Atomically Precise Site-Specific Tailoring and Directional Assembly of Superatomic Silver Nanoclusters.
Wang, Zhao-Yang; Wang, Meng-Qi; Li, Yan-Ling; Luo, Peng; Jia, Tong-Tong; Huang, Ren-Wu; Zang, Shuang-Quan; Mak, Thomas C. W.; Journal of the American Chemical Society  (2018) –; doi:10.1021/jacs.7b11338

data_4127023
_publ_section_title
;
 Atomically Precise Site-Specific Tailoring and Directional Assembly of
 Superatomic Silver Nanoclusters.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11338
_journal_year                    2018
_chemical_formula_moiety         '0.5(C104 H184 Ag28 B120 N16 S24)'
_chemical_formula_sum            'C52 H92 Ag14 B60 N8 S12'
_chemical_formula_weight         3372.83
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           128
_space_group_name_Hall           '-P 4 2n'
_space_group_name_H-M_alt        'P 4/m n c'
_symmetry_space_group_name_Hall  '-P 4 2n'
_symmetry_space_group_name_H-M   'P 4/m n c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.9804(3)
_cell_length_b                   22.9804(3)
_cell_length_c                   20.1589(4)
_cell_measurement_reflns_used    10026
_cell_measurement_temperature    270.00(10)
_cell_measurement_theta_max      71.6020
_cell_measurement_theta_min      2.7240
_cell_volume                     10645.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      270.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9998
_diffrn_measured_fraction_theta_max 0.9849
_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      6.00 121.00   0.50    1.00    --   45.70  37.00 -30.00  230
  2  \w     99.00 135.00   0.50    1.00    --   45.70  82.00 -90.00   72
  3  \w    130.00 182.00   0.50   10.00    --  100.10  77.00-120.00  104
  4  \w    125.00 187.00   0.50   10.00    --  100.10  61.00 -60.00  124
  5  \w     88.00 163.00   0.50   10.00    --  100.10  82.00  90.00  150
  6  \w     80.00 123.00   0.50   10.00    --  100.10  77.00-120.00   86
  7  \w     11.00 134.00   0.50   10.00    --  100.10 -61.00 -60.00  246
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0418479000
_diffrn_orient_matrix_UB_12      0.0335643000
_diffrn_orient_matrix_UB_13      -0.0456199000
_diffrn_orient_matrix_UB_21      0.0358973000
_diffrn_orient_matrix_UB_22      0.0558400000
_diffrn_orient_matrix_UB_23      0.0107879000
_diffrn_orient_matrix_UB_31      0.0382075000
_diffrn_orient_matrix_UB_32      -0.0154986000
_diffrn_orient_matrix_UB_33      -0.0604628000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            31998
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.495
_diffrn_reflns_theta_min         2.719
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.329
_exptl_absorpt_correction_T_max  0.391
_exptl_absorpt_correction_T_min  0.255
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.052
_exptl_crystal_description       block
_exptl_crystal_F_000             3220
_exptl_crystal_size_max          0.183
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.133
_platon_squeeze_details
;
TITL hy        P 4/m n c    R = 0.09
CELL   22.9804   22.9804   20.1589     90.00     90.00     90.00
SPGR P4/mnc
Q101 0.915 0.896 0.113 !       1.31 eA-3
C102 0.429 0.761 0.207 !       1.20 eA-3
C103 0.876 0.180 0.499 !       1.12 eA-3
Q104 0.554 0.164 0.493 !       0.93 eA-3
C105 0.296 0.234 0.000 !       0.84 eA-3
C106 0.797 0.320-0.003 !       0.82 eA-3
C107 0.414 0.108 0.292 !       0.80 eA-3
C108 0.907 0.484 0.003 !       0.80 eA-3
C109 0.327 0.281-0.003 !       0.80 eA-3
C110 0.610 0.204 0.161 !       0.78 eA-3
Q111 0.079 0.016-0.001 !       0.76 eA-3
C112 0.408 0.009 0.458 !       0.74 eA-3
Q113 0.133 0.305 0.003 !       0.73 eA-3
Q114 0.633 0.760 0.233 !       0.73 eA-3
C115 0.860 0.680 0.281 !       0.73 eA-3
C116 0.236 0.106 0.440 !       0.72 eA-3
C117 0.149 0.352 0.248 !       0.72 eA-3
C118 0.665 0.115 0.278 !       0.71 eA-3
C119 0.814 0.200 0.467 !       0.71 eA-3
C120 0.264 0.432 0.112 !       0.70 eA-3
C121 0.657 0.667 0.079 !       0.70 eA-3
C122 0.089 0.544 0.077 !       0.70 eA-3
C123 0.589 0.956 0.423 !       0.70 eA-3
C124 0.963 0.400 0.599 !       0.69 eA-3
C125 0.037 0.601 0.467 !       0.69 eA-3
C126 0.259 0.141 0.502 !       0.69 eA-3
C127 0.624 0.958 0.228 !       0.69 eA-3
Q128 0.505 0.579 0.171 !       0.69 eA-3
C129 0.548 0.986 0.390 !       0.68 eA-3
C130 0.703 0.675 0.082 !       0.68 eA-3
Q131 0.283 0.599 0.278 !       0.68 eA-3
C132 0.300 0.320-0.009 !       0.67 eA-3
Q133 0.016 0.065 0.360 !       0.67 eA-3
C134 0.518 0.978 0.629 !       0.67 eA-3
