Site-specific sulfur-for-metal replacement in silver nanocluster
Wu, Ya-Ge; Huang, Jia-Hong; Zhang, Chong; Dong, Xi-Yan; Guo, Xiang-Kun; Wu, Weina; Zang, Shuang-Quan; Chemical Communications  (2022) –; doi:10.1039/D2CC00794K

data_7130160
_publ_section_title
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 Site-specific sulfur-for-metal replacement in silver nanocluster
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_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00794K
_journal_year                    2022
_chemical_formula_moiety         'C194 H184 Ag36 F30 N4 O24 P2 S18'
_chemical_formula_sum            'C224 H258 Ag36 F30 N14 O36 P2 S18'
_chemical_formula_weight         8814.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-05-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
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2022-05-28 deposited with the CCDC.	2022-05-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.116(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   40.552(10)
_cell_length_b                   30.945(7)
_cell_length_c                   22.193(5)
_cell_measurement_reflns_used    9411
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      26.76
_cell_measurement_theta_min      2.28
_cell_volume                     27498(11)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        SAINT
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1231
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            650255
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.961
_exptl_absorpt_coefficient_mu    2.727
_exptl_absorpt_correction_T_max  0.772
_exptl_absorpt_correction_T_min  0.718
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 2003)'
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.129
_exptl_crystal_description       block
_exptl_crystal_F_000             17072
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.182
_refine_diff_density_min         -1.894
_refine_diff_density_rms         0.227
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1414
_refine_ls_number_reflns         24206
_refine_ls_number_restraints     1100
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.1400
_refine_ls_R_factor_gt           0.0959
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+2145.8477P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2080
_refine_ls_wR_factor_ref         0.2606
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16477
_reflns_number_total             24206
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00794k2.cif
_cod_data_source_block           ag36
_cod_original_cell_volume        27497(11)
_cod_database_code               7130160
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.772
_shelx_estimated_absorpt_t_min   0.718
_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
 C6-C5
 1.51 with sigma of 0.01
 C1AA-C0AA
 1.51 with sigma of 0.01
 C4-C3
 1.51 with sigma of 0.01
 C77-O12
 1.2 with sigma of 0.02
 N2-C79 = N2-C78
 1.45 with sigma of 0.02
 C33-C32
 1.51 with sigma of 0.01
 O11-C74
 1.2 with sigma of 0.02
 N1-C75 = N1-C76
 1.45 with sigma of 0.01
 C10-C9
 1.51 with sigma of 0.01
 C2-C1
 1.51 with sigma of 0.01
 F18-C1AA
 1.45 with sigma of 0.02
 C1AA-F16
 1.45 with sigma of 0.02
 F16-C1AA = F18-C1AA
 1.45 with sigma of 0.01
 F17-C1AA
 1.45 with sigma of 0.01
 S7-C54 = S7-C53
 1.85 with sigma of 0.01
 C55-C54 = C61-C53
 1.51 with sigma of 0.01
 C71-C70 = C71-C72 = C72-C73 = C70-C69 = C69-C68 = C73-C68
 1.39 with sigma of 0.01
 C1AA-O1AA
 2.2 with sigma of 0.04
 F10-C8 \\sim F11-C8 \\sim F12-C8
 with sigma of 0.02
 F11-F12 \\sim F11-F10 \\sim F12-F10
 with sigma of 0.02
 C7-F10 \\sim C7-F11 \\sim C7-F12
 with sigma of 0.02
 F2-C2 \\sim F3-C2 \\sim F1-C2
 with sigma of 0.01
 C1-F1 \\sim C1-F2 \\sim C1-F3
 with sigma of 0.02
 F2A-C2 \\sim F3A-C2 \\sim F3-C2 \\sim F1A-C2
 with sigma of 0.02
 F16-F17 \\sim F16-F18 \\sim F17-F18
 with sigma of 0.02
 O1AA-C0AA \\sim O0AA-C0AA
 with sigma of 0.01
3. Restrained planarity
 F1, F1A, F2, F2A, F3, F3A
 with sigma of 0.1
4. Rigid bond restraints
