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_1551424
_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(C2 H6 O)'
_chemical_formula_sum            'C88 H128 Ag12 F12 N8 O12 S8'
_chemical_formula_weight         3268.90
_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                   17.2793(3)
_cell_length_b                   17.2793(3)
_cell_length_c                   19.8246(6)
_cell_measurement_reflns_used    5327
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.2850
_cell_measurement_theta_min      3.6260
_cell_volume                     5919.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_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    -43.00  26.00   0.50    0.80    --   45.50 -77.00  30.00  138
  2  \w     51.00  78.00   0.50    3.00    --  100.10 -82.00   0.00   54
  3  \w    105.00 144.00   0.50    3.00    --  100.10 -82.00   0.00   78
  4  \w     80.00 114.00   0.50    0.80    --   45.50  77.00 120.00   68
  5  \w     89.00 117.00   0.50    0.80    --   45.50  82.00   0.00   56
  6  \w     89.00 189.00   0.50    3.00    --  100.10  82.00-150.00  200
  7  \w    150.00 183.00   0.50    3.00    --  100.10  82.00 -60.00   66
  8  \w     94.00 188.00   0.50    3.00    --  100.10  82.00  30.00  188
  9  \w     88.00 151.00   0.50    3.00    --  100.10  82.00 -90.00  126
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0056406000
_diffrn_orient_matrix_UB_12      0.0793478000
_diffrn_orient_matrix_UB_13      0.0350015000
_diffrn_orient_matrix_UB_21      -0.0496351000
_diffrn_orient_matrix_UB_22      0.0305954000
_diffrn_orient_matrix_UB_23      -0.0587430000
_diffrn_orient_matrix_UB_31      -0.0739885000
_diffrn_orient_matrix_UB_32      -0.0265347000
_diffrn_orient_matrix_UB_33      0.0368270000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0441
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            9046
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        66.750
_diffrn_reflns_theta_max         72.648
_diffrn_reflns_theta_min         3.393
_diffrn_source                   MM007HF-DW
_diffrn_source_type              'Microfocus Rotating Anode X-ray Source'
_exptl_absorpt_coefficient_mu    17.474
_exptl_absorpt_correction_T_max  0.441
_exptl_absorpt_correction_T_min  0.164
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.834
_exptl_crystal_description       block
_exptl_crystal_F_000             3216
_exptl_crystal_size_max          0.139
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.015
_refine_diff_density_min         -1.099
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Flack x determined using 1163 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(13)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         2959
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0476P)^2^+34.4922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1038
_refine_ls_wR_factor_ref         0.1052
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.956
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                2832
_reflns_number_total             2959
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2718-s11.cif
_cod_data_source_block           ag12bpy_etoh
_cod_original_cell_volume        5919.2(3)
_cod_database_code               1551424
_chemical_oxdiff_formula         'C80 H104 O8 N8 S8 F12 Ag12'
_chemical_oxdiff_usercomment     st
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2. Restrained distances
 C15-C14
 1.53 with sigma of 0.01
 C5-C4 \\sim C6-C4
 with sigma of 0.01
 F3-C8 \\sim F2-C8 \\sim F1-C8
 with sigma of 0.01
 O2-C7 \\sim O1-C7
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C15) \\sim
Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Ag3(0.25) H2A(0.5) H2B(0.5) H2C(0.5) H6A(0.5) H6B(0.5) H6C(0.5)
 O1(0.5) O2(0.5) C7(0.5) C8(0.5) F1(0.5) F2(0.5) F3(0.5) O3(0.5) H3(0.5)
 C14(0.5) H14A(0.5) H14B(0.5) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
5.a Riding coordinates:
 C6(H6A,H6B,H6C), C15(H15A,H15B,H15C)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
5.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13)
5.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C)
5.e Idealised tetrahedral OH refined as rotating group:
Comments:The trifluoroacetate was disordered due to the symmetry. 
"PART -1" was used to suppress the symmetry according to 
the chemistry with 0.5 occupancy. The C-F and C-O distances 
were restrained to be similar with "SADI". The ADPs of fluorine 
atoms were restrained using "ISOR 0.01 0.02". The t-butyl mercaptan 
anions were also disordered, however, the related atoms were not 
split but restrained using "ISOR" and "SADI". The ethanol was 
assigned from a difference Fourier map; however, the ethanol
locates around special position, and the space group symmetry 
has a large influence on its geometry. Therefore, geometry restraint 
with "DFIX" command and the ADP restraints with "ISOR" commands
were applied to this molecule.
 O3(H3)
;
_shelx_res_checksum              7553
_shelx_hkl_checksum              62427