Spontaneous Resolution of Chiral Multi-Thiolate-Protected Ag30 Nanoclusters
Huang, Jia-Hong; Wang, Zhao-Yang; Zang, Shuang-Quan; Mak, Thomas C. W.; ACS Central Science  (2020) –; doi:10.1021/acscentsci.0c01045

data_4518097
_publ_section_title
;
 Spontaneous Resolution of Chiral Multi-Thiolate-Protected Ag30
 Nanoclusters
;
_journal_name_full               'ACS Central Science'
_journal_paper_doi               10.1021/acscentsci.0c01045
_journal_year                    2020
_chemical_formula_moiety         'C166 H204 Ag30 B80 P12 S24, 4(C4 H9 N O)'
_chemical_formula_sum            'C182 H240 Ag30 B80 N4 O4 P12 S24'
_chemical_formula_weight         7789.75
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-08
_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                120
_cell_formula_units_Z            3
_cell_length_a                   34.8668(13)
_cell_length_b                   34.8668(13)
_cell_length_c                   24.0968(6)
_cell_measurement_reflns_used    16956
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.6700
_cell_measurement_theta_min      3.4610
_cell_volume                     25369.6(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_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    -18.00  88.00   0.50    1.00    --    0.00  38.00 120.00  212
  2  \w    -88.00 -42.00   0.50    1.00    --    0.00 -38.00   0.00   92
  3  \w     31.00 116.00   0.50   10.00    --   95.20 -45.00 -30.00  170
  4  \w     12.00 100.00   0.50   10.00    --   95.20 -77.00  90.00  176
  5  \w      6.00  83.00   0.50   10.00    --   95.20 -61.00  90.00  154
  6  \w     79.00 168.00   0.50   10.00    --   95.20  30.00 -30.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0084310000
_diffrn_orient_matrix_UB_12      -0.0383139000
_diffrn_orient_matrix_UB_13      -0.0137323000
_diffrn_orient_matrix_UB_21      0.0494987000
_diffrn_orient_matrix_UB_22      0.0299799000
_diffrn_orient_matrix_UB_23      0.0137835000
_diffrn_orient_matrix_UB_31      -0.0093101000
_diffrn_orient_matrix_UB_32      -0.0154901000
_diffrn_orient_matrix_UB_33      0.0608821000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1020
_diffrn_reflns_av_unetI/netI     0.0952
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            81583
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        65.498
_diffrn_reflns_theta_max         65.498
_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    15.770
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10110
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.530
_exptl_crystal_F_000             11298
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.324
_refine_diff_density_min         -0.943
_refine_diff_density_rms         0.173
_refine_ls_abs_structure_details
;
 Flack x determined using 4912 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.929
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1426
_refine_ls_number_reflns         28374
_refine_ls_number_restraints     1392
_refine_ls_restrained_S_all      0.919
_refine_ls_R_factor_all          0.1286
_refine_ls_R_factor_gt           0.0793
_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^)+(0.1405P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1920
_refine_ls_wR_factor_ref         0.2287
_reflns_Friedel_coverage         0.850
_reflns_Friedel_fraction_full    0.946
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                15195
_reflns_number_total             28374
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            oc0c01045_si_002.cif
_cod_data_source_block           20191217b3_sq
_cod_original_cell_volume        25370(2)
_cod_database_code               4518097
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.506
_shelx_estimated_absorpt_t_min   0.405
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B25-B21 = B27-B21 = B26-B21 = B26-B24 = B30-B24 = B24-B21 = B24-B23 = B23-B21
 = B27-B25 = B24-B22 = B23-B22 = B25-B23 = B30-B26 = B27-B26 = B34-B23 = B34-
 B25 = B34-B22 = B30-B22
 1.65 with sigma of 0.01
 B8-B7 = B19-B11 = B8-B33 = B33-B10 = B8-B10 = B8-C53 = C53-B10 = B19-B10 = B7-
 B33 = B12-B11 = B33-B18 = B7-B18 = B20-B18 = B7-B20 = B20-B11 = B18-B12 = B33-
 B12 = B18-B11 = B19-C53 = B19-B12 = B12-B10
 1.65 with sigma of 0.01
 B39-B14 = B14-B13 = B39-B13 = B9-B29 = B31-B14 = B9-B14 = B35-B29 = B39-B28 =
 B39-B32 = B32-B29 = B28-B13 = B35-B32 = B32-B28 = B39-B29 = B29-B14 = B36-B31 =
  B9-B36 = B31-B13 = B9-B35 = B36-B35 = B9-B31
 1.65 with sigma of 0.01
 C68-B13 = C68-B31 = C68-B28 = C67-B28 = C67-B32 = C67-B35 = C67-B36 = C68-B36
 1.6 with sigma of 0.01
