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_1551428
_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, 3(C6 H12)'
_chemical_formula_sum            'C98 H140 Ag12 F12 N8 O8 S8'
_chemical_formula_weight         3337.09
_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   geom
_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                   17.2498(3)
_cell_length_b                   17.2498(3)
_cell_length_c                   21.1010(16)
_cell_measurement_reflns_used    2521
_cell_measurement_temperature    100.3(5)
_cell_measurement_theta_max      27.2240
_cell_measurement_theta_min      3.6560
_cell_volume                     6278.7(5)
_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      100.3(5)
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.882
_diffrn_measurement_details
;
  1 omega   48.00   92.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104   37.0000  -90.0000 44

  2 omega   -2.00   58.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104  -19.0000  -90.0000 60

  3 omega   50.00   76.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7104  178.0000 -120.0000 26
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0390147000
_diffrn_orient_matrix_UB_12      -0.0128868000
_diffrn_orient_matrix_UB_13      -0.0010380000
_diffrn_orient_matrix_UB_21      -0.0080460000
_diffrn_orient_matrix_UB_22      -0.0273512000
_diffrn_orient_matrix_UB_23      0.0242307000
_diffrn_orient_matrix_UB_31      -0.0101322000
_diffrn_orient_matrix_UB_32      -0.0278495000
_diffrn_orient_matrix_UB_33      -0.0233080000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0724
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.882
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            8193
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.803
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         29.238
_diffrn_reflns_theta_min         3.051
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.027
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78691
_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    1.765
_exptl_crystal_description       block
_exptl_crystal_F_000             3296
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.550
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Flack x determined using 980 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.00(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3586
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0723
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0544P)^2^+3.2454P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1061
_refine_ls_wR_factor_ref         0.1149
_reflns_Friedel_coverage         0.672
_reflns_Friedel_fraction_full    0.891
_reflns_Friedel_fraction_max     0.708
_reflns_number_gt                2851
_reflns_number_total             3586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s15.cif
_cod_data_source_block           ag12bpy_cyclohexane
_cod_database_code               1551428
_chemical_oxdiff_formula         C1H1O1N1S1Ag1
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.676
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17_$1-C17 = C15-C16 = C17-C16 = C15_$1-C15
 1.54 with sigma of 0.02
 C4-C7 \\sim C4-C6
 with sigma of 0.02
 O2-C8 \\sim C8-O1
 with sigma of 0.02
 F3-C9 \\sim F1-C9 \\sim F2-C9
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C7) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(F3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C6) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) = Uanis(O2)
4. Others
 Fixed Sof: Ag3(0.25) H3A(0.5) H3B(0.5) H3C(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(0.5) F2(0.5) F3(0.5) C15(0.75) H15A(0.75) H15B(0.75) C16(0.75)
 H16A(0.75) H16B(0.75) C17(0.75) H17A(0.75) H17B(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B)
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 anion was disordered due to the 
symmetry, for which "Part -1" was applied to suppress the 
symmetry according to the chemistry. The three fluorine 
atoms were also involved in disorder; however, they were 
not split but had strict restraints imposed using 
"ISOR 0.005 0.01" and "SADI 0.01" for clarity. The ADPs 
of O1 and O2 were constrained to be the same because their 
equivalent positions are very close to each other. The 
cyclohexane residue could be clearly assigned from the 
difference Fourier map; however, the high symmetry at 
that site caused its disorder over two positions. Their 
geometries were also affected by the high symmetry, so 
the distance restraints "DFIX" and ADP restraints 
"ISOR 0.01 0.02" were used.
;
_shelx_res_checksum              67825
_shelx_hkl_checksum              50355