --  100.10  45.00  30.00   74
  8  \w    111.00 137.00   0.50    2.50    --  100.10 -61.00  90.00   52
  9  \w     82.00 124.00   0.50    2.50    --  100.10  45.00  30.00   84
 10  \w     33.00  73.00   0.50    2.50    --  100.10 -61.00  90.00   80
 11  \w     16.00 140.00   0.50    2.50    --  100.10 -77.00 -60.00  248
;
_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      0.0346427000
_diffrn_orient_matrix_UB_12      0.0270877000
_diffrn_orient_matrix_UB_13      0.0650503000
_diffrn_orient_matrix_UB_21      0.0361829000
_diffrn_orient_matrix_UB_22      0.0657537000
_diffrn_orient_matrix_UB_23      -0.0354468000
_diffrn_orient_matrix_UB_31      -0.0561001000
_diffrn_orient_matrix_UB_32      0.0592320000
_diffrn_orient_matrix_UB_33      0.0096091000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.739
_diffrn_reflns_Laue_measured_fraction_max 0.926
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            21235
_diffrn_reflns_point_group_measured_fraction_full 0.577
_diffrn_reflns_point_group_measured_fraction_max 0.725
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         58.997
_diffrn_reflns_theta_min         2.156
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.019
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70636
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    2.323
_exptl_crystal_description       block
_exptl_crystal_F_000             4768
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.536
_refine_diff_density_min         -1.357
_refine_diff_density_rms         0.160
_refine_ls_abs_structure_details
;
 Flack x determined using 3517 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.046(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1708
_refine_ls_number_reflns         14721
_refine_ls_number_restraints     378
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0718P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1282
_refine_ls_wR_factor_ref         0.1320
_reflns_Friedel_coverage         0.504
_reflns_Friedel_fraction_full    0.402
_reflns_Friedel_fraction_max     0.506
_reflns_number_gt                11965
_reflns_number_total             14721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12136_si_010.cif
_cod_data_source_block           hy
_cod_database_code               4126965
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C H O N Ag S'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 89.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O15b-N4b
 1.25 with sigma of 0.01
 O15a-N4a
 1.25 with sigma of 0.01
 N9-C26
 1.45 with sigma of 0.01
 H9-H23
 2 with sigma of 0.01
 O11a-O12a \\sim O12a-O10a
 with sigma of 0.01
 O10a-O12a \\sim O12a-O11a
 with sigma of 0.01
 O11a-O10a \\sim O10a-O12a
 with sigma of 0.01
 O14a-N4a \\sim O13a-N4a \\sim O15a-N4a \\sim O15b-N4b \\sim O13b-N4b \\sim
O14b-N4b
 with sigma of 0.01
 N10-C28 \\sim N10-C31 \\sim C28-C29
 with sigma of 0.01
 N10-C28 \\sim C28-C29 \\sim N10-C31
 with sigma of 0.01
 C61a-C58 \\sim C58-C61b \\sim C59a-C58 \\sim C58-C59b \\sim C60a-C58 \\sim
C60b-C58
 with sigma of 0.01
 N9-C23 \\sim N9-C26
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O12b \\sim O11a \\sim O11b \\sim O10a \\sim O10b \\sim O12a: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
O14a \\sim O13a \\sim O15a \\sim O15b \\sim O13b \\sim O14b: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
