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_7123931
_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
'C112 H238 Ag66 Mo9 O64 S28, 4(C H4 O), C4 H6 O4'
_chemical_formula_sum            'C120 H260 Ag66 Mo9 O72 S28'
_chemical_formula_weight         11735.82
_space_group_crystal_system      orthorhombic
_space_group_IT_number           58
_space_group_name_Hall           '-P 2 2n'
_space_group_name_H-M_alt        'P n n m'
_symmetry_space_group_name_Hall  '-P 2 2n'
_symmetry_space_group_name_H-M   'P n n m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-07-14
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.780(2)
_cell_length_b                   21.915(3)
_cell_length_c                   33.362(4)
_cell_measurement_reflns_used    9661
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.509
_cell_measurement_theta_min      2.569
_cell_volume                     14462(3)
_computing_cell_refinement       'SAINT V8.30C (?, 2016)'
_computing_data_reduction        'SAINT V8.30C (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX II'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0518
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            99413
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.451
_exptl_absorpt_coefficient_mu    4.978
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.2624
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1467 before and 0.0688 after correction.
The Ratio of minimum to maximum transmission is 0.3519.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_density_diffrn    2.695
_exptl_crystal_description       block
_exptl_crystal_F_000             10968
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_platon_squeeze_details
;
The lattice contains large solvents and anions accessible voids, 
but they are highly disordered and therefore 
could not be modelled. Instead,they are treated by 
the program SQUEEZE. These electrons removed by SQUEEZE have 
been assigned as 3 CH3OH, 14 DMF and 2 additional 
counter ions (62 electrons/2 OAc) per Formula unit.
Spek, A. L. (2015). Acta Cryst. C71, 9-18
TITL p in Pnnm
CELL   19.7800   21.9150   33.3630     90.00     90.00     90.00
SPGR Pnnm
Q101 0.727 0.786 0.537 !       8.63 eA-3
Q102 0.206 0.502 0.313 !       7.47 eA-3
Q103 0.309 0.400 0.530 !       6.41 eA-3
Q104 0.500 0.999 0.266 !       6.15 eA-3
Q105 0.500 1.001 0.766 !       6.08 eA-3
Q106 0.803 0.812 0.468 !       5.21 eA-3
Q107 0.286 0.050 0.079 !       4.80 eA-3
Q108 0.786 0.087 0.874 !       4.03 eA-3
Q109 0.629 0.088 0.244 !       3.51 eA-3
Q110 0.556 0.400 0.100 !       3.49 eA-3
Q111 0.369 0.389 0.540 !       3.46 eA-3
Q112 0.239 0.446 0.376 !       3.46 eA-3
Q113 0.091 0.662 0.391 !       3.39 eA-3
Q114 0.591 0.866 0.117 !       3.20 eA-3
Q115 0.325 0.439 0.359 !       3.08 eA-3
Q116 0.680 0.208 0.851 !       3.04 eA-3
Q117 0.267 0.508 0.501 !       2.98 eA-3
Q118 0.530 0.235 0.047 !       2.93 eA-3
Q119 0.521 0.086 0.002 !       2.91 eA-3
Q120 0.078 0.219 0.623 !       2.80 eA-3
Q121 0.010 0.272 0.430 !       2.77 eA-3
Q122 0.629 0.870 0.897 !       2.69 eA-3
Q123 0.663 0.605 0.554 !       2.62 eA-3
Q124 0.180 0.427 0.796 !       2.59 eA-3
Q125 0.133 0.260 0.759 !       2.59 eA-3
Q126 0.414 0.693 0.884 !       2.58 eA-3
Q127 0.779 0.470 0.390 !       2.51 eA-3
