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_1551438
_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 Br)'
_chemical_formula_sum            'C92 H114 Ag12 Br2 F12 N8 O8 S8'
_chemical_formula_weight         3398.65
_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                   17.2292(3)
_cell_length_b                   17.2292(3)
_cell_length_c                   20.5453(9)
_cell_measurement_reflns_used    2588
_cell_measurement_temperature    100.15(10)
_cell_measurement_theta_max      28.1170
_cell_measurement_theta_min      3.3530
_cell_volume                     6098.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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      100.15(10)
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.879
_diffrn_measurement_details
;
  1 omega   46.00   88.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104   77.0000 -180.0000 42

  2 omega   41.00   67.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104   77.0000 -120.0000 26

  3 omega   -5.00   76.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104   77.0000   60.0000 81
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0190449000
_diffrn_orient_matrix_UB_12      0.0351457000
_diffrn_orient_matrix_UB_13      -0.0082904000
_diffrn_orient_matrix_UB_21      -0.0269941000
_diffrn_orient_matrix_UB_22      -0.0060097000
_diffrn_orient_matrix_UB_23      0.0255845000
_diffrn_orient_matrix_UB_31      0.0245563000
_diffrn_orient_matrix_UB_32      0.0205762000
_diffrn_orient_matrix_UB_33      0.0216559000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.879
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            8892
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.810
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         29.271
_diffrn_reflns_theta_min         3.086
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.740
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69517
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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    1.851
_exptl_crystal_description
;
;
_exptl_crystal_F_000             3312
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.064
_refine_diff_density_max         1.868
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.139
_refine_ls_abs_structure_details
;
 Flack x determined using 1066 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3512
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0590
_refine_ls_R_factor_gt           0.0433
_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^)+(0.0487P)^2^+4.6572P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0939
_refine_ls_wR_factor_ref         0.1008
_reflns_Friedel_coverage         0.691
_reflns_Friedel_fraction_full    0.914
_reflns_Friedel_fraction_max     0.727
_reflns_number_gt                2923
_reflns_number_total             3512
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s21.cif
_cod_data_source_block           ag12bpy_bromobenzene
_cod_database_code               1551438
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.584
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 C18-C17 = C17-C16 = C16-C15
 1.39 with sigma of 0.02
 C9-F1 \\sim C9-F2 \\sim C9-F1B \\sim C9-F2B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15) = Uanis(Br1)
4. Others
 Fixed Sof: Ag3(0.25) H2A(0.5) H2B(0.5) H2C(0.5) C4(0.5) C5(0.5) H5A(0.5)
 H5B(0.5) H5C(0.5) C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) C7(0.5) H7A(0.5) H7B(0.5)
 H7C(0.5) F1(0.7) F2(0.35) F1B(0.3) F2B(0.15) Br1(0.25) C15(0.25) C16(0.5)
 H16(0.5) C17(0.5) H17(0.5) C18(0.25) H18(0.25)
 Fixed X: Br1(1) C15(1) C18(1)
 Fixed Z: Br1(0) C15(0) C18(0)
5.a Riding coordinates:
 C18(H18)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C16(H16), C17(H17)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C)
Comments: The trifluoroacetate, the t-butyl mercaptan anions and the 
guest bromobenzene molecules were involved in disorder, 
to which restraints and constraints were applied. In detail, 
two parts of the trifluoro-group with fixed occupancies of 0.7 and 0.3 
were assigned, whose ADP and relevant C-F bond lengths were 
restrained by "ISOR 0.01" and "SADI 0.01", respectively. 
One carbon atom (C4) in the t-butyl mercaptan group was also 
disordered. Only strong ADP restraint by the "ISOR 0.01" command 
was used for its thermal vibration. The guest bromobenzene 
molecule was located in the channel of the structure in a disordered 
manner, which can be detected clearly from the difference 
Fourier map. Due to the geometrical symmetry of the molecule 
and its special position in the lattice, this guest molecule is 
distributed over several positions. However, only the main 
part was assigned for clarity; very strong geometrical and 
thermal vibrational restraints and constraints were applied to 
make this model chemically suitable.
;
_shelx_res_checksum              30271
_shelx_hkl_checksum              39892