Polyoxometalate-mediated syntheses of three structurally new silver clusters.
Zhang, Jing; Dong, Yuanyuan; Deng, Lan; Chi, Manzhou; Feng, Yeqin; Zhao, Mengyun; Lv, Hongjin; Yang, Guo-Yu; Nanoscale 16 (2024) 11518–11523; doi:10.1039/d4nr02016b

data_1571724
_publ_section_title
;
 Polyoxometalate-mediated syntheses of three structurally new silver
 clusters.
;
_journal_issue                   24
_journal_name_full               Nanoscale
_journal_page_first              11518
_journal_page_last               11523
_journal_paper_doi               10.1039/d4nr02016b
_journal_volume                  16
_journal_year                    2024
_chemical_formula_moiety
'C195 H231.185 Ag22 Cl Cu O34 P12 S11 Si W9, 2(F6 Sb)'
_chemical_formula_sum
'C195 H231.18 Ag22 Cl Cu F12 O34 P12 S11 Sb2 Si W9'
_chemical_formula_weight         8469.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2jnp0x
_audit_creation_date             2024-03-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.7177(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.8060(3)
_cell_length_b                   32.6834(5)
_cell_length_c                   41.5251(8)
_cell_measurement_reflns_used    71905
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.9660
_cell_measurement_theta_min      2.0620
_cell_volume                     27911.3(8)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            236237
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.934
_exptl_absorpt_coefficient_mu    5.681
_exptl_crystal_colour            'clear brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.016
_exptl_crystal_description       block
_exptl_crystal_F_000             15997
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         6.898
_refine_diff_density_min         -6.663
_refine_diff_density_rms         0.329
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2453
_refine_ls_number_reflns         49117
_refine_ls_number_restraints     4635
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1655
_refine_ls_R_factor_gt           0.1165
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1600P)^2^+1407.8883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2989
_refine_ls_wR_factor_ref         0.3435
_reflns_Friedel_coverage         0.000
_reflns_number_gt                31327
_reflns_number_total             49117
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr02016b2.cif
_cod_data_source_block           test_sq
_cod_depositor_comments
'Adding full bibliography for 1571724--1571726.cif.'
_cod_database_code               1571724
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.412
_shelx_estimated_absorpt_t_min   0.382
_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
 C322-C323 = C323-C324
 1.5 with sigma of 0.02
 C313-C314 = C314-C315
 1.5 with sigma of 0.02
 C303-C305 = C309-C311 = C319-C321
 2.2 with sigma of 0.02
 C309-C310 = C310-C311
 1.5 with sigma of 0.02
 C326-C327 = C316-C317 = C317-C318
 1.5 with sigma of 0.02
 S2-C311
 2.8 with sigma of 0.02
 C301-C300 = C300-C302
 1.5 with sigma of 0.02
 P18-C316
 1.9 with sigma of 0.02
 P18-C91
 1.8 with sigma of 0.02
 P21-C114
 2.7 with sigma of 0.02
 Ag7-S7
 2.5 with sigma of 0.02
 F131-F86
 2.4 with sigma of 0.02
 C164-C166
 1.54 with sigma of 0.02
 C150-C148
 1.54 with sigma of 0.02
 C320-C319 = C321-C320
 1.54 with sigma of 0.02
 C321-C320 = C320-C319
 1.54 with sigma of 0.02
 C149-C148
 1.54 with sigma of 0.02
 S7-C164
 1.7 with sigma of 0.02
 C153-C152 = C152-C151
 1.54 with sigma of 0.02
 Ag2-S8
 2 with sigma of 0.02
 Sb1-F56 \\sim Sb1-F97 \\sim Sb1-F110 \\sim Sb1-F124 \\sim Sb1-F145 \\sim
Sb1-F213
 with sigma of 0.02
 Sb2-F86 \\sim Sb2-F131 \\sim Sb2-F161 \\sim Sb2-F174 \\sim Sb2-F185 \\sim
Sb2-F134
 with sigma of 0.02
 F56-F97 \\sim F56-F110 \\sim F56-F145 \\sim F56-F213 \\sim F97-F110 \\sim
F97-F124 \\sim F97-F145 ~
 F110-F124 \\sim F110-F213 \\sim F124-F145 \\sim F124-F213 \\sim F145-F213
 with sigma of 0.04
 F86-F131 \\sim F86-F174 \\sim F86-F185 \\sim F86-F134 \\sim F131-F161 \\sim
F131-F174 \\sim F131-F134