Q128 0.064 0.520 0.545 !       2.50 eA-3
Q129 0.084 0.576 0.712 !       2.47 eA-3
Q130 0.367 0.674 0.946 !       2.42 eA-3
Q131 0.322 0.141 0.002 !       2.39 eA-3
C132 0.742 0.602 0.003 !       2.37 eA-3
Q133 0.312 0.284 0.397 !       2.29 eA-3
Q134 0.084 0.492 0.469 !       2.28 eA-3
Q135 0.496 0.829 0.180 !       2.28 eA-3
C136 0.237 0.352-0.001 !       2.23 eA-3
Q137 0.268 0.477 0.501 !       2.22 eA-3
Q138 0.811 0.007 0.070 !       2.22 eA-3
Q139 0.526 0.062 0.001 !       2.19 eA-3
Q140 0.062 0.099 0.633 !       2.17 eA-3
Q141 0.347 0.297 0.500 !       2.15 eA-3
Q142 0.585 0.901 0.197 !       2.13 eA-3
Q143 0.803 0.920 0.538 !       2.13 eA-3
Q144 0.744 0.995 0.188 !       2.11 eA-3
Q145 0.822 0.116 0.782 !       2.06 eA-3
Q146 0.366 0.172 0.001 !       2.02 eA-3
Q147 0.435 0.361 0.610 !       1.94 eA-3
Q148 0.338 0.800 0.820 !       1.93 eA-3
C149 0.686 0.172 0.540 !       1.89 eA-3
Q150 0.105 0.641 0.499 !       1.87 eA-3
Q151 0.466 0.231 0.888 !       1.85 eA-3
Q152 0.351 0.118 0.986 !       1.85 eA-3
Q153 0.239 0.384 0.314 !       1.83 eA-3
Q154 0.715 0.172 0.148 !       1.82 eA-3
Q155 0.786 0.328 0.717 !       1.80 eA-3
Q156 0.749 0.359-0.001 !       1.79 eA-3
C157 0.722 0.532 0.071 !       1.77 eA-3
Q158 0.798 0.789 0.390 !       1.77 eA-3
Q159 0.029 0.311 0.686 !       1.76 eA-3
Q160 0.250 0.326 0.242 !       1.75 eA-3
Q161 0.093 0.245 0.694 !       1.75 eA-3
Q162 0.749 0.742 0.547 !       1.74 eA-3
C163 0.340 0.768 0.447 !       1.72 eA-3
Q164 0.099 0.638 0.470 !       1.71 eA-3
C165 0.842 0.720 0.072 !       1.69 eA-3
Q166 0.369 0.573 0.076 !       1.68 eA-3
Q167 0.688 0.905 0.164 !       1.68 eA-3
Q168 0.024 0.875 0.500 !       1.67 eA-3
Q169 0.752 0.391 0.003 !       1.66 eA-3
Q170 0.446 0.070 0.205 !       1.66 eA-3
Q171 0.157 0.507 0.220 !       1.64 eA-3
Q172 0.781 0.822 0.938 !       1.64 eA-3
Q173 0.857 0.983 0.783 !       1.60 eA-3
Q174 0.349 0.638 0.046 !       1.60 eA-3
Q175 0.146 0.336 0.266 !       1.59 eA-3
C176 0.114 0.275 0.061 !       1.58 eA-3
C177 0.329 0.819 0.600 !       1.57 eA-3
Q178 0.917 0.798 0.350 !       1.56 eA-3
Q179 0.513 0.118 0.233 !       1.56 eA-3
Q180 0.962 0.368 0.787 !       1.50 eA-3
Q181 0.452 0.204 0.721 !       1.48 eA-3
C182 0.812 0.701 0.172 !       1.48 eA-3
C183 0.872 0.748 0.927 !       1.46 eA-3
Q184 0.177 0.507 0.718 !       1.46 eA-3
Q185 0.135 0.488 0.165 !       1.44 eA-3
C186 0.123 0.358 0.933 !       1.42 eA-3
Q187 0.242 0.150 0.623 !       1.42 eA-3
C188 0.612 0.147 0.585 !       1.42 eA-3
Q189 0.634 0.401 0.570 !       1.40 eA-3
C190 0.308 0.454 0.063 !       1.40 eA-3
Q191 0.832 0.703 0.500 !       1.40 eA-3
C192 0.339 0.807 0.360 !       1.38 eA-3
Q193 0.653 0.019 0.204 !       1.38 eA-3
Q194 0.245 0.664 0.329 !       1.37 eA-3
C195 0.419 1.000 0.390 !       1.37 eA-3
Q196 0.600 0.008-0.001 !       1.36 eA-3
Q197 0.923 0.813 0.498 !       1.35 eA-3
Q198 0.053 0.180 0.501 !       1.34 eA-3
C199 0.137 0.317 0.920 !       1.30 eA-3
;
_refine_diff_density_max         7.014
_refine_diff_density_min         -4.645
_refine_diff_density_rms         0.397
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.867
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         12945
_refine_ls_number_restraints     246
_refine_ls_restrained_S_all      2.056
_refine_ls_R_factor_all          0.1544