 C68-C67
 1.5 with sigma of 0.01
 C84-O1
 1.2 with sigma of 0.01
 N1-C86 = N1-C83
 1.5 with sigma of 0.01
 C85-C86
 2.85 with sigma of 0.01
 H85b-H86b
 2.5 with sigma of 0.01
 B76-B26 = B76-B30 = C75-B30 = C75-B22 = C75-B34 = C75-C40 = B76-C40 = B76-B27
 1.6 with sigma of 0.01
 B76-C75
 1.5 with sigma of 0.01
 B76-C40 = B76-B27 = B76-B26 = B76-B30
 1.5 with sigma of 0.01
 N1-C84
 1.5 with sigma of 0.01
 C85-C84
 1.45 with sigma of 0.01
 O2-C88
 1.2 with sigma of 0.01
 C89-C88
 1.51 with sigma of 0.01
 B49-B20 = B49-B11 = B49-B19
 1.5 with sigma of 0.01
 C37-B49
 1.5 with sigma of 0.01
 N2-C90 = N2-C91 = N2-C88
 1.45 with sigma of 0.01
 C56-C90_$1
 3.8 with sigma of 0.01
 C90_$2-C37
 3.5 with sigma of 0.01
 C53-C91_$2
 4 with sigma of 0.01
 C4-C21
 1.38 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C67 \\sim C68 \\sim B9 \\sim B13 \\sim B14 \\sim B28 \\sim B29 \\sim B31 \\sim
B32 \\sim B35 \\sim B36 \\sim B39: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04
P5 \\sim C6 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04
Ag14 \\sim P3 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04
C18 \\sim C33 \\sim C46 \\sim C55 \\sim C58 \\sim C65: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04
C50 \\sim C66 \\sim B1 \\sim B2 \\sim B3 \\sim B4 \\sim B5 \\sim B6 \\sim B15
\\sim B16 \\sim B17 \\sim B38: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
O1 \\sim N1 \\sim C84: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C75 \\sim B76 \\sim B21 \\sim B22 \\sim B23 \\sim B24 \\sim B25 \\sim B26 \\sim
B27 \\sim B30 \\sim B34 \\sim C40: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
Ag4: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
B49 \\sim C53 \\sim B7 \\sim B8 \\sim B10 \\sim B11 \\sim B12 \\sim B18 \\sim
B19 \\sim B20 \\sim B33 \\sim C37: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
O2 \\sim N2 \\sim C88 \\sim C89 \\sim C90 \\sim C91: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.01
Uanis(B35) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(B22) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C16) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(B25) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C70) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C70) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C79) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(B26) \\sim Ueq, Uanis(B76) \\sim Ueq, Uanis(C40) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C85) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C83)
\\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(Ag16) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37) \\sim Ueq, Uanis(B49) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(O2)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C89) \\sim Ueq,
Uanis(C91) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Ag16(0.5)
5.a Riding coordinates:
 C89(H89a,H89b,H89c), C90(H90a,H90b,H90c)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3a,H3b), C6(H6a,H6b), C87(H87a,H87b)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C20(H20), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
  C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C1AA(H1AA),
 C38(H38), C26(H26), C57(H57), C56(H56), C43(H43), C25(H25), C41(H41), C42(H42),
  C44(H44), C46(H46), C47(H47), C48(H48), C51(H51), C54(H54), C55(H55),
 C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C69(H69),
  C70(H70), C71(H71), C72(H72), C73(H73), C77(H77), C78(H78), C79(H79),
 C81(H81), C82(H82), C4(H4a), C16(H16a), C52(H52), C45(H45), C19(H19a)
5.d Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,C14), C27(C28,C29,C30,C31,C32), C34(C35,C36,C1AA,C38,C39),
 C0AA(C26,C57,C56,C43,C25), C59(C60,C61,C62,C63,C64), C69(C70,C71,C72,C73,C74),
 C77(C78,C79,C80,C81,C82), C21(C4,C16,C52,C45,C19)
5.e Idealised Me refined as rotating group:
 C83(H83a,H83b,H83c), C85(H85a,H85b,H85c), C86(H86a,H86b,H86c), C91(H91a,H91b,
 H91c)
5.f Boron cage BH refined with riding coordinates:
 B49(H49), C50(H50), C53(H53), C66(H66), C67(H67), C68(H68), C75(H75),
 B76(H76), B2(H2a), B3(H3), B4(H4), B6(H6), B7(H7), B8(H8a), B9(H9), B10(H10a),
 B11(H11a), B13(H13a), B15(H15), B16(H16), B17(H17), B19(H19), B20(H20a),
 B22(H22a), B25(H25a), B26(H26a), B27(H27a), B28(H28a), B30(H30), B31(H31a),
 B32(H32a), B34(H34a), B35(H35a), B36(H36a), C37(H37), C40(H40)
;
_shelx_res_checksum              62569
_shelx_hkl_checksum              7091
_shelx_fab_checksum              31537
_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 4.306
_oxdiff_exptl_absorpt_empirical_full_min 0.581