C135 0.482 0.022 0.371 !       0.67 eA-3
C136 0.978 0.483 0.371 !       0.67 eA-3
C137 0.408 0.238 0.095 !       0.67 eA-3
C138 0.422 0.125 0.002 !       0.67 eA-3
C139 0.478 0.967 0.138 !       0.66 eA-3
C140 0.551 0.931 0.107 !       0.66 eA-3
C141 0.764 0.563 0.077 !       0.66 eA-3
C142 0.492 0.002 0.892 !       0.66 eA-3
C143 0.783 0.535 0.113 !       0.65 eA-3
C144 0.500 1.004 0.344 !       0.65 eA-3
C145 0.452 0.133-0.005 !       0.64 eA-3
C146 0.492 0.297 0.000 !       0.64 eA-3
Q147 0.291 0.304 0.262 !       0.64 eA-3
C148 0.063 0.227 0.451 !       0.63 eA-3
C149 0.713 0.858 0.452 !       0.63 eA-3
C150 0.359 0.251 0.067 !       0.63 eA-3
C151 0.983 0.501 0.060 !       0.63 eA-3
C152 0.732 0.544 0.030 !       0.62 eA-3
Q153 0.421 0.356 0.422 !       0.62 eA-3
C154 0.962 0.761 0.473 !       0.62 eA-3
C155 0.383 0.221 0.066 !       0.61 eA-3
C156 0.032 0.260 0.435 !       0.61 eA-3
C157 0.968 0.740 0.565 !       0.61 eA-3
C158 0.507 0.041 0.329 !       0.61 eA-3
C159 0.541 0.736 0.090 !       0.61 eA-3
C160 0.128 0.646 0.486 !       0.60 eA-3
C161 0.484 0.146 0.747 !       0.59 eA-3
C162 0.516 0.854 0.253 !       0.59 eA-3
C163 0.822 0.398 0.043 !       0.59 eA-3
C164 0.134 0.182 0.439 !       0.59 eA-3
C165 0.523 0.838 0.771 !       0.58 eA-3
C166 0.061 0.227 0.501 !       0.58 eA-3
C167 0.731 0.039 0.488 !       0.57 eA-3
C168 0.571 0.881 0.076 !       0.57 eA-3
Q169 0.461 0.353 0.361 !       0.57 eA-3
C170 0.967 0.435 0.143 !       0.56 eA-3
C171 0.656 0.023 0.500 !       0.56 eA-3
Q172 0.673 0.666 0.291 !       0.56 eA-3
C173 0.033 0.306 0.465 !       0.56 eA-3
C174 0.414 0.187 0.109 !       0.55 eA-3
C175 0.119 0.375 0.248 !       0.55 eA-3
C176 0.431 0.012 0.189 !       0.54 eA-3
C177 0.852 0.412 0.126 !       0.54 eA-3
C178 0.342 0.014 0.512 !       0.52 eA-3
C179 0.658 0.986 0.488 !       0.52 eA-3
C180 0.577 0.038 0.233 !       0.52 eA-3
C181 0.108 0.195 0.506 !       0.51 eA-3
C182 0.640 0.898 0.426 !       0.51 eA-3
C183 0.431 0.980 0.392 !       0.51 eA-3
;
_refine_diff_density_max         1.213
_refine_diff_density_min         -1.048
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         4960
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0755
_refine_ls_R_factor_gt           0.0686
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1657P)^2^+2.9518P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2279
_refine_ls_wR_factor_ref         0.2359
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3909
_reflns_number_total             4960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11338_si_008.cif
_cod_data_source_block           hy_sq
_cod_database_code               4127023
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C52 H92 N8 Ag14 S12 B60'
_chemical_oxdiff_usercomment     st
_shelx_estimated_absorpt_t_max   0.314
_shelx_estimated_absorpt_t_min   0.231
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All B(H,H) groups, All C(H) groups
2. Shared sites
{B8, C6}
{C7, B7}
{C8, B6}
{B11, C9}
3. Restrained distances
 N1-C1
 1.25 with sigma of 0.01
 C5-C1
 2.1 with sigma of 0.02
 C2-C4
 2.1 with sigma of 0.01
 B1-B2
 2 with sigma of 0.01
 B6-B3
 2.3 with sigma of 0.01
 B5-B7
 1.9 with sigma of 0.01
4. Restrained planarity
 N1, C1, C2, C3, C4, C5
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
B3 \\sim B2 \\sim B4 \\sim B5 \\sim B1: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B2) \\sim Ueq, Uanis(B4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(B3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B5) \\sim Ueq, Uanis(B1) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(B8) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B9) \\sim Ueq, Uanis(B10) \\sim Ueq, Uanis(B11) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(B11) = Uanis(C9)
Uanis(C7) = Uanis(B7)
Uanis(B8) = Uanis(C6)
Uanis(C8) = Uanis(B6)
6. Others
 Fixed Sof: S1(0.25) S2(0.5) S3(0.25) S4(0.5) C6(0.25) C7(0.5) C8(0.25)
 C9(0.5) H4A(0.5) H4B(0.5) H5B(0.5) H5A(0.5) B6(0.25) H6(0.25) B7(0.5) H7(0.5)
 B8(0.25) H8(0.25) H10A(0.5) H10(0.5) B11(0.5) H11(0.5)
7.a Ternary CH refined with riding coordinates:
 B2(H2A)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5)
7.c Boron cage BH refined with riding coordinates:
 B1(H1A), B3(H3), B4(H4A), B4(H4B), B5(H5B), B5(H5A), B6(H6), B7(H7), B8(H8),
 B9(H9), B10(H10A), B10(H10), B11(H11)
;
_platon_squeeze_void_probe_radius 1.20
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 16.655
_oxdiff_exptl_absorpt_empirical_full_min 0.533