_refine_ls_R_factor_gt           0.1224
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3605
_refine_ls_wR_factor_ref         0.4347
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9267
_reflns_number_total             12945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05044b2.cif
_cod_data_source_block           SD_Ag66d
_cod_database_code               7123931
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.636
_shelx_estimated_absorpt_t_min   0.317
_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, All O(H) groups
2. Restrained distances
 O2-O1A
 2.45 with sigma of 0.01
 O20-C26
 2.45 with sigma of 0.01
 C20-O1A
 1.45 with sigma of 0.01
 C20-O2
 1.45 with sigma of 0.01
 O14-C8
 1.25 with sigma of 0.01
 C8-O15
 1.25 with sigma of 0.01
 C25-C26
 1.55 with sigma of 0.01
 O20-C25
 1.25 with sigma of 0.01
 C32-S5
 2.75 with sigma of 0.01
 O14-C7
 2.45 with sigma of 0.01
 C8-C7
 1.55 with sigma of 0.01
 C30-S5
 2.75 with sigma of 0.01
 C30-C32
 2.35 with sigma of 0.01
 C31-S5
 1.85 with sigma of 0.01
 C32-C31
 1.55 with sigma of 0.01
 C31-C30
 1.55 with sigma of 0.01
 C22-S8
 2.75 with sigma of 0.01
 C23-C22
 1.55 with sigma of 0.01
 S8-C23
 1.85 with sigma of 0.01
 C24-C22
 2.35 with sigma of 0.01
 C24-S8
 2.75 with sigma of 0.01
 C24-C23
 1.55 with sigma of 0.01
 C10-C11
 1.55 with sigma of 0.01
 C9-C10
 1.55 with sigma of 0.01
 C9-C11
 2.35 with sigma of 0.01
 S8-C23A
 1.85 with sigma of 0.01
 O16A-C15A = O17A-C15A
 1.25 with sigma of 0.01
 S7-C28
 1.85 with sigma of 0.01
 C16-C15
 1.55 with sigma of 0.01
 C29-C28
 1.55 with sigma of 0.01
 S7-C29
 2.85 with sigma of 0.01
 O21-O22
 2.17 with sigma of 0.01
 C34-O21
 2.43 with sigma of 0.01
 C34-O22
 2.43 with sigma of 0.01
 C23A-C24A
 1.55 with sigma of 0.01
 C27-C28
 1.55 with sigma of 0.01
 C23A-C22A
 1.55 with sigma of 0.01
 C24A-C22A
 2.35 with sigma of 0.01
 C1-C2
 1.55 with sigma of 0.01
 C2-C3
 2.35 with sigma of 0.01
 C1-C3
 1.55 with sigma of 0.01
 O20-O19
 2.35 with sigma of 0.01
 C25-O19
 1.25 with sigma of 0.01
 C35-O21
 1.25 with sigma of 0.01
 C35-O22
 1.25 with sigma of 0.01
 C35-C34
 1.55 with sigma of 0.01
 C17-C19
 1.55 with sigma of 0.01
 C33-O18
 1.45 with sigma of 0.01
 S2-C5
 1.85 with sigma of 0.01
 C5-C6A
 1.55 with sigma of 0.01
 C5-C4 = C6-C5
 1.55 with sigma of 0.01
 C4-C6
 2.35 with sigma of 0.01
 C2A-C3A
 2.35 with sigma of 0.01
 C2A-C1 = C3A-C1
 1.55 with sigma of 0.01
 C4A-C5
 1.55 with sigma of 0.01
 S2-C4A
 2.75 with sigma of 0.01
 C4A-C6A
 2.35 with sigma of 0.01
 C15A-C16A
 1.55 with sigma of 0.01
 O17A-C16A
 2.35 with sigma of 0.01
 C16A-O16A
 2.35 with sigma of 0.01
3. Restrained planarity
 C34, C35, O21, O22
 with sigma of 0.01
 C15A, C16A, O16A, O17A
 with sigma of 0.005
4. Uiso/Uaniso restraints and constraints
C20 \\sim C21 \\sim O1 \\sim O1A \\sim O2 \\sim O2A: within 1.7A with sigma of
0.004 and sigma for terminal atoms of 0.08
C7 \\sim C8 \\sim O14 \\sim O15: 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
0.008
Ag2 \\sim Ag2A: 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
0.008
Ag4 \\sim Ag4A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
Ag5 \\sim Ag5A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
Ag6 \\sim Ag6A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
Ag7 \\sim Ag7A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
