# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email NEIL.CHAMPNESS@NOTTINGHAM.AC.UK _publ_contact_author_name 'Dr Neil Champness' _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_address ; School of Chemistry University of Nottingham University Park Nottingham NG7 2RD UNITED KINGDOM ; _publ_section_title ; A design strategy for four connected coordination frameworks ; loop_ _publ_author_name 'Neil Champness' 'Alexander J. Blake' 'David B. Cordes' 'Olege V. Dolomanov' 'Lyall R. Hanton' ; G.B.Jameson ; 'Martin Schroder' 'Claire Wilson' data_Compound_1_(CUPYTP) _database_code_depnum_ccdc_archive 'CCDC 225249' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene copper tetrafluoroborate' _refine_special_details ; Distance and similarity restraints were applied to B-F bonds. The PLATON SQUEEZE procedure was used to treat regions of diffuse solvent which could not be sensibly modelled in terms of atomic sites. Their contribution to the diffraction pattern was removed and modified F(obs)**2 written to a new HKL file. The number of electrons thus located, 3409 per unit cell, are included in the formula, formula weight, calculated density, mu and F(000). This residual electron density was assigned to three molecules of CHCl3, 3/2 molecules of MeCN solvents and 1/4 counteranions [3409/16 = 213 e per ligand; 213 - 41*0.25(BF4) - 58*3(CHCl3) = 29 e. Three halfs of MeCN molecules would give 33e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene copper tetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H23.50 B Cl9 Cu F4 N5.50 S' _chemical_formula_weight 962.50 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+1/4, x+3/4, z+1/4' 'y+1/4, -x+1/4, z+3/4' '-x+1/2, y, -z+1/2' 'x, -y, -z' 'y+1/4, x+3/4, -z+1/4' '-y+1/4, -x+1/4, -z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+3/4, x+5/4, z+3/4' 'y+3/4, -x+3/4, z+5/4' '-x+1, y+1/2, -z+1' 'x+1/2, -y+1/2, -z+1/2' 'y+3/4, x+5/4, -z+3/4' '-y+3/4, -x+3/4, -z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-1/4, -x-3/4, -z-1/4' '-y-1/4, x-1/4, -z-3/4' 'x-1/2, -y, z-1/2' '-x, y, z' '-y-1/4, -x-3/4, z-1/4' 'y-1/4, x-1/4, z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y+1/4, -x-1/4, -z+1/4' '-y+1/4, x+1/4, -z-1/4' 'x, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' '-y+1/4, -x-1/4, z+1/4' 'y+1/4, x+1/4, z-1/4' _cell_length_a 22.522(3) _cell_length_b 22.522(3) _cell_length_c 33.600(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 17043(3) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 2927 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 28.65 _exptl_crystal_description tablet _exptl_crystal_colour orange _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.500 _exptl_crystal_density_method ? _exptl_crystal_F_000 7696 _exptl_absorpt_coefficient_mu 1.173 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.570 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'Bruker SADABS, 1996' _exptl_special_details ? _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD area