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_1551437
_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 Cl)'
_chemical_formula_sum            'C92 H114 Ag12 Cl2 F12 N8 O8 S8'
_chemical_formula_weight         3309.73
_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                   17.23734(16)
_cell_length_b                   17.23734(16)
_cell_length_c                   20.5923(4)
_cell_measurement_reflns_used    12012
_cell_measurement_temperature    99.6(2)
_cell_measurement_theta_max      28.5080
_cell_measurement_theta_min      3.6700
_cell_volume                     6118.51(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41k (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.6(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_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    -24.00   3.20   0.80   10.00    --  -15.18 -99.00 -30.00   34
  2  \w    -25.00  23.00   0.80   10.00    --  -15.18 -99.00  90.00   60
  3  \w    -46.20  37.00   0.80   10.00    --   18.07 -37.00 120.00  104
  4  \w     11.00  44.60   0.80   10.00    --   18.07 -77.00 -60.00   42
  5  \w      0.00  72.00   0.80   10.00    --   18.07  37.00 -30.00   90
  6  \w      0.00  78.40   0.80   10.00    --   18.07  77.00-150.00   98
  7  \w     38.00  76.40   0.80   10.00    --   18.07 178.00-180.00   48
  8  \w     39.00  66.20   0.80   10.00    --   18.07 178.00   0.00   34
  9  \w    -48.20  35.00   0.80   10.00    --   18.07 -57.00  30.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0104962000
_diffrn_orient_matrix_UB_12      -0.0151616000
_diffrn_orient_matrix_UB_13      -0.0307901000
_diffrn_orient_matrix_UB_21      -0.0391900000
_diffrn_orient_matrix_UB_22      0.0105362000
_diffrn_orient_matrix_UB_23      0.0057352000
_diffrn_orient_matrix_UB_31      0.0068536000
_diffrn_orient_matrix_UB_32      0.0367641000
_diffrn_orient_matrix_UB_33      -0.0143609000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29746
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         26.367
_diffrn_reflns_theta_min         3.682
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.121
_exptl_absorpt_correction_T_max  0.877
_exptl_absorpt_correction_T_min  0.661
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.796
_exptl_crystal_description       block
_exptl_crystal_F_000             3240
_exptl_crystal_size_max          0.251
_exptl_crystal_size_mid          0.219
_exptl_crystal_size_min          0.072
_refine_diff_density_max         2.085
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
;
 Flack x determined using 1365 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.019(16)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         3285
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0425P)^2^+35.4434P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0880
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3140
_reflns_number_total             3285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s20.cif
_cod_data_source_block           ag12bpy_chlorobenzene
_cod_original_cell_volume        6118.52(15)
_cod_database_code               1551437
_chemical_oxdiff_formula         C80H104O8N8S8F12Ag12
_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-Cl1
 1.8 with sigma of 0.02
 C9-F1 \\sim C9-F2 \\sim C9B-F1B \\sim C9B-F2B
 with sigma of 0.01
 C9B-C8 \\sim C8-C9
 with sigma of 0.01
 C6-C4 \\sim C4-C5
 with sigma of 0.005
 C15-C17 \\sim C16-C18
 with sigma of 0.01
 C18-C17 \\sim C17-C16 \\sim C16-C15
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C18) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F1) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1) = Uanis(F1B)
Uanis(C9) = Uanis(C9B)
Uanis(Cl1) = Uanis(C15)
4. Others
 Sof(F1B)=1-FVAR(1)
 Sof(C9B)=Sof(F2B)=0.5*(1-FVAR(2))
 Sof(C9)=Sof(F2)=0.5*FVAR(2)
 Sof(F1)=FVAR(1)
 Fixed Sof: Ag3(0.25) 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) H7A(0.5) H7B(0.5) H7C(0.5)
 Cl1(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: Cl1(0) C15(0) C18(0)
 Fixed Z: Cl1(0.5) C15(0.5) C18(0.5)
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 anion 
and the guest chlorobenzene molecule were found disordered. 
The trifluoromethyl group and the t-butyl group in one of the 
t-butyl mercaptan anions were split over two parts with 
refined occupancies. To make them chemically reasonable, 
geometrical and ADP restraints were applied to the disordered 
residuals. The lattice chlorobenzene molecule suffered serious 
disorder. Only the major part was assigned for clarity with 
strict geometrical and thermal vibrational restraints. 
For C18, the H atoms were attached with "AFIX 3" 
because of the otherwise nonconvergent refinement. 
;
_shelx_res_checksum              13020
_shelx_hkl_checksum              58448