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_1551436
_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, 4(C6 H5 F)'
_chemical_formula_sum            'C104 H124 Ag12 F16 N8 O8 S8'
_chemical_formula_weight         3469.02
_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                   17.3073(6)
_cell_length_b                   17.3073(6)
_cell_length_c                   20.4745(9)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    100.1
_cell_measurement_theta_max      27.555
_cell_measurement_theta_min      2.594
_cell_volume                     6133.0(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100.1
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0107
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            81627
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.250
_diffrn_reflns_theta_max         27.562
_diffrn_reflns_theta_min         2.813
_exptl_absorpt_coefficient_mu    2.083
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5966
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1029 before and 0.0508 after correction.
The Ratio of minimum to maximum transmission is 0.8002.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.879
_exptl_crystal_description       block
_exptl_crystal_F_000             3408
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.685
_refine_diff_density_min         -0.778
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Flack x determined using 1636 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.026(6)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3697
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0214
_refine_ls_R_factor_gt           0.0206
_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^)+(0.0326P)^2^+14.9038P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0559
_refine_ls_wR_factor_ref         0.0566
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3615
_reflns_number_total             3697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s19.cif
_cod_data_source_block           ag12bpy_fluorobenzene
_cod_original_cell_volume        6133.0(5)
_cod_database_code               1551436
_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
 C14B-F3B
 1.34 with sigma of 0.02
 C8-F1 \\sim C8-F2 \\sim C8-F1B \\sim C8-F2B
 with sigma of 0.005
 C15B-F3B \\sim F3B-C19B \\sim C19-F3 \\sim F3-C15
 with sigma of 0.01
3. Restrained planarity
 F3B, C14B, C15B, C16B, C17B, C18B, C19B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(F2B) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1B)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uiso(F3) = Uiso(C17) = Uiso(C18) = Uiso(C16) = Uiso(C19) = Uiso(C15) = Uiso(C14)
Uiso(C14B) = Uiso(C15B) = Uiso(C19B) = Uiso(F3B) = Uiso(C16B) = Uiso(C18B) =
Uiso(C17B)
5. Others
 Fixed Sof: Ag3(0.25) H3A(0.5) H3B(0.5) H3C(0.5) H5A(0.5) H5B(0.5) H5C(0.5)
 F1(0.25) F2(0.5) F1B(0.25) F2B(0.5) F3(0.3) C17(0.3) H17(0.3) C18(0.3)
 H18(0.3) C19(0.3) H19(0.3) C14(0.3) C15(0.3) H15(0.3) C16(0.3) H16(0.3)
 F3B(0.2) C14B(0.2) C15B(0.2) H15B(0.2) C16B(0.2) H16B(0.2) C17B(0.2) H17B(0.2)
 C18B(0.2) H18B(0.2) C19B(0.2) H19B(0.2)
6.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13), C17(H17), C18(H18), C19(H19), C15(H15),
 C16(H16), C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B), C19B(H19B)
6.b Fitted hexagon refined as free rotating group:
 C17(C18,C19,C14,C15,C16), C14B(C15B,C16B,C17B,C18B,C19B)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
Comments: Disorder over two sites was observed for the trifluoro 
group in the trifluoroacetate anion. The related C-F distances 
were restrained to be similar with "SADI 0.005" or "SADI 0.01", 
and the ADPs for fluorine atoms were restrained with 
"ISOR 0.005". The fluorobenzene can be clearly observed from 
the difference Fourier map; however, severe disorder occurred 
to this residue due to the high symmetry and rotation around 
the benzene centre. To make the model chemically reasonable, 
two entire fluorobenzene groups with fixed occupancies of 0.3 
and 0.2, were modelled according to the charge density. 
The benzene groups were constrained with "AFIX 66", 
and the ADPs for the atoms in the same part were 
constrained to be the same with "EADP" commands.
;
_shelx_res_checksum              28943
_shelx_hkl_checksum              85691