 \\sim F161-F174 \\sim F161-F185 \\sim F161-F134 \\sim F174-F185 \\sim F185-F134
 with sigma of 0.04
3. Restrained planarity
 P21, C109, C110, C111, C112, C113, C114
 with sigma of 0.1
 P13, C121, C122, C123, C124, C125, C126
 with sigma of 0.1
 P13, C127, C128, C129, C130, C131, C132
 with sigma of 0.1
 P21, C139, C140, C141, C142, C143, C144
 with sigma of 0.1
 P18, C91, C92, C93, C94, C95, C96
 with sigma of 0.1
4. Rigid bond restraints
 Sb2, F86, F131, F161, F174, F185, F134
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Sb1, F56, F97, F110, F124, F145, F213
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
F56 \\sim F86 \\sim F97 \\sim F110 \\sim F124 \\sim F131 \\sim F145 \\sim F161
\\sim F174 \\sim F213 \\sim F185 \\sim F134: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C30A \\sim C30B \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7
\\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15
\\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23
\\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31
\\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39
\\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47
\\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55
\\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63
\\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71
\\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79
\\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87
\\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95
\\sim C96 \\sim C97 \\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim
C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim
C110 \\sim C111 \\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim
C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim
C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim
C131 \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim
C138 \\sim C139 \\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim
C300 \\sim C301 \\sim C302 \\sim C303 \\sim C304 \\sim C305 \\sim C313 \\sim
C314 \\sim C315 \\sim C316 \\sim C317 \\sim C318 \\sim C319 \\sim C320 \\sim
C321 \\sim C322 \\sim C323 \\sim C324 \\sim C309 \\sim C310 \\sim C311 \\sim
C325 \\sim C326 \\sim C327 \\sim C328 \\sim C329 \\sim C146 \\sim C157 \\sim
C145 \\sim C171 \\sim C201 \\sim C147 \\sim C154 \\sim C156 \\sim C151 \\sim
C148 \\sim C149 \\sim C155 \\sim C152 \\sim C150 \\sim C153 \\sim C161 \\sim
C160 \\sim C159 \\sim C158 \\sim C163 \\sim C162 \\sim C165 \\sim C164 \\sim
C166: within 4A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
4A
Uanis(Sb2) \\sim Ueq, Uanis(Sb1) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(Ag1A) \\sim Ueq, Uanis(Ag2A) \\sim Ueq, Uanis(Ag3A) \\sim Ueq,
Uanis(Ag1B) \\sim Ueq, Uanis(Ag2B) \\sim Ueq, Uanis(Ag3B) \\sim Ueq, Uanis(Ag4)
\\sim Ueq, Uanis(Ag5A) \\sim Ueq, Uanis(Ag5B) \\sim Ueq, Uanis(Ag6) \\sim Ueq,
Uanis(Ag7) \\sim Ueq, Uanis(Ag8A) \\sim Ueq, Uanis(Ag8B) \\sim Ueq, Uanis(Ag9A)
\\sim Ueq, Uanis(Ag9B) \\sim Ueq, Uanis(Ag10) \\sim Ueq, Uanis(Ag11) \\sim Ueq,
Uanis(Ag12) \\sim Ueq, Uanis(Ag13) \\sim Ueq, Uanis(Ag14) \\sim Ueq,
Uanis(Ag15) \\sim Ueq, Uanis(Ag18) \\sim Ueq, Uanis(Ag19) \\sim Ueq,
Uanis(Ag20) \\sim Ueq, Uanis(Ag35) \\sim Ueq, Uanis(Ag38) \\sim Ueq,
Uanis(Ag39) \\sim Ueq, Uanis(Ag41) \\sim Ueq, Uanis(Ag1) \\sim Ueq, Uanis(Ag2)
\\sim Ueq, Uanis(Ag3) \\sim Ueq, Uanis(S4) \\sim Ueq, Uanis(S10) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F145) \\sim Ueq, Uanis(F56) \\sim Ueq, Uanis(F213) \\sim Ueq, Uanis(F124)
\\sim Ueq, Uanis(F97) \\sim Ueq, Uanis(F110) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(O1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4) \\sim
Ueq, Uanis(O5) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(O17) \\sim Ueq, Uanis(O19)
\\sim Ueq, Uanis(P18) \\sim Ueq, Uanis(P19) \\sim Ueq, Uanis(P20) \\sim Ueq,
Uanis(P21) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Ag15) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(S9B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F185) \\sim Ueq, Uanis(F86) \\sim Ueq, Uanis(F134) \\sim Ueq, Uanis(F131)