detector' _diffrn_measurement_method omega _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% none _diffrn_reflns_number 49351 _diffrn_reflns_av_R_equivalents 0.295 _diffrn_reflns_av_sigmaI/netI 0.1069 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -44 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 1.09 _diffrn_reflns_theta_max 24.99 _reflns_number_total 5871 _reflns_number_gt 1930 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART version 5.624 (Bruker, 2001)' _computing_cell_refinement 'Bruker SAINT version 6.02a (Bruker, 2000)' _computing_data_reduction 'Bruker SAINT; Bruker SHELXTL (Bruker, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'OLEX (Oleg V.Dolomanov, 2001)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0987P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3967 _refine_ls_number_parameters 168 _refine_ls_number_restraints 11 _refine_ls_R_factor_all 0.1116 _refine_ls_R_factor_gt 0.0662 _refine_ls_wR_factor_ref 0.1745 _refine_ls_wR_factor_gt 0.1593 _refine_ls_goodness_of_fit_ref 0.859 _refine_ls_restrained_S_all 0.902 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu Cu 0.32392(2) 0.07392(2) 0.6250 0.0340(3) Uani 1 2 d S . . N1 N 0.23688(16) 0.08135(17) 0.64243(12) 0.0367(10) Uani 1 1 d . . . C2 C 0.2202(2) 0.1139(2) 0.67355(16) 0.0404(13) Uani 1 1 d . . . H2 H 0.2505 0.1335 0.6881 0.048 Uiso 1 1 calc R . . C3 C 0.1633(2) 0.1213(2) 0.68613(15) 0.0440(14) Uani 1 1 d . . . H3 H 0.1548 0.1461 0.7083 0.053 Uiso 1 1 calc R . . C4 C 0.1177(2) 0.0920(2) 0.66610(15) 0.0407(13) Uani 1 1 d . . . C5 C 0.1343(2) 0.0576(2) 0.63369(16) 0.0478(15) Uani 1 1 d . . . H5 H 0.1048 0.0375 0.6187 0.057 Uiso 1 1 calc R . . C6 C 0.19282(19) 0.0524(2) 0.62312(15) 0.0420(13) Uani 1 1 d . . . H6 H 0.2029 0.0275 0.6013 0.050 Uiso 1 1 calc R . . C7 C 0.0552(2) 0.0960(2) 0.67830(16) 0.0399(13) Uani 1 1 d . . . S7 S 0.0000 0.09321(9) 0.64275(6) 0.0458(5) Uani 1 2 d S . . C8 C 0.03207(19) 0.1005(2) 0.71567(15) 0.0343(12) Uani 1 1 d . . . C9 C 0.0670(2) 0.0965(2) 0.75313(15) 0.0384(12) Uani 1 1 d . . . C10 C 0.0909(3) 0.0440(2) 0.76507(19) 0.0652(19) Uani 1 1 d . . . H10 H 0.0876 0.0099 0.7486 0.078 Uiso 1 1 calc R . . C11 C 0.1203(3) 0.0404(3) 0.80151(17) 0.0662(19) Uani 1 1 d . . . H11 H 0.1355 0.0029 0.8095 0.079 Uiso 1 1 calc R . . N12 N 0.12803(17) 0.08557(17) 0.82541(12) 0.0349(10) Uani 1 1 d . . . C13 C 0.1041(2) 0.1369(2) 0.81397(15) 0.0482(14) Uani 1 1 d . . . H13 H 0.1073 0.1701 0.8312 0.058 Uiso 1 1 calc R . . C14 C 0.0744(2) 0.1441(2) 0.77775(17) 0.0550(16) Uani 1 1 d . . . H14 H 0.0595 0.1820 0.7703 0.066 Uiso 1 1 calc R . . B1 B 0.2500 0.2500 0.7500 0.125(8) Uiso 1 4 d SD . . F1 F 0.2500 0.1926(3) 0.7500 0.138(5) Uani 0.67 2 d SPD . . F2 F 0.1954(5) 0.2500 0.7248(5) 0.233(9) Uani 0.67 2 d SPD . . F3 F 0.2845(6) 0.2500 0.7133(3) 0.202(6) Uani 0.67 2 d SPD . . B2 B 0.0000 0.2500 0.8750 0.113(10) Uani 1 8 d SD . . F4 F 0.0643(3) 0.2500 0.8711(3) 0.083(3) Uani 0.50 2 d SPD . . F5 F 0.0000 0.2500 0.9163(2) 0.184(5) Uani 1 4 d SD . