Flexible Thioether−Ag(I) Interactions for Assembling Large Organic Ligands into Crystalline Networks
Huang, Guo; Tsang, Chun-Kwan; Xu, Zhengtao; Li, Kunhao; Zeller, Matthias; Hunter, Allen D.; Chui, Stephen Sin-Yin; Che, Chi-Ming; Crystal Growth & Design 9 (2009) 1444–; doi:10.1021/cg800869u

data_4511063
_publ_section_title
;
 Flexible Thioether&#x2212;Ag(I) Interactions for Assembling Large Organic
 Ligands into Crystalline Networks
;
_journal_issue                   3
_journal_name_full               'Crystal Growth &amp; Design'
_journal_page_first              1444
_journal_paper_doi               10.1021/cg800869u
_journal_volume                  9
_journal_year                    2009
_chemical_formula_moiety         'C124 H100 Ag5 F12 O14 S16, 4(C6 H5 N O2)'
_chemical_formula_sum            'C148 H120 Ag5 F12 N4 O22 S16'
_chemical_formula_weight         3586.96
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                73.2160(10)
_cell_angle_beta                 84.3200(10)
_cell_angle_gamma                73.0120(10)
_cell_formula_units_Z            1
_cell_length_a                   13.0479(9)
_cell_length_b                   19.1477(14)
_cell_length_c                   19.9355(14)
_cell_measurement_reflns_used    8687
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.42
_cell_measurement_theta_min      2.20
_cell_volume                     4559.8(6)
_computing_cell_refinement       'SAINT+ 6.45 (Bruker, 2003)'
_computing_data_collection       'SMART 5.630 (Bruker, 1997-2002)'
_computing_data_reduction        'SAINT+ 6.45'
_computing_molecular_graphics    'SHELXTL 6.14'
_computing_publication_material  'SHELXTL 6.14'
_computing_structure_refinement  'SHELXTL 6.14'
_computing_structure_solution    'SHELXTL 6.14 (Bruker, 2000-2003)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker AXS SMART APEX CCD diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_av_sigmaI/netI    0.0529
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41427
_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         1.16
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.779
_exptl_absorpt_correction_T_max  0.904
_exptl_absorpt_correction_T_min  0.736
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2007)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1811
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.13
_platon_squeeze_details
;
;
_refine_diff_density_max         4.307
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.178
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     953
_refine_ls_number_reflns         18642
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1162
_refine_ls_R_factor_gt           0.0955
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2768
_refine_ls_wR_factor_ref         0.2964
_reflns_number_gt                12904
_reflns_number_total             18642
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            cg800869u_si_002.cif
_cod_data_source_block           3
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Triclinic' changed to 'triclinic'
according to
/usr/data/users/saulius/automatic-downloads/retrospective/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_original_sg_symbol_H-M      P-1
_cod_original_formula_sum        '    C148 H120 Ag5 F12 N4 O22 S16'
_cod_database_code               4511063
_comments
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Large fractions of the unit cell volume are filled with diffuse 
solvent and/or heavily disordered triflate anions. The residual 
electron density within the voids shows partially some patterns 
that resemble additional nitrobenzene molecules, but attempts to 
define and refine these did not give a significantly better 
model (even with disorder and heavy restraints), so all 
ambiguous solvate molecules were not included in the final 
model. This resulted in an ultimate fraction of 26.2% of 
unfilled voids (1192.6 &#x00C5;3 per unit cell). Thus the solvent 
was "squeezed out" using the program Platon by Ton Spek. 
The number of the electrons "squeezed out" as estimated by 
the program was 238.
 
For the whole structure a mild antibumping restraint was 
applied (standrad deviation 0.02). 

Two nitrobenzene molecules were well enough defined to be 
included in the model. One was refined as disordered over 
two positions with an occupancy ratio of 0.72(2) to 0.28(2). 
The benzene rings were restrained to resemble ideal hexagons 
with C-C distances of 1.39 &#x00C5;, the nitro groups were restrained
 to be flat with equivalent C-N and N-O distances restrained 
to be the same and the ADPs of equivalent atoms were set to 
be identical in both moieties. Neighboring atoms were also 
restrained to similar ADPs (SIMU and DELU command).
 
Based on close contacts between the minor component of this 
nitrobenzene molecule with one of the triflate anions it can 
be assumed that the disorder is dynamic and not static 
(as the triflate anion also shows larger than usual 
anisotropic displacement parameters). 

Two silver cations are bridged by what appears to be a single 
atom with an electron count close to that of an oxygen atom. 
There is no clear indication about the nature of this atom. 
No other large residual electron density that might indicate 
either other non-hydrogen atoms or H atoms are discernable. 
A search of the Cambridge Crystallographic Database revealed 
only one example of a Ag-O-Ag bridge, but 11 cases of a Ag-OH2-Ag 
bridge and multiple others with Ag-OR-Ag fragments. Based on this 
the fragment was tentatively assigned to be Ag-OH2-Ag and the 
H atoms were placed in meaningful positions using positional 
restraints. O-H distances were restrained to be 0.84(2) &#x00C5;, 
H...H distances to be 1.30(2) &#x00C5;, and the distance of the H 
atoms to the carbon atom of a neigboring methyl group were 
restrained to be larger than 3.50(2) &#x00C5;.
 
One of the silver cations is disordered across an inversion 
center with each of the sites being half occupied. A triflate 
anion (the same that is showing the close contact), despite 
exhibiting relatively large ADPs seems to be not half occupied. 
A tentative refinement of an occupancy rate refined to 94%, and 
a forced half occupancy raised the R values by several percent 
and resulted in ill defined ADPs. It thus has to be assumed 
that the disordered Ag cation is surrounded by two triflate 
anions (but only very loosly bonded to it). This would give a 
silver to triflate ratio of 5 to 4 for the resolved parts of the 
unit cell, which would lead to the assumption that one triflate 
anion is located in the voids occupied by diffuse solvent. 

Treatment of hydrogen atoms:
Water H atoms were placed in meaningful positions (see above). 
All other hydrogen atoms were placed in calculated positions 
and all H atoms were refined with an isotropic displacement 
parameter 1.5 (methyl, water) or 1.2 times (all others) that 
of the adjacent carbon or oxygen atom. Methyl H atoms were 
allowed to rotate to best fit the experimental electron density. 

;