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_1551435
_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(C7 H8)'
_chemical_formula_sum            'C94 H120 Ag12 F12 N8 O8 S8'
_chemical_formula_weight         3268.89
_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                   17.26652(13)
_cell_length_b                   17.26652(13)
_cell_length_c                   20.5352(3)
_cell_measurement_reflns_used    12812
_cell_measurement_temperature    100.2(6)
_cell_measurement_theta_max      29.0860
_cell_measurement_theta_min      3.6590
_cell_volume                     6122.21(11)
_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_environment      N~2~
_diffrn_ambient_temperature      100.2(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.947
_diffrn_measurement_details
;
  1 omega  -23.00   16.20   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1755  -99.0000  -90.0000 49

  2 omega   -9.00   23.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1755  -99.0000  -30.0000 40

  3 omega  -25.00   23.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.1755  -99.0000 -150.0000 60

  4 omega  -41.00   -5.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -37.0000    0.0000 45

  5 omega   53.00   80.20   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   57.0000 -120.0000 34

  6 omega    3.40   37.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -37.0000    0.0000 42

  7 omega  -22.20   37.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -37.0000  -60.0000 74

  8 omega   33.00   87.40   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661 -178.0000  -90.0000 68

  9 omega  -51.00  -15.80   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661    0.0000 -180.0000 44

 10 omega    5.00   81.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661    0.0000 -180.0000 95

 11 omega   33.00   65.00   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661 -178.0000  -60.0000 40

 12 omega   35.00   76.60   0.8000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0661 -142.0000  168.0000 52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0017707000
_diffrn_orient_matrix_UB_12      0.0119802000
_diffrn_orient_matrix_UB_13      -0.0329984000
_diffrn_orient_matrix_UB_21      -0.0012222000
_diffrn_orient_matrix_UB_22      -0.0392905000
_diffrn_orient_matrix_UB_23      -0.0100357000
_diffrn_orient_matrix_UB_31      -0.0410294000
_diffrn_orient_matrix_UB_32      0.0006636000
_diffrn_orient_matrix_UB_33      0.0017181000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            33499
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         29.425
_diffrn_reflns_theta_min         3.337
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.077
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81175
_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    1.773
_exptl_crystal_description       block
_exptl_crystal_F_000             3208
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.997
_refine_diff_density_min         -0.564
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details
;
 Flack x determined using 1531 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.033(18)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         4122
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0387
_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^)+(0.0307P)^2^+36.1915P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0842
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.803
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.908
_reflns_number_gt                3710
_reflns_number_total             4122
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s18.cif
_cod_data_source_block           ag12bpy_toluene
_cod_original_cell_volume        6122.22(14)
_cod_database_code               1551435
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.658
_reflns_odcompleteness_completeness 99.56
_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
 C15-C16 = C16-C17 = C17-C18
 1.39 with sigma of 0.01
 C15-C19
 1.5 with sigma of 0.01
 C9-F1 \\sim C9-F2 \\sim C9-F1B \\sim C9-F2B
 with sigma of 0.01
 C4-C5 \\sim C4-C6 \\sim C4-C7 \\sim C1-C2 \\sim C1-C3
 with sigma of 0.01
 C18-C16 \\sim C17-C15
 with sigma of 0.01
 O1-C8 \\sim O2-C8
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C18) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(F2) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(O2) = Uanis(O1)
Uanis(F2B) = Uanis(F2)
4. Others
 Fixed Sof: Ag3(0.25) C3(0.5) H3A(0.5) H3B(0.5) H3C(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) O1(0.5) O2(0.5) F1(0.25) F1B(0.25) F2(0.5) F2B(0.5) C15(0.25)
 C16(0.5) H16(0.5) C17(0.5) H17(0.5) C18(0.25) H18(0.25) C19(0.25) H19A(0.25)
 H19B(0.25) H19C(0.25)
 Fixed Y: C18(0)
 Fixed Z: C18(0)
5.a Riding coordinates:
 C18(H18), C19(H19A,H19B,H19C)
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: Disorder was observed in the trifluoroacetate, 
the t-butyl mercaptan anion, and the toluene molecule. 
Among them, the trifluoroacetate was split over two equal 
parts as rotation along the C-C bond; the t-butyl group in one 
of the t-butyl mercaptan anions was also found to have 
two equal parts. For another t-butyl mercaptan, only half was 
found in the asymmetric unit due to the symmetry. 
The lattice toluene molecule was seriously disordered 
because of its geometry and lattice symmetry. Its assignment 
was from the difference Fourier map, where some minor 
parts could also be observed; however, only the major part 
was assigned for clarity. For the disordered residuals, 
strict distance restraints of "DFIX" or "SADI" and ADP 
restraints of "ISOR 0.01 0.02" or "ISOR 0.005 0.01" or 
constraints "EADP" were applied.
;
_shelx_res_checksum              57328
_shelx_hkl_checksum              10935