Hierarchical Multi-Shell 66-Nuclei Silver Nanoclusters Trapping Subvalent Ag6 Kernels
wang , zhi; Yang, Feng-Lei; Yang, Yang; Liu, Qingyun; Sun, Di; Chemical Communications  (2019) –; doi:10.1039/C9CC05044B

data_7123930
_publ_section_title
;
 Hierarchical Multi-Shell 66-Nuclei Silver Nanoclusters Trapping Subvalent
 Ag6 Kernels
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC05044B
_journal_year                    2019
_chemical_formula_moiety         'C211 H289 Ag66 Mo9 O73 S28, C H3 O'
_chemical_formula_sum            'C212 H292 Ag66 Mo9 O74 S28'
_chemical_formula_weight         12905.00
_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
_audit_creation_date             2019-07-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-24 deposited with the CCDC.    2019-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                112.6803(13)
_cell_angle_beta                 108.2811(12)
_cell_angle_gamma                99.7127(12)
_cell_formula_units_Z            1
_cell_length_a                   16.3935(2)
_cell_length_b                   23.8317(3)
_cell_length_c                   24.0155(3)
_cell_measurement_reflns_used    54180
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      29.9640
_cell_measurement_theta_min      3.3290
_cell_volume                     7757.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -37.00  12.00   0.50    5.00    --   -9.12  74.00  53.00   98
  2  \w    -82.00  17.00   0.50    5.00    --   -9.12 -74.00 -75.00  198
  3  \w    -19.00  29.00   0.50    5.00    --   -9.12 -99.00   0.00   96
  4  \w    -20.00  40.00   0.50    5.00    --   10.30 -99.00  30.00  120
  5  \w    -26.00  45.00   0.50    5.00    --   10.30 -99.00 -90.00  142
  6  \w     16.00  43.00   0.50    5.00    --   10.30 -99.00-120.00   54
  7  \w    -23.00  48.00   0.50    5.00    --   10.30 -99.00-180.00  142
  8  \w    -26.00  13.00   0.50    5.00    --   10.30 -99.00-120.00   78
  9  \w    -25.00  27.00   0.50    5.00    --   10.30 -99.00 150.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0254069000
_diffrn_orient_matrix_UB_12      0.0273196000
_diffrn_orient_matrix_UB_13      0.0316046000
_diffrn_orient_matrix_UB_21      -0.0370061000
_diffrn_orient_matrix_UB_22      -0.0054369000
_diffrn_orient_matrix_UB_23      0.0087043000
_diffrn_orient_matrix_UB_31      0.0177131000
_diffrn_orient_matrix_UB_32      -0.0197731000
_diffrn_orient_matrix_UB_33      0.0127856000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            102945
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.385
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.654
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.762
_exptl_crystal_description       block
_exptl_crystal_F_000             6084
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.952
_refine_diff_density_min         -3.482
_refine_diff_density_rms         0.232
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2013
_refine_ls_number_reflns         31603
_refine_ls_number_restraints     760
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0137P)^2^+191.4343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25242
_reflns_number_total             31603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05044b2.cif
_cod_data_source_block           SD_Ag66b
_cod_database_code               7123930
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         AgS
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2. Restrained distances
 C1A-O20A
 1.25 with sigma of 0.01
 O19A-C1A
 1.25 with sigma of 0.01
 O19-O20
 2.15 with sigma of 0.01
 C1-O20
 1.25 with sigma of 0.01
 O19-C1
 1.25 with sigma of 0.01
 C1-O19
 1.25 with sigma of 0.01
 C1A-C2A
 1.55 with sigma of 0.01
 C1A-C7A
 2.35 with sigma of 0.01
 C2A-C1A
 1.55 with sigma of 0.01
 C7A-C1A
 2.35 with sigma of 0.01
 C3A-C1A
 2.35 with sigma of 0.01
 O20A-O19A
 2.15 with sigma of 0.01
 C29-O37
 1.25 with sigma of 0.01
 O37-C29
 1.25 with sigma of 0.01
 O37A-C29
 1.25 with sigma of 0.01
 C94-C93
 1.55 with sigma of 0.01
 C1-C2
 1.55 with sigma of 0.01
 C7-C1
 2.35 with sigma of 0.01
 C3-C1
 2.35 with sigma of 0.01
 C1A-C7
 2.35 with sigma of 0.01
 O20-C2
 2.35 with sigma of 0.01
 C1-C7
 2.35 with sigma of 0.01
 C1-C3
 2.35 with sigma of 0.01
 C2-O19
 2.35 with sigma of 0.01
 C2-C1
 1.55 with sigma of 0.01
 O37A-O36
 2.15 with sigma of 0.01
 C29-O36
 1.25 with sigma of 0.01
 O37-O36
 2.15 with sigma of 0.01
 O36A-O37
 2.15 with sigma of 0.01
 O36A-C29
 1.25 with sigma of 0.01
 C76-C77
 1.55 with sigma of 0.01
 C76-C78
 1.55 with sigma of 0.01
 C78-C77
 2.35 with sigma of 0.01
3. Restrained planarity
 O19A, O20A, C1A, C3A, C2A, C7A, C6A, C5A, C4A
 with sigma of 0.001
 O33, O34A, C8, C9
