Carboxylic acid stimulated silver shell isomerism in a triple core–shell Ag <sub>84</sub> nanocluster
Wang, Zhi; Sun, Hao-Tian; Kurmoo, Mohamedally; Liu, Qing-Yun; Zhuang, Gui-Lin; Zhao, Quan-Qin; Wang, Xing-Po; Tung, Chen-Ho; Sun, Di; Chemical Science 10 (2019) 4862–4867; doi:10.1039/C8SC05666H

data_1550817
_publ_section_title
;
 Carboxylic acid stimulated silver shell isomerism in a triple core--shell
 Ag <sub>84</sub> nanocluster
;
_journal_issue                   18
_journal_name_full               'Chemical Science'
_journal_page_first              4862
_journal_page_last               4867
_journal_paper_doi               10.1039/C8SC05666H
_journal_volume                  10
_journal_year                    2019
_chemical_formula_moiety         'C192 H406 Ag84 O88 S42 W14, 2(C H3 O)'
_chemical_formula_sum            'C194 H412 Ag84 O90 S42 W14'
_chemical_formula_weight         17166.71
_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     dual
_audit_creation_date             2018-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-11-14 deposited with the CCDC.    2019-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                109.7140(10)
_cell_angle_beta                 100.1000(10)
_cell_angle_gamma                109.0090(10)
_cell_formula_units_Z            1
_cell_length_a                   20.2607(2)
_cell_length_b                   20.6711(2)
_cell_length_c                   26.2425(3)
_cell_measurement_reflns_used    57340
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      30.8580
_cell_measurement_theta_min      3.3780
_cell_volume                     9266.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30d (Rigaku OD, 2017)'
_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      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     -6.00  75.00   0.50   40.00    --    6.48  57.00  60.00  162
  2  \w     -5.00  75.00   0.50   40.00    --    6.48  46.00-177.00  160
  3  \w    -21.00  28.00   0.50   40.00    --   -5.30 -99.00   0.00   98
  4  \w    -63.00  20.00   0.50   40.00    --    6.48 -46.00  33.00  166
  5  \w    -64.00  17.00   0.50   40.00    --    6.48 -19.00 -90.00  162
;
_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      0.0385537000
_diffrn_orient_matrix_UB_12      0.0120603000
_diffrn_orient_matrix_UB_13      0.0053443000
_diffrn_orient_matrix_UB_21      -0.0009383000
_diffrn_orient_matrix_UB_22      0.0207212000
_diffrn_orient_matrix_UB_23      -0.0166404000
_diffrn_orient_matrix_UB_31      0.0063822000
_diffrn_orient_matrix_UB_32      0.0321038000
_diffrn_orient_matrix_UB_33      0.0247638000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            96913
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.123
_diffrn_reflns_theta_max         25.123
_diffrn_reflns_theta_min         3.270
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    8.936
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56599
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.076
_exptl_crystal_description       block
_exptl_crystal_F_000             7952
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         3.937
_refine_diff_density_min         -1.789
_refine_diff_density_rms         0.272
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2033
_refine_ls_number_reflns         32790
_refine_ls_number_restraints     383
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0578
_refine_ls_shift/su_max          0.039
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0906P)^2^+124.7965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1548
_refine_ls_wR_factor_ref         0.1596
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29005
_reflns_number_total             32790
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05666h2.cif
_cod_data_source_block           SD_Ag84a
_cod_original_cell_volume        9266.29(18)
_cod_database_code               1550817
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         AgS
_shelx_estimated_absorpt_t_max   0.664
_shelx_estimated_absorpt_t_min   0.535
_reflns_odcompleteness_completeness 99.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O36-O35
 2.35 with sigma of 0.01
 C65-C66
 1.55 with sigma of 0.01
 C64-C65
 1.55 with sigma of 0.01
 C64-C66
 2.35 with sigma of 0.01
 C66-O35
 2.35 with sigma of 0.01
 C73-C74
 1.55 with sigma of 0.01
 C72-C73
 1.55 with sigma of 0.01
 C72-C74
 2.35 with sigma of 0.01
 C68-C70
 2.35 with sigma of 0.01
 C69-C68
 1.55 with sigma of 0.01
 C70-C69
 1.55 with sigma of 0.01
 C69-C71
 2.35 with sigma of 0.01
 C70-C71
 1.55 with sigma of 0.01
 C77-C78
 1.55 with sigma of 0.01
 C91-C90
 1.55 with sigma of 0.01
 O36-C67
 1.25 with sigma of 0.01
 C67-O35
 1.25 with sigma of 0.01
 C67-C66
 1.55 with sigma of 0.01
 C67-C65
 2.35 with sigma of 0.01
 C82-C83
 1.55 with sigma of 0.01
 C5-S6