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu 0.0305(3) 0.0305(3) 0.0411(5) -0.0016(3) 0.0016(3) 0.0002(4) N1 0.031(2) 0.043(3) 0.036(2) -0.013(2) 0.0095(19) -0.003(2) C2 0.024(3) 0.045(3) 0.052(3) -0.003(3) -0.004(2) -0.004(2) C3 0.031(3) 0.052(3) 0.050(3) -0.011(3) 0.004(2) -0.008(3) C4 0.037(3) 0.043(3) 0.042(3) -0.001(3) 0.004(3) -0.001(2) C5 0.028(3) 0.061(4) 0.054(4) -0.014(3) -0.004(3) -0.009(3) C6 0.021(3) 0.056(3) 0.049(3) -0.016(3) 0.000(2) -0.002(2) C7 0.028(3) 0.047(3) 0.045(3) -0.003(3) -0.003(2) 0.001(2) S7 0.0276(10) 0.0630(13) 0.0468(12) -0.0043(10) 0.000 0.000 C8 0.023(2) 0.035(3) 0.045(3) -0.005(2) 0.006(2) -0.002(2) C9 0.023(3) 0.045(3) 0.047(3) -0.001(3) 0.001(2) -0.001(2) C10 0.092(5) 0.024(3) 0.079(5) -0.015(3) -0.025(4) 0.016(3) C11 0.101(5) 0.039(3) 0.058(4) -0.009(3) -0.037(4) 0.022(4) N12 0.032(2) 0.031(2) 0.043(2) -0.0065(19) -0.0055(19) -0.0037(18) C13 0.058(4) 0.038(3) 0.049(3) -0.011(3) -0.015(3) 0.008(3) C14 0.061(4) 0.036(3) 0.067(4) -0.006(3) -0.025(3) 0.015(3) F1 0.293(15) 0.030(4) 0.093(7) 0.000 -0.109(8) 0.000 F2 0.251(18) 0.059(7) 0.39(2) 0.000 -0.147(18) 0.000 F3 0.115(10) 0.251(18) 0.240(17) 0.000 0.036(11) 0.000 B2 0.126(18) 0.126(18) 0.09(2) 0.000 0.000 0.000 F4 0.108(9) 0.031(5) 0.109(9) 0.000 0.019(8) 0.000 F5 0.106(9) 0.262(18) 0.185(12) 0.000 0.000 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu N12 2.004(4) 4_554 ? Cu N12 2.004(4) 5_556 ? Cu N1 2.053(4) 7_546 ? Cu N1 2.053(4) . ? N1 C2 1.331(6) . ? N1 C6 1.353(6) . ? C2 C3 1.359(6) . ? C3 C4 1.395(7) . ? C4 C5 1.387(7) . ? C4 C7 1.468(7) . ? C5 C6 1.370(7) . ? C7 C8 1.363(7) . ? C7 S7 1.726(5) . ? S7 C7 1.726(5) 22 ? C8 C8 1.444(9) 22 ? C8 C9 1.487(7) . ? C9 C10 1.359(7) . ? C9 C14 1.365(7) . ? C10 C11 1.394(8) . ? C11 N12 1.309(6) . ? N12 C13 1.332(6) . ? N12 Cu 2.004(4) 3_545 ? C13 C14 1.398(7) . ? B1 F1 1.293(6) 25_556 ? B1 F1 1.293(6) . ? B1 F3 1.457(8) . ? B1 F3 1.457(8) 25_556 ? B1 F2 1.494(8) . ? B1 F2 1.494(8) 25_556 ? B2 F5 1.387(8) 19_567 ? B2 F5 1.387(8) . ? B2 F4 1.454(8) 28_557 ? B2 F4 1.454(8) . ? B2 F4 1.454(8) 10_454 ? B2 F4 1.454(8) 19_567 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Cu N12 123.4(2) 4_554 5_556 ? N12 Cu N1 105.53(16) 4_554 7_546 ? N12 Cu N1 108.56(15) 5_556 7_546 ? N12 Cu N1 108.56(15) 4_554 . ? N12 Cu N1 105.53(16) 5_556 . ? N1 Cu N1 103.7(2) 7_546 . ? C2 N1 C6 115.8(4) . . ? C2 N1 Cu 122.6(3) . . ? C6 N1 Cu 121.6(3) . . ? N1 C2 C3 125.3(5) . . ? C2 C3 C4 119.1(5) . . ? C5 C4 C3 116.4(5) . . ? C5 C4 C7 120.8(5) . . ? C3 C4 C7 122.8(5) . . ? C6 C5 C4 120.7(5) . . ? N1 C6 C5 122.7(5) . . ? C8 C7 C4 128.9(5) . . ? C8 C7 S7 111.4(4) . . ? C4 C7 S7 119.7(4) . . ? C7 S7 C7 92.3(4) . 22 ? C7 C8 C8 112.5(3) . 22 ? C7 C8 C9 124.9(4) . . ? C8 C8 C9 121.9(2) 22 . ? C10 C9 C14 117.1(5) . . ? C10 C9 C8 120.9(5) . . ? C14 C9 C8 122.0(5) . . ? C9 C10 C11 119.9(5) . . ? N12 C11 C10 123.8(5) . . ? C11 N12 C13 116.4(4) . . ? C11 N12 Cu 118.7(4) . 3_545 ? C13 N12 Cu 124.9(3) . 