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_4127020
_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
'C38 H90.5 Ag14 B60 N12.5 O S12, 2(C3 H7 N O)'
_chemical_formula_sum            'C44 H104.5 Ag14 B60 N14.5 O3 S12'
_chemical_formula_weight         3428.41
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_symmetry_space_group_name_Hall  'P 32'
_symmetry_space_group_name_H-M   'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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                120
_cell_formula_units_Z            3
_cell_length_a                   15.30020(12)
_cell_length_b                   15.30020(12)
_cell_length_c                   42.6670(4)
_cell_measurement_reflns_used    18796
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.4610
_cell_measurement_theta_min      3.1100
_cell_volume                     8650.02(13)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.973
_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     29.00 116.00   0.50    0.50    --   45.50  57.00 -30.00  174
  2  \w     18.00  95.00   0.50    0.50    --   45.50  57.00  90.00  154
  3  \w     78.00 188.00   0.50    2.19    --  100.10  61.00 -90.00  220
  4  \w    127.00 173.00   0.50    2.19    --  100.10  45.00 150.00   92
  5  \w     65.00 155.00   0.50    2.19    --  100.10  45.00-101.00  180
  6  \w     85.00 118.00   0.50    2.19    --  100.10  61.00 -30.00   66
  7  \w     66.00 186.00   0.50    2.19    --  100.10  41.00-140.00  240
;
_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      -0.0266588000
_diffrn_orient_matrix_UB_12      -0.0735868000
_diffrn_orient_matrix_UB_13      -0.0277101000
_diffrn_orient_matrix_UB_21      0.0671378000
_diffrn_orient_matrix_UB_22      -0.0387056000
_diffrn_orient_matrix_UB_23      0.0139914000
_diffrn_orient_matrix_UB_31      -0.0911037000
_diffrn_orient_matrix_UB_32      -0.0811740000
_diffrn_orient_matrix_UB_33      0.0184514000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            30617
_diffrn_reflns_point_group_measured_fraction_full 0.820
_diffrn_reflns_point_group_measured_fraction_max 0.790
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.557
_diffrn_reflns_theta_min         3.107
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    20.961
_exptl_absorpt_correction_T_max  0.842
_exptl_absorpt_correction_T_min  0.796
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.974
_exptl_crystal_description       block
_exptl_crystal_F_000             4932
_exptl_crystal_size_max          0.131
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.711
_refine_diff_density_min         -0.936
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Flack x determined using 6393 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.044(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1386
_refine_ls_number_reflns         18070
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0603P)^2^+16.7801P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.624
_reflns_Friedel_fraction_full    0.647
_reflns_Friedel_fraction_max     0.607
_reflns_number_gt                17362
_reflns_number_total             18070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11338_si_006.cif
_cod_data_source_block           hy
_cod_original_cell_volume        8650.01(16)
_cod_original_formula_sum        'C44 H104.50 Ag14 B60 N14.50 O3 S12'
_cod_database_code               4127020
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C44 H105.5 O3 N14.5 S12 B60 Ag14'
_shelx_estimated_absorpt_t_max   0.285
_shelx_estimated_absorpt_t_min   0.170
_reflns_odcompleteness_completeness 96.40
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.11
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C36
 1.54 with sigma of 0.01
 N14-C36
 1.2 with sigma of 0.01
 O3-C45
 1.25 with sigma of 0.01
 N12-C35 \\sim N12-C32 \\sim N13-C33 \\sim N13-C34
 with sigma of 0.01
 C32-C33 \\sim C34-C35
 with sigma of 0.01
 C34-N12 \\sim N12-C33
 with sigma of 0.01
3. Restrained planarity
 N12, N13, C32, C33, C34, C35
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C34) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C26)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C27) \\sim Ueq, Uanis(C46) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N12) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(N13)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(N16)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(N6) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N11) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Others
 Sof(Ag15)=1-FVAR(1)
 Sof(Ag14)=FVAR(1)
 Fixed Sof: N12(0.5) N13(0.5) N14(0.5) C32(0.5) H32(0.5) C33(0.5) H33(0.5)
 C34(0.5) H34(0.5) C35(0.5) H35(0.5) C36(0.5) C37(0.5) H37A(0.5) H37B(0.5)
 H37C(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C32(H32), C33(H33), C34(H34), C35(H35), C38(H38),
 C39(H39), C40(H40), C41(H41), C42(H42A), C45(H45A)
6.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C37(H37A,H37B,H37C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C)
6.c Boron cage BH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3), B4(H4), B5(H5), B6(H6), B7(H7), B8(H8), B9(H9),
 B10(H10), B11(H11), B12(H12), B13(H13A), B14(H14A), B15(H15A), B16(H16A),
 B17(H17A), B18(H18A), B19(H19A), B20(H20A), B21(H21A), B22(H22A), B23(H23A),
 B24(H24A), B25(H25A), B26(H26A), B27(H27A), B28(H28A), B29(H29A), B30(H30),
 B31(H31), B32(H32A), B33(H33A), B34(H34A), B35(H35A), B36(H36), B37(H37),
 B38(H38A), B39(H39A), B40(H40A), B41(H41A), B42(H42), B43(H43), B44(H44),
 B45(H45), B46(H46), B47(H47), B48(H48), B49(H49), B50(H50), B51(H51), B52(H52),
  B53(H53), B54(H54), B55(H55), B56(H56), B57(H57), B58(H58), B59(H59), B60(H60)
;
_olex2_submission_original_sample_id SCAM-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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.288
_oxdiff_exptl_absorpt_empirical_full_min 0.755