 F4, F5, F6, O3, O4, C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F7, F8, F9, O5, O6, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O12, N2, C77, C78, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F10, F11, F12, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S4, C32, C33, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F13, F14, F15, O9, O10, C9, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S7, C54, C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S7, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C70,
  C71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Ag15 \\sim F16 \\sim F18 \\sim O1AA \\sim C0AA \\sim C1AA: within 3A with sigma
of 0.01 and sigma for terminal atoms of 0.01
Ag15 \\sim F16 \\sim F17 \\sim F18 \\sim O0AA \\sim O1AA \\sim C1AA: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.01
Ag23 \\sim O11 \\sim N1 \\sim C74 \\sim C75 \\sim C76: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.01
Ag15: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.01
Ag19 \\sim Ag20: within 3A with sigma of 0.01 and sigma for terminal atoms of
0.01
Uanis(Ag1) \\sim Ueq, Uanis(Ag2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(F6) \\sim
Ueq, Uanis(F5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(F7) \\sim
Ueq, Uanis(F8) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(O5) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C78) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(O12) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C98)
\\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C102) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C32) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C68) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C71) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3)
\\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C53) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C60) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C54) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Ag7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O0AA) = Uanis(C0AA)
6. Same fragment restrains
{F1, F2, F3, O1, O2, C1, C2} sigma for 1-2: 0.02, 1-3: 0.04
as
{F4, F5, F6, O3, O4, C3, C4}
{F1, F2, F3, O1, O2, C1, C2} sigma for 1-2: 0.02, 1-3: 0.04
as
{F7, F8, F9, O5, O6, C5, C6}
{F1, F2, F3, O1, O2, C1, C2} sigma for 1-2: 0.02, 1-3: 0.04
as
{F13, F14, F15, O9, O10, C9, C10}
7. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=1-FVAR(2)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=FVAR(2)
 Sof(Ag2)=1-FVAR(3)
 Sof(Ag1)=FVAR(3)
 Fixed Sof: F10(0.5) F11(0.5) F12(0.5) F16(0.5) F17(0.5) F18(0.5) O0AA(0.5)
 O1AA(0.5) C0AA(0.5) C1AA(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C25(H25A,H25B), C32(H32A,H32B), C39(H39A,
 H39B), C46(H46A,H46B), C53(H53A,H53B), C54(H54A,H54B), C67(H67A,H67B),
 C98(H98A,H98B)
8.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C14(H14), C13(H13), C17(H17), C16(H16), C23(H23), C24(H24),
 C20(H20), C21(H21), C22(H22), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
  C34(H34), C35(H35), C37(H37), C36(H36), C38(H38), C41(H41), C42(H42),
 C43(H43), C44(H44), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52),
  C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73),
  C74(H74), C77(H77), C81(H81), C82(H82), C83(H83), C84(H84), C85(H85),
 C90(H90), C89(H89), C88(H88), C87(H87), C91(H91), C94(H94), C93(H93), C97(H97),
  C96(H96), C95(H95), C104(H104), C103(H103), C102(H102), C101(H101), C100(H100)
8.c Fitted hexagon refined as free rotating group:
 C15(C14,C13,C12,C17,C16), C23(C24,C19,C20,C21,C22), C33(C34,C35,C37,C36,C38),
 C40(C41,C42,C43,C44,C45), C55(C56,C57,C58,C59,C60), C61(C62,C63,C64,C65,C66),
 C80(C81,C82,C83,C84,C85), C90(C89,C88,C87,C86,C91), C94(C93,C92,C97,C96,C95),
 C104(C103,C102,C101,C100,C99)
8.d Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,
 H79C)
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_shelx_res_checksum              68714
_shelx_fab_checksum              98217
_olex2_submission_special_instructions 'No special instructions were received'