3_545 ? N12 C13 C14 123.1(5) . . ? C9 C14 C13 119.7(5) . . ? F1 B1 F1 180.000(4) 25_556 . ? F1 B1 F3 90.000(5) 25_556 . ? F1 B1 F3 90.000(1) . . ? F1 B1 F3 90.000(1) 25_556 25_556 ? F1 B1 F3 90.000(3) . 25_556 ? F3 B1 F3 180.000(3) . 25_556 ? F1 B1 F2 90.000(1) 25_556 . ? F1 B1 F2 90.000(3) . . ? F3 B1 F2 87.6(7) . . ? F3 B1 F2 92.4(7) 25_556 . ? F1 B1 F2 90.000(7) 25_556 25_556 ? F1 B1 F2 90.000(1) . 25_556 ? F3 B1 F2 92.4(7) . 25_556 ? F3 B1 F2 87.6(7) 25_556 25_556 ? F2 B1 F2 180.0(11) . 25_556 ? F5 B2 F5 180.000(5) 19_567 . ? F5 B2 F4 95.1(4) 19_567 28_557 ? F5 B2 F4 84.9(4) . 28_557 ? F5 B2 F4 84.9(4) 19_567 . ? F5 B2 F4 95.1(4) . . ? F4 B2 F4 90.45(8) 28_557 . ? F5 B2 F4 84.9(4) 19_567 10_454 ? F5 B2 F4 95.1(4) . 10_454 ? F4 B2 F4 90.45(8) 28_557 10_454 ? F4 B2 F4 169.8(9) . 10_454 ? F5 B2 F4 95.1(4) 19_567 19_567 ? F5 B2 F4 84.9(4) . 19_567 ? F4 B2 F4 169.8(9) 28_557 19_567 ? F4 B2 F4 90.45(8) . 19_567 ? F4 B2 F4 90.45(8) 10_454 19_567 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.681 _refine_diff_density_min -0.840 _refine_diff_density_rms 0.080 #===END data_Compound_2a_(THPYAG) _database_code_depnum_ccdc_archive 'CCDC 225250' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene silver tetrafluoroborate' _refine_special_details ; After failing to model regions of diffuse electron density, we resorted to the PLATON SQUEEZE procedure. This removed the contribution of the diffuse regions to the diffraction pattern and gave a new HKL file. The number of electrons thus estimated were included in the final formula, formula weight, calculated density, mu and F(000) is 4240 per unit cell. The residual electron density was assigned to four molecules of the chloroform solvent, half a counteranion and half a molecule of acetonitrile (solvent) [4240/16 = 265 e per ligand molecule. 265 - 41*0.5(BF4) - 58*4(CHCl3) = 12.5 e. One half of molecule of MeCN would give 11 e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene silver tetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29 H21.50 Ag B Cl12 F4 N4.5 S' _chemical_formula_weight 1085.16 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+1/4, x+3/4, z+1/4' 'y+1/4, -x+1/4, z+3/4' '-x+1/2, y, -z+1/2' 'x, -y, -z' 'y+1/4, x+3/4, -z+1/4' '-y+1/4, -x+1/4, -z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+3/4, x+5/4, z+3/4' 'y+3/4, -x+3/4, z+5/4' '-x+1, y+1/2, -z+1' 'x+1/2, -y+1/2, -z+1/2' 'y+3/4, x+5/4, -z+3/4' '-y+3/4, -x+3/4, -z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-1/4, -x-3/4, -z-1/4' '-y-1/4, x-1/4, -z-3/4' 'x-1/2, -y, z-1/2' '-x, y, z' '-y-1/4, -x-3/4, z-1/4' 'y-1/4, x-1/4, z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y+1/4, -x-1/4, -z+1/4' '-y+1/4, x+1/4, -z-1/4' 'x, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' '-y+1/4, -x-1/4, z+1/4' 'y+1/4, x+1/4, z-1/4' _cell_length_a 22.5430(5) _cell_length_b 22.5430(5) _cell_length_c 35.5167(12) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 18049.1(8) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 14765 _cell_measurement_theta_min 2.3 _cell_measurement_theta_max 28.75 _exptl_crystal_description cube _exptl_crystal_colour