 1.85 with sigma of 0.01
 Ag3B-C5
 3 with sigma of 0.01
 C34-C36
 1.55 with sigma of 0.01
 C29-C28
 1.55 with sigma of 0.01
 C81-C82
 1.55 with sigma of 0.01
 C80-C81
 1.55 with sigma of 0.01
 C80-C82
 2.64 with sigma of 0.01
 C5-C4
 1.55 with sigma of 0.01
 C4-S6
 2.75 with sigma of 0.01
 C62-Ag3A
 3 with sigma of 0.01
 C29-C30
 1.55 with sigma of 0.01
 C28-C30
 2.35 with sigma of 0.01
 C20-S13
 1.85 with sigma of 0.01
 C5-C6
 1.55 with sigma of 0.01
 S6-C6
 2.75 with sigma of 0.01
 C6-C4
 2.35 with sigma of 0.01
 C6-Ag3B
 3.2 with sigma of 0.01
 C61-C62
 1.55 with sigma of 0.01
 C62-C63
 1.55 with sigma of 0.01
3. Restrained planarity
 C66, C67, O35, O36
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C72 \\sim C73 \\sim C74 \\sim C75 \\sim O27 \\sim O28: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C68 \\sim C69 \\sim C70 \\sim C71 \\sim O33 \\sim O34: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C76 \\sim C77 \\sim C78 \\sim C79 \\sim O29 \\sim O30: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C7 \\sim C8 \\sim C9 \\sim C88 \\sim O37 \\sim O38: within 1.7A with sigma of
0.004 and sigma for terminal atoms of 0.008
C34 \\sim C35 \\sim C36: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.08
C13 \\sim C14 \\sim C15: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C55 \\sim C56 \\sim C57: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C89 \\sim C90 \\sim C91 \\sim C92 \\sim O41 \\sim O42: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
Ag4 \\sim Ag4A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag9 \\sim Ag9A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag6 \\sim Ag6A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag7B \\sim Ag16: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
Ag17: within 1.7A with sigma of 0.004 and sigma for terminal atoms of 0.008
Ag8B \\sim Ag17: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
C64 \\sim C65 \\sim C66 \\sim C67 \\sim O35 \\sim O36: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
Ag3 \\sim Ag3A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag1 \\sim Ag1A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag8 \\sim Ag8A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.08
Ag1B \\sim Ag10: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
Ag2B \\sim Ag11: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
Ag3B \\sim Ag12 \\sim Ag38: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.004
Ag5B \\sim Ag14: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.08
Ag4B \\sim Ag13 \\sim Ag31: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.08
C80 \\sim C81 \\sim C82 \\sim C83 \\sim O25 \\sim O26: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C28 \\sim C29 \\sim C30 \\sim S16: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
C45 \\sim C44 \\sim C43: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.08
C21 \\sim C20 \\sim C19 \\sim S13: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.08
C4 \\sim C5 \\sim C6 \\sim S6: within 1.7A with sigma of 0.002 and sigma for
terminal atoms of 0.004
C62 \\sim S21 \\sim C63 \\sim C61: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
5. Others
 Sof(Ag1A)=1-FVAR(1)
 Sof(Ag1)=FVAR(1)
 Sof(Ag2A)=1-FVAR(2)
 Sof(Ag2)=FVAR(2)
 Sof(Ag3A)=1-FVAR(3)
 Sof(Ag3)=FVAR(3)
 Sof(Ag4A)=1-FVAR(4)
 Sof(Ag4)=FVAR(4)
 Sof(Ag5A)=1-FVAR(5)
 Sof(Ag5)=FVAR(5)
 Sof(Ag6A)=1-FVAR(6)
 Sof(Ag6)=FVAR(6)
 Sof(Ag7A)=1-FVAR(7)
 Sof(Ag7)=FVAR(7)
 Sof(Ag8A)=1-FVAR(8)
 Sof(Ag8)=FVAR(8)
 Sof(Ag9A)=1-FVAR(9)
 Sof(Ag9)=FVAR(9)
 Sof(Ag1B)=1-FVAR(10)
 Sof(Ag10)=FVAR(10)
 Sof(Ag2B)=1-FVAR(11)
 Sof(Ag11)=FVAR(11)
 Sof(Ag3B)=1-FVAR(12)
 Sof(Ag12)=FVAR(12)
 Sof(Ag4B)=Sof(Ag5B)=1-FVAR(13)
 Sof(Ag13)=Sof(Ag14)=FVAR(13)
 Sof(Ag7B)=1-FVAR(14)
 Sof(Ag16)=FVAR(14)
 Sof(Ag9B)=1-FVAR(15)
 Sof(Ag18)=FVAR(15)
 Fixed Sof: Ag8B(0.1) Ag17(0.9)
6.a Riding coordinates:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C),
 C62(H62), C64(H64A,H64B,H64C), C68(H68A,H68B,H68C), C72(H72A,H72B,H72C),
 C76(H76A,H76B,H76C), C84(H84A,H84B,H84C), C89(H89A,H89B,H89C), C93(H93A,H93B,
 H93C)
6.b Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C11(H11), C14(H14), C17(H17), C20(H20), C23(H23), C26(H26),
 C29(H29), C32(H32), C36(H36), C38(H38), C41(H41), C44(H44), C47(H47), C50(H50),
  C53(H53), C56(H56), C59(H59)
6.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C65(H65A,H65B), C66(H66A,H66B), C69(H69A,H69B),
 C70(H70A,H70B), C73(H73A,H73B), C74(H74A,H74B), C77(H77A,H77B), C78(H78A,H78B),
  C81(H81A,H81B), C82(H82A,H82B), C85(H85A,H85B), C86(H86A,H86B), C90(H90A,
 H90B), C91(H91A,H91B), C94(H94A,H94B), C95(H95A,H95B)
6.d Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C),
 C80(H80A,H80B,H80C)
6.e Idealised Me refined as rotating group:
 C97(H97A,H97B,H97C)
;
_shelx_res_checksum              84924
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.723