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_1551427
_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, 1(C3 H6 O1)'
_chemical_formula_sum            'C83 H110 Ag12 F12 N8 O9 S8'
_chemical_formula_weight         3142.70
_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                   17.270(2)
_cell_length_b                   17.270(2)
_cell_length_c                   20.040(4)
_cell_measurement_reflns_used    10060
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      27.8600
_cell_measurement_theta_min      3.6680
_cell_volume                     5977.0(15)
_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
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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      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.892
_diffrn_measurement_details
;
  1 omega  -11.00   23.40   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -15.3317  -99.0000  -60.0000 43

  2 omega  -49.00  -13.00   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -77.0000   60.0000 45

  3 omega    5.00   81.00   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   57.0000  -60.0000 95

  4 omega   44.00   71.20   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000    0.0000 34

  5 omega   -5.00   83.00   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   77.0000 -180.0000 110

  6 omega   36.00   77.60   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000  120.0000 52

  7 omega    5.00   43.40   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -77.0000   60.0000 48

  8 omega    5.00   49.00   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   57.0000  120.0000 55

  9 omega  -19.00   29.00   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  -37.0000   60.0000 60

 10 omega   37.00   76.20   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661   37.0000    0.0000 49

 11 omega   46.00   73.20   0.8000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       18.0661  178.0000   60.0000 34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0347439000
_diffrn_orient_matrix_UB_12      0.0003856000
_diffrn_orient_matrix_UB_13      -0.0183594000
_diffrn_orient_matrix_UB_21      -0.0220800000
_diffrn_orient_matrix_UB_22      -0.0008964000
_diffrn_orient_matrix_UB_23      0.0289030000
_diffrn_orient_matrix_UB_31      -0.0001433000
_diffrn_orient_matrix_UB_32      0.0411298000
_diffrn_orient_matrix_UB_33      0.0007944000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            33451
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.865
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         30.445
_diffrn_reflns_theta_min         3.731
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.124
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57656
_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    1.746
_exptl_crystal_description       block
_exptl_crystal_F_000             3072
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.868
_refine_diff_density_min         -0.919
_refine_diff_density_rms         0.139
_refine_ls_abs_structure_details
;
 Flack x determined using 1485 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.047(17)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.195
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         4108
_refine_ls_number_restraints     56
_refine_ls_restrained_S_all      1.209
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0297P)^2^+65.2042P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1183
_refine_ls_wR_factor_ref         0.1218
_reflns_Friedel_coverage         0.787
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.834
_reflns_number_gt                3669
_reflns_number_total             4108
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s14.cif
_cod_data_source_block           ag12bpy_acetone
_cod_original_cell_volume        5977(2)
_cod_database_code               1551427
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_reflns_odcompleteness_completeness 99.50
_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-O3
 1.2 with sigma of 0.02
 C15-C16
 1.45 with sigma of 0.02
 F1B-C9 = F2-C9 = F2B-C9 = F1-C9
 1.34 with sigma of 0.01
 O2-C8
 1.2 with sigma of 0.02
 O2-O1
 2.2 with sigma of 0.02
 C9-C8
 1.54 with sigma of 0.02
 O3-C16
 2.3 with sigma of 0.04
 C4-C5 \\sim C4-C6 \\sim C4-C7
 with sigma of 0.02
 O2-C8 \\sim C8-O1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O1 \\sim C8: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2B) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(O2) = Uanis(O1)
4. Others
 Sof(F2B)=1-FVAR(1)
 Sof(F1B)=0.5*(1-FVAR(2))
 Sof(F1)=0.5*FVAR(2)
 Sof(F2)=FVAR(1)
 Fixed Sof: Ag3(0.25) H3A(0.5) H3C(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)
 O1(0.5) O2(0.5) O3(0.125) C15(0.125) C16(0.25) H16A(0.25) H16B(0.25) H16C(0.25)
5.a Riding coordinates:
 C16(H16A,H16B,H16C)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14)
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, one of the t-butyl mercaptan anions, 
and the guest acetone were found to be disordered. Among 
them, for t-butyl mercaptan, the C-C distances in the t-butyl 
group were restrained to be similar using "SADI". The ADPs 
for C6 and C7 were also restrained using "ISOR 0.01 0.02". 
The trifluoroacetate anion was split over two parts. All the 
C-F and C-O bonds were restrained to have similar lengths 
using "SADI 0.01", respectively. The C8-O2 and O1-O2 
bonds were restrained to be 1.2 and 2.2 angstrom with 
default esd, respectively. The anisotropic displacement 
parameters for the fluorine atoms were restrained using 
"ISOR 0.01 0.02". The symmetry for O1 and O2 was suppressed 
for chemical reasonability. They were constrained to have the 
same ADPs because their equivalent positions are very close; 
the ADPs for the acetate group were restrained using 
"SIMU 0.01 0.02 2". The guest acetone was seriously 
disordered due to its small size compared with the cavity size. 
Only the main residue was assigned according to the difference 
Fourier map. The geometry was restrained, and the thermal 
parameters were kept isotropic.
;
_shelx_res_checksum              75609
_shelx_hkl_checksum              23402