O14a \\sim N4a \\sim O13a \\sim O15b \\sim N4b \\sim O13b \\sim O14b \\sim
O15a: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
O22 \\sim C17 \\sim O23: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C32 \\sim O28 \\sim O29: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O18 \\sim C7 \\sim O19: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C3 \\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C37 \\sim O31: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C60a \\sim C60b \\sim C61a \\sim C61b \\sim C59a \\sim C59b: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N9) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C84) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C72) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C56) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C58) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O30) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C79) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N4a) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C31) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O32) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C60b)=Sof(H60d)=Sof(H60e)=Sof(H60f)=Sof(C61b)=Sof(H61d)=Sof(H61e)=
 Sof(H61f)=Sof(C59b)=Sof(H59d)=Sof(H59e)=Sof(H59f)=1-FVAR(1)
 Sof(C61a)=Sof(H61a)=Sof(H61b)=Sof(H61c)=Sof(C60a)=Sof(H60a)=Sof(H60b)=
 Sof(H60c)=Sof(C59a)=Sof(H59a)=Sof(H59b)=Sof(H59c)=FVAR(1)
 Sof(Ag1b)=1-FVAR(2)
 Sof(Ag20)=FVAR(2)
 Sof(O12b)=Sof(O11b)=Sof(O10b)=1-FVAR(3)
 Sof(O10a)=Sof(O12a)=Sof(O11a)=FVAR(3)
 Sof(O14b)=Sof(N4b)=Sof(O13b)=Sof(O15b)=1-FVAR(4)
 Sof(O15a)=Sof(O13a)=Sof(O14a)=Sof(N4a)=FVAR(4)
5.a Riding coordinates:
 C59b(H59d,H59e,H59f)
5.b Free rotating group:
 O33(H33a,H33b), O35(H35c,H35d)
5.c Rotating group:
 O32(H32a,H32b)
5.d Ternary CH refined with riding coordinates:
 C38(H38), C3(H3), N12(H12), N6(H6), N5(H5), N7(H7), N11(H11), C28(H28),
 N9(H9), C13(H13), N10(H10), C33(H33), C18(H18), N8(H8), C23(H23), C8(H8a)
5.e Secondary CH2 refined with riding coordinates:
 C29(H29a,H29b), C14(H14a,H14b), C11(H11a,H11b), C26(H26a,H26b), C41(H41a,
 H41b), C6(H6a,H6b), C35(H35a,H35b), C4(H4a,H4b), C20(H20a,H20b), C34(H34a,
 H34b), C10(H10a,H10b), C25(H25a,H25b), C36(H36a,H36b), C39(H39a,H39b), C9(H9a,
 H9b), C21(H21a,H21b), C40(H40a,H40b), C16(H16a,H16b), C24(H24a,H24b), C19(H19a,
 H19b), C5(H5a,H5b), C15(H15a,H15b), C31(H31a,H31b)
5.f Idealised Me refined as rotating group:
 C68(H68a,H68b,H68c), C77(H77a,H77b,H77c), C72(H72a,H72b,H72c), C69(H69a,H69b,
 H69c), C80(H80a,H80b,H80c), C53(H53a,H53b,H53c), C46(H46a,H46b,H46c), C55(H55a,
 H55b,H55c), C67(H67a,H67b,H67c), C81(H81a,H81b,H81c), C64(H64a,H64b,H64c),
 C48(H48a,H48b,H48c), C63(H63a,H63b,H63c), C49(H49a,H49b,H49c), C79(H79a,H79b,
 H79c), C43(H43a,H43b,H43c), C76(H76a,H76b,H76c), C73(H73a,H73b,H73c), C51(H51a,
 H51b,H51c), C61a(H61a,H61b,H61c), C44(H44a,H44b,H44c), C65(H65a,H65b,H65c),
 C57(H57a,H57b,H57c), C45(H45a,H45b,H45c), C60a(H60a,H60b,H60c), C75(H75a,H75b,
 H75c), C52(H52a,H52b,H52c), C83(H83a,H83b,H83c), C89(H89a,H89b,H89c), C87(H87a,
 H87b,H87c), C85(H85a,H85b,H85c), C71(H71a,H71b,H71c), C59a(H59a,H59b,H59c),
 C56(H56a,H56b,H56c), C60b(H60d,H60e,H60f), C61b(H61d,H61e,H61f)
;
_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 1.278
_oxdiff_exptl_absorpt_empirical_full_min 0.764