Ag8 \\sim Ag8A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
Ag9 \\sim Ag9A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
C30 \\sim C31 \\sim C32: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.08
C22 \\sim C23 \\sim C24 \\sim S8: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008
C9 \\sim C10 \\sim C11: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
Ag1B \\sim Ag2B: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.008
Ag1C \\sim Ag2C: within 1.7A with sigma of 0.004 and sigma for terminal atoms
of 0.008
C27 \\sim C28 \\sim C29: within 2A with sigma of 0.004 and sigma for terminal
atoms of 0.004
C22A \\sim C23A \\sim C24A: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008
C25 \\sim C26 \\sim O19 \\sim O20: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.08
C34 \\sim C35 \\sim O21 \\sim O22: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008
C17 \\sim C18 \\sim C19: within 1.7A with sigma of 0.004 and sigma for terminal
atoms of 0.008
C2A \\sim C1 \\sim C2 \\sim C3 \\sim C3A \\sim S1: within 1.7A with sigma of
0.004 and sigma for terminal atoms of 0.008
C4 \\sim C4A \\sim C6 \\sim C6A \\sim C5 \\sim S2: within 1.7A with sigma of
0.004 and sigma for terminal atoms of 0.008
C15 \\sim C15A \\sim C16 \\sim C16A \\sim O16 \\sim O16A \\sim O17 \\sim O17A:
within 2A 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)=0.5*(1-FVAR(9))
 Sof(Ag8)=0.5*FVAR(9)
 Sof(Ag9A)=1-FVAR(9)
 Sof(Ag9)=FVAR(9)
 Sof(Ag2B)=1-FVAR(10)
 Sof(Ag1B)=FVAR(10)
 Sof(Ag2C)=0.5*(1-FVAR(12))
 Sof(Ag1C)=0.5*FVAR(12)
 Fixed Sof: H1A(0.5) H1B(0.5) C2(0.5) H2A(0.5) H2B(0.5) H2C(0.5) C3(0.5)
 H3A(0.5) H3B(0.5) H3C(0.5) H5A(0.5) H5B(0.5) C6(0.5) H6A(0.5) H6B(0.5)
 H6C(0.5) C15(0.7) C15A(0.3) C16(0.7) H16A(0.7) H16B(0.7) H16C(0.7) C16A(0.3)
 H16D(0.3) H16E(0.3) H16F(0.3) C22(0.7) H22A(0.7) H22B(0.7) H22C(0.7) C22A(0.3)
 H22D(0.3) H22E(0.3) H22F(0.3) C23(0.7) H23(0.7) C23A(0.3) H23A(0.3) C24(0.7)
 H24A(0.7) H24B(0.7) H24C(0.7) C24A(0.3) H24D(0.3) H24E(0.3) H24F(0.3) C25(0.5)
 C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5) H27A(0.5) H27B(0.5) H27C(0.5) H28(0.5)
 C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) H30A(0.5) H30B(0.5) H30C(0.5) H31(0.5)
 H32A(0.5) H32B(0.5) H32C(0.5) H34A(0.5) H34B(0.5) H34C(0.5) Mo1(0.5) Mo1A(0.5)
 Mo2(0.5) Mo2A(0.25) O1(0.5) O1A(0.5) O2(0.5) O2A(0.5) O16(0.7) O16A(0.3)
 O17(0.7) O17A(0.3) O19(0.5) O20(0.5) C2A(0.5) H2AA(0.5) H2AB(0.5) H2AC(0.5)
 C3A(0.5) H3AA(0.5) H3AB(0.5) H3AC(0.5) C4(0.5) H4A(0.5) H4B(0.5) H4C(0.5)
 C6A(0.5) H6AA(0.5) H6AB(0.5) H6AC(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5) H4AC(0.5)
6.a Riding coordinates:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,
 H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C16A(H16D,H16E,H16F),
 C19(H19A,H19B,H19C), C22A(H22D,H22E,H22F), C24A(H24D,H24E,H24F), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C28(H28), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
  C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), O18(H18),
 C2A(H2AA,H2AB,H2AC), C3A(H3AA,H3AB,H3AC), C4(H4A,H4B,H4C), C6A(H6AA,H6AB,H6AC),
  C4A(H4AA,H4AB,H4AC)
6.b Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C5(H5A), C5(H5B), C10(H10), C13(H13), C17(H17), C23(H23),
 C23A(H23A), C31(H31)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'