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_4511062
_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
'C122 H85 Ag2 F6 N5 O7 S14 Zn, 3.619(C6 H6), C6 H5 N0.625 O1.25'
_chemical_formula_sum            'C149.75 H111.75 Ag2 F6 N5.5 O8.25 S14 Zn'
_chemical_formula_weight         2964.15
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           9
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 94.452(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   34.231(5)
_cell_length_b                   21.783(5)
_cell_length_c                   18.171(3)
_cell_measurement_reflns_used    9731
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.45
_cell_measurement_theta_min      2.38
_cell_volume                     13508(4)
_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 6.10'
_computing_publication_material  'SHELXTL 6.10'
_computing_structure_refinement  'SHELXTL 6.10'
_computing_structure_solution    'SHELXTL 6.10 (Bruker, 2000)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0423
_diffrn_reflns_av_sigmaI/netI    0.0635
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            59475
_diffrn_reflns_theta_full        26.40
_diffrn_reflns_theta_max         26.40
_diffrn_reflns_theta_min         1.11
_diffrn_standards_decay_%        none
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.749
_exptl_absorpt_correction_T_max  0.96
_exptl_absorpt_correction_T_min  0.7701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS in SAINT+ (Bruker, 2003)'
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             6069.5
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.294
_refine_diff_density_min         -0.680
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
'Flack H D (1983), Acta Cryst. A39, 876-881; 13372 Friedel pairs'
_refine_ls_abs_structure_Flack   0.113(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     1637
_refine_ls_number_reflns         27229
_refine_ls_number_restraints     395
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0643
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0827P)^2^+46.7466P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1640
_refine_ls_wR_factor_ref         0.1716
_reflns_number_gt                23365
_reflns_number_total             27229
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            cg800869u_si_002.cif
_cod_data_source_block           2
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
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_cell_volume        13509(4)
_cod_original_sg_symbol_H-M      Cc
_cod_original_formula_sum        'C149.75 H111.75 Ag2 F6 N5.50 O8.25 S14 Zn'
_cod_database_code               4511062
_comments
;
Large parts of the structure are either disordered, are ill defined solvent 
molecules, or both and a multitude of restraints was applied in order 
to deal with those moieties (see below).

The number of parameters for a full anisotropic refinement exceeded the 
threshold for a full matrix least square (L.S.)procedure and the structure 
was thus first refined using XH instead.

The structure was found to be racemically twinned, the BASF parameter 
refined to 0.113(17).

One of the two triflate anions is disordered over three positions. 
The occupancy ratios are 0.381(3) to 0.362(3) to 0.257(3). All bond 
lengths within the three disordered triflate moieties and the not disordered 
triflate anion were restraint to be equal to all their equivalent 
counterparts using SADI commands, as were the oxygen-oxygen and the 
fluorine-fluorine distances (Standard deviation: 0.02). The anisotropic 
displacement parameters within each disordered triflate 
moiety were restraint to be similar to each other using a SIMU 
command with a standard deviation of 0.005 for s and 0.01 for st. 
Each the sulfur and carbon atoms of the disordered triflate ions 
were further restraint to have identical thermal displacement parameters. 

The dimethyl acetamide molecule coordinated to the porphyrine zinc 
atom is disordered over two positions (including the Zn atom) on 
opposite sides of the porphyrine disk. The occupancy ratios 
refined to be 0.619(2) to 0.381(3). All bond lengths within the 
two moieties were restraint to be equal to all their equivalent 
counterparts using SADI commands (Standard deviation: 0.02). All 
anisotropic displacement parameters of chemically equivalent atoms 
within the two moieties were also restraint to be identical, and 
carbon atom C1a was restraint to be isotropic within a standard 
deviation of 0.001 (necessary due to direct overlap of C2A 
(restraint to C1A via EADP) with a carbon atom of the disordered 
partial occupied benzene ring described next).

The minor dimethyl acetamide molecule is further disordered with a 
benzene solvate molecule. Altogether six solvate benzene molecules are 
found in the asymmetric unit. All of them were  restraint to be 
ideal hexagons using an AFIX 66 command, all atoms of one ring were 
restraint to have the same anisotropic displacement parameters, and 
all carbon atoms were restraint to be isotropic within a standard 
deviation of 0.01. Two of the benzene rings are disordered with 
each other (C117 to C122 with C147 to C152) with an occupancy 
ratio of 0.47(2) to 0.53(2). All their atoms were restraint to 
have the same anisotropic displacement parameters. 

One of the other benzene molecules is disordered with a molecule of 
nitrobenzene. The atom positions for the two aromatic rings were to 
close to be effectively 
distinguished from each other and have been refined as one moiety. 
The atoms of the nitro 
group were restraint to have the same anisotropic displacement 
parameters as the carbon atoms of 
the aromatic ring, and the nitro group was assigned an occupancy 
factor which refined to 0.625(1).
The hydrogen atom of the benzene ring at the position of the 
nitro group was omitted.

Treatment of hydrogen atoms:
All hydrogen atoms were placed in calculated positions and were 
refined with an isotropic displacement parameter 1.5 (methyl) 
or 1.2 times (all others) that 
of the adjacent carbon atom. 

;