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_4126963
_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 H155 Ag24 N10 O26 S10, 2(N O3), 4(C2 H3 N), 2(H2 O), O'
_chemical_formula_sum            'C89 H171 Ag24 N16 O35 S10'
_chemical_formula_weight         4934.89
_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                 94.2166(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.56346(16)
_cell_length_b                   16.62466(15)
_cell_length_c                   20.64665(18)
_cell_measurement_reflns_used    18741
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.6030
_cell_measurement_theta_min      2.1800
_cell_volume                     7039.17(10)
_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 0.796
_diffrn_measured_fraction_theta_max 0.997
_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    -30.00  75.00   0.50    0.50    --   45.50 -19.00 150.00  210
  2  \w     85.00 122.00   0.50    1.50    --  100.10 -82.00   0.00   74
  3  \w     54.00 128.00   0.50    1.50    --  100.10 -82.00 -60.00  148
  4  \w     35.00 143.00   0.50    1.50    --  100.10 -82.00-120.00  216
  5  \w    138.00 189.00   0.50    1.50    --  100.10  61.00  90.00  102
  6  \w    110.00 184.00   0.50    1.50    --  100.10  82.00  30.00  148
  7  \w     91.00 132.00   0.50    0.50    --   45.50  82.00   0.00   82
  8  \w     80.00 160.00   0.50    1.50    --  100.10  77.00 120.00  160
  9  \w     78.00 130.00   0.50    1.50    --  100.10  61.00  90.00  104
 10  \w     88.00 185.00   0.50    1.50    --  100.10  82.00-180.00  194
 11  \w     22.00  54.00   0.50    1.50    --  100.10 -82.00   0.00   64
 12  \w    -29.00  81.00   0.50    0.50    --   45.50 -82.00 150.00  220
;
_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      0.0105671000
_diffrn_orient_matrix_UB_12      0.0901244000
_diffrn_orient_matrix_UB_13      0.0146101000
_diffrn_orient_matrix_UB_21      0.0261051000
_diffrn_orient_matrix_UB_22      -0.0207765000
_diffrn_orient_matrix_UB_23      0.0698209000
_diffrn_orient_matrix_UB_31      0.0696638000
_diffrn_orient_matrix_UB_32      -0.0059630000
_diffrn_orient_matrix_UB_33      -0.0224798000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0714
_diffrn_reflns_Laue_measured_fraction_full 0.796
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            32308
_diffrn_reflns_point_group_measured_fraction_full 0.636
_diffrn_reflns_point_group_measured_fraction_max 0.799
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         58.993
_diffrn_reflns_theta_min         2.927
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.04555
_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    2.328
_exptl_crystal_description       block
_exptl_crystal_F_000             4770
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.764
_refine_diff_density_min         -1.186
_refine_diff_density_rms         0.162
_refine_ls_abs_structure_details
;
 Flack x determined using 4508 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.030(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1677
_refine_ls_number_reflns         16190
_refine_ls_number_restraints     284
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0550P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1141
_refine_ls_wR_factor_ref         0.1169
_reflns_Friedel_coverage         0.540
_reflns_Friedel_fraction_full    0.464
_reflns_Friedel_fraction_max     0.584
_reflns_number_gt                14345
_reflns_number_total             16190
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b12136_si_011.cif
_cod_data_source_block           hy
_cod_original_cell_volume        7039.17(11)
_cod_database_code               4126963