 with sigma of 0.01
 O19, O20, C1, C3, C2, C7, C6, C5, C4
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
Ag2 \\sim Ag2A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.004
Ag9 \\sim Ag9A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
O25 \\sim O26 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim
C28: within 1.7A with sigma of 0.004 and sigma for terminal atoms of 0.008
O33 \\sim O34 \\sim O34A \\sim C8 \\sim C8A \\sim C9 \\sim C10 \\sim C11 \\sim
C12 \\sim C13 \\sim C14: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.004
C67 \\sim C68 \\sim C69: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C83 \\sim C84 \\sim C85: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C92 \\sim C93 \\sim C94: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C104 \\sim C105 \\sim C106: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008
O21 \\sim O22 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56: within 1.7A with sigma of 0.004 and sigma for terminal atoms of 0.008
O23 \\sim O24 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim
C63: within 1.7A with sigma of 0.004 and sigma for terminal atoms of 0.008
C86 \\sim C87 \\sim C88: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
S11 \\sim C79 \\sim C80 \\sim C81: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.004
O35 \\sim C82 \\sim O35A \\sim C82A: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.004
O19 \\sim O19A \\sim O20 \\sim O20A \\sim C1 \\sim C1A \\sim C3 \\sim C2 \\sim
C7 \\sim C6 \\sim C5 \\sim C4 \\sim C3A \\sim C2A \\sim C7A \\sim C6A \\sim C5A
\\sim C4A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of 0.004
O36 \\sim O36A \\sim O37 \\sim O37A \\sim C29 \\sim C30 \\sim C31 \\sim C32
\\sim C33 \\sim C34 \\sim C35: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008
C76 \\sim C77 \\sim C78: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.004
C83A \\sim C83 \\sim C84 \\sim C85A \\sim C84A \\sim C85: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(O36A) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.01
5. Others
 Sof(Ag6A)=1-FVAR(1)
 Sof(Ag6)=FVAR(1)
 Sof(Ag7A)=1-FVAR(2)
 Sof(Ag7)=FVAR(2)
 Sof(Ag5A)=1-FVAR(3)
 Sof(Ag5)=FVAR(3)
 Sof(Ag1A)=1-FVAR(4)
 Sof(Ag1)=FVAR(4)
 Sof(Ag8A)=1-FVAR(5)
 Sof(Ag8)=FVAR(5)
 Sof(Ag2A)=1-FVAR(6)
 Sof(Ag2)=FVAR(6)
 Sof(Ag3)=Sof(Ag4A)=Sof(Ag9)=1-FVAR(7)
 Sof(Ag3A)=Sof(Ag4)=Sof(Ag9A)=FVAR(7)
 Fixed Sof: Mo1(0.5) Mo1A(0.5) Mo2(0.5) Mo2A(0.5) Mo3(0.5) Mo3A(0.5) Mo4(0.5)
 O19(0.5) O19A(0.5) O20(0.5) O20A(0.5) O34(0.5) O34A(0.5) O35(0.5) O36(0.5)
 O36A(0.5) O37(0.5) O37A(0.5) C1(0.5) C1A(0.5) C3(0.5) H3(0.5) C2(0.5) C7(0.5)
 H7(0.5) C6(0.5) H6(0.5) C5(0.5) H5(0.5) C4(0.5) H4(0.5) C3A(0.5) H3A(0.5)
 C2A(0.5) C7A(0.5) H7A(0.5) C6A(0.5) H6A(0.5) C5A(0.5) H5A(0.5) C4A(0.5)
 H4A(0.5) C8(0.5) C8A(0.5) C82(0.5) H82A(0.5) H82B(0.5) H82C(0.5) C83(0.5)
 H83A(0.5) H83B(0.5) H83C(0.5) C84(0.5) H84(0.5) C85(0.5) H85A(0.5) H85B(0.5)
 H85C(0.5) O35A(0.5) C82A(0.5) H82D(0.5) H82E(0.5) H82F(0.5) C83A(0.5)
 H83D(0.5) H83E(0.5) H83F(0.5) C84A(0.5) H84A(0.5) C85A(0.5) H85D(0.5)
 H85E(0.5) H85F(0.5)
6.a Riding coordinates:
 C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,
 H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C),
 C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C86(H86A,H86B,H86C), C88(H88A,H88B,
 H88C), C89(H89A,H89B,H89C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C94(H94A,
 H94B,H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C),
 C100(H10A,H10B,H10C), C101(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,
 H10K,H10L), C106(H10M,H10N,H10O), C82A(H82D,H82E,H82F)
6.b Ternary CH refined with riding coordinates:
 C65(H65), C68(H68), C71(H71), C74(H74), C76(H76), C80(H80), C84(H84),
 C87(H87), C90(H90), C93(H93), C96(H96), C99(H99), C102(H102), C105(H105),
 C84A(H84A)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C6(H6), C5(H5), C4(H4), C3A(H3A), C7A(H7A), C6A(H6A),
 C5A(H5A), C4A(H4A), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C17(H17),
  C18(H18), C19(H19), C20(H20), C21(H21), C24(H24), C25(H25), C26(H26),
 C27(H27), C28(H28), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C38(H38),
  C39(H39), C40(H40), C41(H41), C42(H42), C45(H45), C46(H46), C47(H47),
 C48(H48), C49(H49), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C59(H59),
  C60(H60), C61(H61), C62(H62), C63(H63)
6.d Fitted hexagon refined as free rotating group:
 C3(C2,C7,C6,C5,C4), C3A(C2A,C7A,C6A,C5A,C4A)
6.e Idealised Me refined as rotating group:
 C83(H83A,H83B,H83C), C85(H85A,H85B,H85C), C83A(H83D,H83E,H83F), C85A(H85D,
 H85E,H85F)
;
_shelx_res_checksum              4821
_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 1.307
_oxdiff_exptl_absorpt_empirical_full_min 0.690