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_4127021
_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         'C28 H84 Ag14 B60 N8 S12, 4(C2 H3 N)'
_chemical_formula_sum            'C36 H96 Ag14 B60 N12 S12'
_chemical_formula_weight         3240.74
_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   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                84.784(4)
_cell_angle_beta                 60.966(6)
_cell_angle_gamma                84.106(4)
_cell_formula_units_Z            1
_cell_length_a                   14.7109(9)
_cell_length_b                   14.8752(6)
_cell_length_c                   15.1420(9)
_cell_measurement_reflns_used    10399
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      72.3120
_cell_measurement_theta_min      3.3350
_cell_volume                     2878.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41k (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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.985
_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    -43.00  82.00   0.50    0.50    --   45.50 -57.00 150.00  250
  2  \w     53.00 142.00   0.50    2.12    --   99.50 -82.00 150.00  178
  3  \w     79.00 130.00   0.50    2.12    --   99.50 -82.00 -60.00  102
  4  \w     47.00 123.00   0.50    2.12    --   99.50 -82.00  30.00  152
  5  \w     41.00  75.00   0.50    2.12    --   99.50 -82.00 -60.00   68
  6  \w     37.00 129.00   0.50    2.12    --   99.50 -82.00-120.00  184
  7  \w     44.00 103.00   0.50    2.12    --   99.50  30.00  60.00  118
  8  \w    124.00 181.00   0.50    2.12    --   99.50  45.00  90.00  114
  9  \w    136.00 173.00   0.50    2.12    --   99.50  30.00  60.00   74
 10  \w     90.00 134.00   0.50    0.50    --   45.50  82.00  30.00   88
 11  \w     89.00 134.00   0.50    0.50    --   45.50  82.00-120.00   90
 12  \w     89.00 133.00   0.50    0.50    --   45.50  82.00-180.00   88
 13  \w     59.00 108.00   0.50    2.12    --   99.50  45.00  90.00   98
 14  \w     20.00 155.00   0.50    2.12    --   99.50 -30.00  90.00  270
 15  \w     25.00 138.00   0.50    2.12    --   99.50 -82.00  90.00  226
 16  \w     23.00  51.00   0.50    2.12    --   99.50 -82.00 150.00   56
 17  \w     16.00 188.00   0.50    2.12    --   99.50 -15.00  60.00  344
 18  \w     11.00 117.00   0.50    2.12    --   99.50 -45.00 -90.00  212
 19  \w    -43.00  82.00   0.50    0.50    --   45.50 -57.00 -30.00  250
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0176242000
_diffrn_orient_matrix_UB_12      0.0717764000
_diffrn_orient_matrix_UB_13      0.0563902000
_diffrn_orient_matrix_UB_21      -0.0898367000
_diffrn_orient_matrix_UB_22      0.0613887000
_diffrn_orient_matrix_UB_23      -0.0017534000
_diffrn_orient_matrix_UB_31      -0.0772557000
_diffrn_orient_matrix_UB_32      -0.0443941000
_diffrn_orient_matrix_UB_33      0.1018946000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0698
_diffrn_reflns_av_unetI/netI     0.0698
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25260
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.498
_diffrn_reflns_theta_min         3.342
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    20.924
_exptl_absorpt_correction_T_max  0.269
_exptl_absorpt_correction_T_min  0.100
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.869
_exptl_crystal_description       block
_exptl_crystal_F_000             1546
_exptl_crystal_size_max          0.182
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.124
_refine_diff_density_max         2.752
_refine_diff_density_min         -1.844
_refine_diff_density_rms         0.280
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     693
_refine_ls_number_reflns         10224
_refine_ls_number_restraints     208
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0826
_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^)+(0.1877P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2236