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.30
_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
 C61a-C60a
 2.4 with sigma of 0.01
 C60a-C59a
 2.4 with sigma of 0.01
 O30a-N1
 1.22 with sigma of 0.01
 O30a-N1 \\sim O30b-N1 \\sim O31a-N1 \\sim O31b-N1 \\sim O29a-N1 \\sim O29b-N1
 with sigma of 0.01
 C61b-C58 \\sim C58-C60a \\sim C58-C60b \\sim C58-C59a \\sim C58-C59b \\sim
C61a-C58
 with sigma of 0.01
 O26-N3 \\sim O28-N3
 with sigma of 0.01
 N3-O26 \\sim N3-O27 \\sim N3-O28
 with sigma of 0.01
3. Rigid bond restraints
 C17, C18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C59b \\sim C61a \\sim C61b \\sim C60a \\sim C60b \\sim C59a: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
O26 \\sim O28: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O27 \\sim O26 \\sim O28 \\sim N3: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O31a \\sim O31b \\sim O29a \\sim O29b \\sim O30a \\sim O30b: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C12 \\sim C13 \\sim C14: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C45 \\sim C44 \\sim C43 \\sim C42: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O30b) \\sim Ueq, Uanis(O29a) \\sim Ueq, Uanis(O30a) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O29b) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C72) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(N11)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C36) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O28) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O27) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O28) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(Ag1a)=1-FVAR(1)
 Sof(Ag20)=FVAR(1)
 Sof(O31b)=Sof(O29b)=Sof(O30b)=1-FVAR(2)
 Sof(O30a)=Sof(O31a)=Sof(O29a)=FVAR(2)
 Sof(C59b)=Sof(H59d)=Sof(H59e)=Sof(H59f)=Sof(C61b)=Sof(H61d)=Sof(H61e)=
 Sof(H61f)=Sof(C60b)=Sof(H60d)=Sof(H60e)=Sof(H60f)=1-FVAR(3)
 Sof(C60a)=Sof(H60a)=Sof(H60b)=Sof(H60c)=Sof(C59a)=Sof(H59a)=Sof(H59b)=
 Sof(H59c)=Sof(C61a)=Sof(H61a)=Sof(H61b)=Sof(H61c)=FVAR(3)
6.a Free rotating group:
 O33(H33a,H33b), O34(H34c,H34d)
6.b Rotating group:
 O32(H32a,H32b)
6.c Ternary CH refined with riding coordinates:
 C18(H18), N16(H16), N8(H8), C23(H23), N6(H6), N7(H7), N5(H5), C8(H8a), N9(H9),
  C28(H28), C33(H33), C38(H38), C13(H13), N10(H10), N11(H11), C3(H3)
6.d Secondary CH2 refined with riding coordinates:
 C9(H9a,H9b), C15(H15a,H15b), C5(H5a,H5b), C21(H21a,H21b), C31(H31a,H31b),
 C29(H29a,H29b), C14(H14a,H14b), C30(H30a,H30b), C40(H40a,H40b), C16(H16a,H16b),
  C19(H19a,H19b), C11(H11a,H11b), C39(H39a,H39b), C6(H6a,H6b), C4(H4a,H4b),
 C20(H20a,H20b), C10(H10a,H10b), C26(H26a,H26b), C24(H24a,H24b), C25(H25a,H25b),
  C34(H34a,H34b), C36(H36a,H36b), C35(H35a,H35b)
6.e Aromatic/amide H refined with riding coordinates:
 C41(H41)
6.f Idealised Me refined as rotating group:
 C69(H69a,H69b,H69c), C76(H76a,H76b,H76c), C67(H67a,H67b,H67c), C49(H49a,H49b,
 H49c), C68(H68a,H68b,H68c), C47(H47a,H47b,H47c), C55(H55a,H55b,H55c), C79(H79a,
 H79b,H79c), C81(H81a,H81b,H81c), C65(H65a,H65b,H65c), C51(H51a,H51b,H51c),
 C80(H80a,H80b,H80c), C53(H53a,H53b,H53c), C73(H73a,H73b,H73c), C71(H71a,H71b,
 H71c), C75(H75a,H75b,H75c), C63(H63a,H63b,H63c), C48(H48a,H48b,H48c), C45(H45a,
 H45b,H45c), C43(H43a,H43b,H43c), C77(H77a,H77b,H77c), C64(H64a,H64b,H64c),
 C44(H44a,H44b,H44c), C85(H85a,H85b,H85c), C89(H89a,H89b,H89c), C52(H52a,H52b,
 H52c), C72(H72a,H72b,H72c), C87(H87a,H87b,H87c), C83(H83a,H83b,H83c), C56(H56a,
 H56b,H56c), C60a(H60a,H60b,H60c), C57(H57a,H57b,H57c), C59a(H59a,H59b,H59c),
 C61a(H61a,H61b,H61c), C59b(H59d,H59e,H59f), C61b(H61d,H61e,H61f), C60b(H60d,
 H60e,H60f)
;
_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 11.566
_oxdiff_exptl_absorpt_empirical_full_min 0.461