Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal-organic framework
Ren-Wu Huang; Yong-Sheng Wei; Xi-Yan Dong; Xiao-Hui Wu; Chen-Xia Du; Shuang-Quan Zang; Thomas C. W. Mak; Nature Chemistry 9 (2017) 689–697; doi:10.1038/nchem.2718

data_1551439
_publ_section_title
;
 Hypersensitive dual-function luminescence switching of a
 silver-chalcogenolate cluster-based metal-organic framework
;
_journal_name_full               'Nature Chemistry'
_journal_page_first              689
_journal_page_last               697
_journal_paper_doi               10.1038/nchem.2718
_journal_volume                  9
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C80 H104 Ag12 F12 N8 O8 S8, 2(C6 H5 I)'
_chemical_formula_sum            'C92 H114 Ag12 F12 I2 N8 O8 S8'
_chemical_formula_weight         3492.63
_space_group_crystal_system      tetragonal
_space_group_IT_number           121
_space_group_name_Hall           'I -4 2'
_space_group_name_H-M_alt        'I -4 2 m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.2105(2)
_cell_length_b                   17.2105(2)
_cell_length_c                   20.6982(8)
_cell_measurement_reflns_used    6520
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.9990
_cell_measurement_theta_min      3.8870
_cell_volume                     6130.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_temperature      100
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.935
_diffrn_measurement_details
;
  1 omega   45.00   89.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000 -150.0000 88

  2 omega    0.00   80.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   37.0000  -30.0000 160

  3 omega   35.00   60.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000 -120.0000 50

  4 omega  -51.00    2.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661    0.0000 -180.0000 106

  5 omega   60.00   86.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661    0.0000 -180.0000 52

  6 omega   61.00   91.00   0.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661 -178.0000  -60.0000 60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            17060
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.873
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         29.447
_diffrn_reflns_theta_min         3.348
_exptl_absorpt_coefficient_mu    2.577
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.892
_exptl_crystal_density_meas      .
_exptl_crystal_description       block
_exptl_crystal_F_000             3384
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.18
_refine_diff_density_max         3.488
_refine_diff_density_min         -1.668
_refine_diff_density_rms         0.202
_refine_ls_abs_structure_details
;
 Flack x determined using 1268 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         3887
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.134
_refine_ls_R_factor_all          0.0666
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0822P)^2^+55.0663P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1510
_refine_ls_wR_factor_ref         0.1583
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.941
_reflns_Friedel_fraction_max     0.798
_reflns_number_gt                3368
_reflns_number_total             3887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s22.cif
_cod_data_source_block           ag12bpy_iodobenzene
_cod_database_code               1551439
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C14, C14B}
{C17, C17B}
3. Restrained distances
 C14-C15 = C15-C16 = C16-C17
 1.39 with sigma of 0.01
 C5-C4
 1.53 with sigma of 0.01
 C15_$1-C15 \\sim C16-C16_$1
 with sigma of 0.01
 C17-I2 \\sim C14-I1B
 with sigma of 0.01
 C14-C17 \\sim C15-C16_$1 \\sim C15_$1-C16
 with sigma of 0.01
 F2-C8 \\sim C8-F1
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C5) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C14) = Uanis(I2) = Uanis(C17) = Uanis(C16) = Uanis(C15) = Uanis(I1B) =
Uanis(C14B) = Uanis(C17B)
5. Others
 Fixed Sof: Ag3(0.25) H3A(0.5) H3B(0.5) H3C(0.5) H6A(0.5) H6B(0.5) H6C(0.5)
 I1B(0.05) I2(0.2) C14(0.2) H14(0.2) C17(0.2) C14B(0.05) C17B(0.05) H17B(0.05)
 C15(0.5) H15(0.5) C16(0.5) H16(0.5)
 Fixed X: I1B(1) I2(1) C14(1) C17(1) C14B(1) C17B(1)
 Fixed Z: I1B(0.5) I2(0.5) C14(0.5) C17(0.5) C14B(0.5) C17B(0.5)
6.a Riding coordinates:
 C14(H14), C17B(H17B), C15(H15), C16(H16)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
Comments: The fluorine atoms in the trifluoroacetate anion were 
disordered. However, no split was made; rather, 
they were treated with strict restraints for geometry and thermal 
vibration using "SADI 0.01" and "ISOR 0.005 0.01", respectively. 
One of the carbon atoms in the t-butyl mercaptan group was also 
restrained with "DFIX 1.53 0.01" and "ISOR 0.005 0.01" for its 
geometry and ADPs, respectively, due to the disorder. The 
guest molecule iodobenzene can be clearly observed from 
the difference Fourier map, but the molecule suffered seriously 
positional disorder as observed in the strong peaks over several 
locations along the lattice voids. Because of the bad disorder and 
the geometrical symmetry of the molecule as well as the lattice 
symmetry, it is complicated and unnecessary to separate all 
the parts of the guest molecule. Instead, a simple model was 
made in the position of majority, for which very strong restraints 
and constraints were applied to this modelled molecule.
;
_shelx_res_checksum              67467
_shelx_hkl_checksum              63848