_refine_ls_wR_factor_ref         0.2364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8455
_reflns_number_total             10224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11338_si_002.cif
_cod_data_source_block           hy
_cod_database_code               4127021
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C36 H96 N12 S12 Ag14 B60'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 94.02
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.35
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All B(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C14A, B10B}
{C13A, B9B}
{B9A, C14B}
{B10A, C13B}
{C15A, B20B}
{C16A, B19B}
{B20A, C15B}
{B19A, C16B}
{C18A, B30B}
{B30A, C17B}
{B29A, C18B}
{C17A, B29B}
3. Restrained distances
 N5-C10
 1.15 with sigma of 0.01
 C9-C10
 1.54 with sigma of 0.01
 C13-C14
 1.54 with sigma of 0.01
 N7-C14
 1.15 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(N7) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N5) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C3) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(B23) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(B18) \\sim Ueq, Uanis(C14A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(B19A) \\sim Ueq, Uanis(B12) \\sim Ueq, Uanis(B13) \\sim Ueq, Uanis(B17)
\\sim Ueq, Uanis(B14) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(B26) \\sim Ueq,
Uanis(B28) \\sim Ueq, Uanis(B22) \\sim Ueq, Uanis(B24) \\sim Ueq, Uanis(B27)
\\sim Ueq, Uanis(B30A) \\sim Ueq, Uanis(B9A) \\sim Ueq, Uanis(B6) \\sim Ueq,
Uanis(B2) \\sim Ueq, Uanis(B3) \\sim Ueq, Uanis(B4) \\sim Ueq, Uanis(B1) \\sim
Ueq, Uanis(B10A) \\sim Ueq, Uanis(B5) \\sim Ueq, Uanis(B8) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14A) = Uanis(B10B)
Uanis(C13A) = Uanis(B9B)
Uanis(B9A) = Uanis(C14B)
Uanis(B10A) = Uanis(C13B)
Uanis(C15A) = Uanis(B20B)
Uanis(C16A) = Uanis(B19B)
Uanis(B20A) = Uanis(C15B)
Uanis(B19A) = Uanis(C16B)
Uanis(C18A) = Uanis(B30B)
Uanis(B30A) = Uanis(C17B)
Uanis(B29A) = Uanis(C18B)
Uanis(C17A) = Uanis(B29B)
5. Others
 Sof(S1B)=Sof(S2B)=Sof(S3B)=Sof(S4B)=Sof(S5B)=Sof(S6B)=Sof(C13B)=Sof(C14B)=
 Sof(C15B)=Sof(C16B)=Sof(C17B)=Sof(C18B)=Sof(H1BB)=Sof(H2B)=Sof(H4B)=Sof(H6B)=
 Sof(H7BB)=Sof(H8B)=Sof(B9B)=Sof(H9B)=Sof(B10B)=Sof(H10B)=Sof(H11A)=Sof(H12A)=
 Sof(H14A)=Sof(H15A)=Sof(H17A)=Sof(H18A)=Sof(B19B)=Sof(H19B)=Sof(B20B)=
 Sof(H20B)=Sof(H21A)=Sof(H23A)=Sof(H26A)=Sof(H27A)=Sof(H28A)=Sof(B29B)=
 Sof(H29B)=Sof(B30B)=Sof(H30B)=1-FVAR(1)
 Sof(S1A)=Sof(S2A)=Sof(S3A)=Sof(S4A)=Sof(S5A)=Sof(S6A)=Sof(C13A)=Sof(C14A)=
 Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=Sof(H1AA)=Sof(H2A)=Sof(H4A)=Sof(H6A)=
 Sof(H7AA)=Sof(H8A)=Sof(B9A)=Sof(H9A)=Sof(B10A)=Sof(H10A)=Sof(H11)=Sof(H12)=
 Sof(H14)=Sof(H15)=Sof(H17)=Sof(H18)=Sof(B19A)=Sof(H19A)=Sof(B20A)=Sof(H20A)=
 Sof(H21)=Sof(H23)=Sof(H26)=Sof(H27)=Sof(H28)=Sof(B29A)=Sof(H29A)=Sof(B30A)=
 Sof(H30A)=FVAR(1)
 Fixed Sof: N7(0.5) C13(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C14(0.5) N5(0.5)
 C9(0.5) H9C(0.5) H9D(0.5) H9E(0.5) C10(0.5)
6.a Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C11(H11B,
 H11C,H11D), C13(H13A,H13B,H13C), C9(H9C,H9D,H9E)
6.b Boron cage BH refined with riding coordinates:
 B1(H1BB), B1(H1AA), B2(H2A), B2(H2B), B3(H3), B4(H4B), B4(H4A), B5(H5),
 B6(H6B), B6(H6A), B7(H7BB), B7(H7AA), B8(H8B), B8(H8A), B9A(H9A), B9B(H9B),
 B10B(H10B), B10A(H10A), B11(H11), B11(H11A), B12(H12A), B12(H12), B13(H13),
 B14(H14), B14(H14A), B15(H15A), B15(H15), B16(H16), B17(H17A), B17(H17),
 B18(H18A), B18(H18), B19A(H19A), B19B(H19B), B20B(H20B), B20A(H20A), B21(H21A),
  B21(H21), B22(H22), B23(H23A), B23(H23), B24(H24), B25(H25), B26(H26),
 B26(H26A), B27(H27A), B27(H27), B28(H28), B28(H28A), B29B(H29B), B29A(H29A),
 B30A(H30A), B30B(H30B)
;
_olex2_submission_original_sample_id NC-1
_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 1.834
_oxdiff_exptl_absorpt_empirical_full_min 0.521