\\sim Ueq, Uanis(F174) \\sim Ueq, Uanis(F161) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Ag3A) = Uanis(Ag3B)
Uanis(Ag2) = Uanis(Ag41)
Uanis(Cu6A) = Uanis(Cu6B)
Uanis(Ag1) = Uanis(Ag39)
Uanis(Ag5A) = Uanis(Ag5B)
Uanis(Ag2A) = Uanis(Ag2B)
Uanis(Ag1A) = Uanis(Ag1B)
Uanis(Ag9A) = Uanis(Ag9B)
Uanis(Ag8A) = Uanis(Ag8B)
Uanis(S7) = Uanis(S10)
Uanis(S8) = Uanis(S11)
Uanis(C152) = Uanis(C320)
Uanis(S10) = Uanis(S5)
Uanis(F213) = Uanis(F97)
Uanis(F185) = Uanis(F131)
6. Same fragment restrains
{C309, C310, C311, S2} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C325, C326, C327, S4}
7. Others
 Sof(Ag1B)=Sof(Ag2B)=Sof(Ag3B)=1-FVAR(1)
 Sof(Ag1A)=Sof(Ag2A)=Sof(Ag3A)=FVAR(1)
 Sof(C30B)=Sof(H30C)=Sof(H30D)=Sof(P1B)=Sof(Ag9B)=1-FVAR(2)
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(P1A)=Sof(Ag9A)=Sof(H32R)=Sof(H32S)=FVAR(2)
 Sof(Ag8B)=1-FVAR(3)
 Sof(Ag8A)=FVAR(3)
 Sof(Ag5B)=1-FVAR(4)
 Sof(Ag5A)=FVAR(4)
 Fixed Sof: Ag38(0.5) Ag39(0.5) Ag41(0.5) Ag1(0.5) Cu6A(0.5) Ag2(0.5)
 Cu6B(0.5) H152(0.5) Ag3(0.5)
 Fixed X: C313(0.34662)
8.a Ternary CH refined with riding coordinates:
 C300(H300), C304(H304), C314(H314), C320(H320), C323(H323), C310(H310),
 C326(H326), C154(H154), C148(H148), C152(H152), C164(H164)
8.b Secondary CH2 refined with riding coordinates:
 C30A(H30A,H30B), C30B(H30C,H30D), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C316(H31G,H31H), C317(H31I,
 H31J), C318(H31K,H31L), C328(H32P,H32Q), C329(H32R,H32S)
8.c Me refined with riding coordinates:
 C322(H32D,H32E,H32F), C324(H32G,H32H,H32I), C309(H30Q,H30R,H30S)
8.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
  C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
 C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48),
  C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
 C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75),
 C76(H76), C77(H77), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84),
  C86(H86), C87(H87), C88(H88), C89(H89), C90(H90), C92(H92), C93(H93),
 C94(H94), C95(H95), C96(H96), C98(H98), C99(H99), C100(H100), C101(H101),
 C102(H102), C104(H104), C105(H105), C106(H106), C107(H107), C108(H108),
 C110(H110), C111(H111), C112(H112), C113(H113), C114(H114), C116(H116),
 C117(H117), C118(H118), C119(H119), C120(H120), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C128(H128), C129(H129), C130(H130),
 C131(H131), C132(H132), C134(H134), C135(H135), C136(H136), C137(H137),
 C138(H138), C139(H139), C140(H140), C141(H141), C142(H142), C143(H143),
 C146(H146), C145(H145), C171(H171), C201(H201), C147(H147), C160(H160),
 C159(H159), C158(H158), C163(H163), C162(H162)
8.e Fitted hexagon refined as free rotating group:
 C13(C14,C15,C16,C17,C18), C19(C20,C21,C22,C23,C24), C25(C26,C27,C28,C29,C30),
 C31(C32,C33,C34,C35,C36), C37(C38,C39,C40,C41,C42), C43(C44,C45,C46,C47,C48),
 C49(C50,C51,C52,C53,C54), C55(C56,C57,C58,C59,C60), C61(C62,C63,C64,C65,C66),
 C67(C68,C69,C70,C71,C72), C73(C74,C75,C76,C77,C78), C79(C80,C81,C82,C83,C84),
 C85(C86,C87,C88,C89,C90), C91(C92,C93,C94,C95,C96), C97(C98,C99,C100,C101,
 C102), C103(C104,C105,C106,C107,C108), C109(C110,C111,C112,C113,C114),
 C115(C116,C117,C118,C119,C120), C121(C122,C123,C124,C125,C126), C127(C128,C129,
 C130,C131,C132), C133(C134,C135,C136,C137,C138), C139(C140,C141,C142,C143,
 C144), C146(C157,C145,C171,C201,C147), C161(C160,C159,C158,C163,C162)
8.f Idealised Me refined as rotating group:
 C301(H30E,H30F,H30G), C302(H30H,H30I,H30J), C303(H30K,H30L,H30M), C305(H30N,
 H30O,H30P), C313(H31A,H31B,H31C), C315(H31D,H31E,H31F), C319(H31M,H31N,H31O),
 C321(H32A,H32B,H32C), C311(H31P,H31Q,H31R), C325(H32J,H32K,H32L), C327(H32M,
 H32N,H32O), C156(H15A,H15B,H15C), C151(H15D,H15E,H15F), C149(H14A,H14B,H14C),
 C155(H15G,H15H,H15I), C150(H15J,H15K,H15L), C153(H15M,H15N,H15O), C165(H16A,
 H16B,H16C), C166(H16D,H16E,H16F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              29875
_shelx_hkl_checksum              73577
_shelx_fab_checksum              44263
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'