colourless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.50 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.597 _exptl_crystal_density_method ? _exptl_crystal_F_000 8560 _exptl_absorpt_coefficient_mu 1.250 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.837 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details '(SADABS version 2.03; Bruker, 2001)' _exptl_special_details ? _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD area detector' _diffrn_measurement_method omega _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% none _diffrn_reflns_number 52661 _diffrn_reflns_av_R_equivalents 0.029 _diffrn_reflns_av_sigmaI/netI 0.0172 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -47 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 1.07 _diffrn_reflns_theta_max 29.09 _reflns_number_total 6203 _reflns_number_gt 4274 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART version 5.624 (Bruker, 2001)' _computing_cell_refinement 'Bruker SAINT version 6.02a (Bruker, 2000)' _computing_data_reduction 'Bruker SAINT; Bruker SHELXTL (Bruker, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'OLEX (Dolomanov, 2003)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5917 _refine_ls_number_parameters 159 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0604 _refine_ls_R_factor_gt 0.0466 _refine_ls_wR_factor_ref 0.1618 _refine_ls_wR_factor_gt 0.1504 _refine_ls_goodness_of_fit_ref 1.191 _refine_ls_restrained_S_all 1.191 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ag Ag 0.338573(8) 0.088573(8) 0.6250 0.03189(12) Uani 1 2 d S . . N1 N 0.23632(10) 0.09176(9) 0.64109(7) 0.0440(5) Uani 1 1 d . . . C2 C 0.21900(12) 0.12319(14) 0.67091(8) 0.0531(7) Uani 1 1 d . . . H2 H 0.2483 0.1441 0.6848 0.064 Uiso 1 1 calc R . . C3 C 0.16087(11) 0.12711(14) 0.68276(9) 0.0473(7) Uani 1 1 d . . . H3 H 0.1506 0.1514 0.7036 0.057 Uiso 1 1 calc R . . C4 C 0.11773(10) 0.09512(10) 0.66383(7) 0.0344(5) Uani 1 1 d . . . C5 C 0.13575(11) 0.06162(13) 0.63315(8) 0.0450(6) Uani 1 1 d . . . H5 H 0.1077 0.0391 0.6192 0.054 Uiso 1 1 calc R . . C6 C 0.19464(11) 0.06127(14) 0.62305(7) 0.0441(6) Uani 1 1 d . . . H6 H 0.2062 0.0379 0.6020 0.053 Uiso 1 1 calc R . . C7 C 0.05506(10) 0.09613(10) 0.67555(7) 0.0342(5) Uani 1 1 d . . . S7 S 0.0000 0.09296(4) 0.64217(3) 0.0372(2) Uani 1 2 d S . . C8 C 0.03178(10) 0.10078(10) 0.71134(7) 0.0336(5) Uani 1 1 d . . . C9 C 0.06565(10) 0.10069(10) 0.74718(7) 0.0328(5) Uani 1 1 d . . . C10 C 0.08374(14) 0.04801(12) 0.76310(9) 0.0550(8) Uani 1 1 d . . . H10 H 0.0773 0.0116 0.7503 0.066 Uiso 1 1 calc R . . C11 C 0.11120(14) 0.04843(12) 0.79768(8) 0.0553(8) Uani 1 1 d . . . H11 H 0.1229 0.0115 0.8083 0.066 Uiso 1 1 calc R . . N12 N 0.12238(9) 0.09776(9) 0.81718(6) 0.0357(4) Uani 1 1 d . . . C13 C 0.10661(15) 0.14722(13) 0.80118(9) 0.0565(8) Uani 1 1 d . . . H13 H 0.1159 0.1832 0.8138 0.068 Uiso 1 1 calc R . . C14 C 0.07743(16) 0.15108(13) 0.76721(10) 0.0604(8) Uani 1 1 d . . . H14 H 0.0655 0.1886 0.7577 0.073 Uiso 1 1 calc R . . B1 B 0.2500 0.2500 0.7500 0.103(4) Uani 1 4 d S . . F1 F 0.2500 0.1910(2) 0.7500 0.125(2) Uani 0.75 2 d SP . . F2 F 0.2213(3) 0.2500 0.7880(2) 0.157(2) Uani 0.75 2 d SP . . F3 F 0.1913(4) 0.2500 0.7287(2) 0.163(3) Uani 0.75 2 d SP . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ag 0.03453(14) 0.03453(14) 0.02660(17) -0.00088(6) 0.00088(6) 0.00095(9) N1 0.0320(11) 0.0572(14) 0.0426(13) -0.0107(10) 0.0030(10) -0.0025(9) C2 0.0357(13) 0.0700(19) 0.0534(17) -0.0188(15) 0.0058(12) -0.0090(13) C3 0.0365(14) 0.0601(18) 0.0455(16) -0.0179(14) 0.0029(10) -0.0040(12) C4 0.0279(11) 0.0420(13) 0.0334(12) -0.0030(9) -0.0014(9) -0.0003(9) C5 0.0333(13) 0.0563(16) 0.0453(14) -0.0093(13) 0.0042(11) -0.0055(12) C6 0.0349(13) 0.0582(17) 0.0392(14) -0.0140(12) 0.0044(10) -0.0014(13) C7 0.0280(11) 0.0427(13) 0.0320(12) -0.0017(9) -0.0047(9) -0.0012(9) S7 0.0295(4) 0.0518(5) 0.0304(4) -0.0038(3) 0.000 0.000 C8 0.0298(12) 0.0370(12) 0.0340(12) -0.0020(9) 0.0014(9) 0.0016(9) C9 0.0283(11) 0.0396(12) 0.0305(11) -0.0007(9) 0.0003(9) -0.0016(10) C10 0.072(2) 0.0415(15) 0.0513(16) -0.0070(12) -0.0231(15) 0.0042(13) C11 0.079(2) 0.0416(14) 0.0457(16) -0.0017(12) -0.0172(15) 0.0068(14) N12 0.0344(11) 0.0435(11) 0.0290(10) 0.0007(8) -0.0025(8) 0.0026(8) C13 0.079(2) 0.0442(15) 0.0458(17) -0.0044(12) -0.0204(15) 0.0058(15) C14 0.088(2) 0.0431(16) 0.0498(17) 0.0010(13) -0.0247(16) 0.0070(15) B1 0.139(11) 0.102(9) 0.067(7) 0.000 -0.004(7) 0.000 F1 0.192(6) 0.090(4) 0.093(4) 0.000 -0.037(4) 0.000 F2 0.177(7) 0.139(5) 0.154(6) 0.000 0.012(5) 0.000 F3 0.182(7) 0.128(5) 0.179(7) 0.000 -0.038(6) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ag N12 2.244(2) 5_556 ? Ag N12 2.244(2) 4_554 ? Ag N1 2.376(2) 7_546 ? Ag N1 2.376(2) . ? N1 C6 1.329(3) . ? N1 C2 1.333(3) . ? C2 C3 1.379(3) . ? C3 C4 1.385(4) . ? C4 C5 1.386(4) . ? C4 C7 1.473(3) . ? C5 C6 1.375(4) . ? C7 C8 1.379(3) . ? C7 S7 1.718(2) . ? S7 C7 1.718(2) 22 ? C8 C8 1.433(4) 22 ? C8 C9 1.484(3) . ? C9 C14 1.366(4) . ? C9 C10 1.377(4) . ? C10 C11 1.375(4) . ? C11 N12 1.334(3) . ? N12 C13 1.301(3) . ? N12 Ag 2.244(2) 3_545 ? C13 C14 1.377(4) . ? B1 F1 1.329(5) . ? B1 F1 1.329(5) 25_556 ? B1 F2 1.495(8) . ? B1 F2 1.495(8) 25_556 ? B1 F3 1.524(8) 25_556 ? B1 F3 1.524(8) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Ag N12 139.92(11) 5_556 4_554 ? N12 Ag N1 107.33(8) 5_556 7_546 ? N12 Ag N1 99.07(8) 4_554 7_546 ? N12 Ag N1 99.07(8) 5_556 . ? N12 Ag N1 107.33(8) 4_554 . ? N1 Ag N1 96.69(10) 7_546 . ? C6 N1 C2 116.8(2) . . ? C6 N1 Ag 123.66(18) . . ? C2 N1 Ag 119.44(18) . . ? N1 C2 C3 123.7(3) . . ? C2 C3 C4 119.1(3) . . ? C3 C4 C5 117.3(2) . . ? C3 C4 C7 121.9(2) . . ? C5 C4 C7 120.8(2) . . ? C6 C5 C4 119.4(2) . . ? N1 C6 C5 123.6(2) . . ? C8 C7 C4 128.8(2) . . ? C8 C7 S7 111.36(18) . . ? C4 C7 S7 119.82(18) . . ? C7 S7 C7 92.52(17) 22 . ? C7 C8 C8 112.37(14) . 22 ? C7 C8 C9 126.5(2) . . ? C8 C8 C9 120.96(13) 22 . ? C14 C9 C10 116.5(2) . . ? C14 C9 C8 123.0(2) . . ? C10 C9 C8 120.4(2) . . ? C11 C10 C9 119.6(2) . . ? N12 C11 C10 123.7(3) . . ? C13 N12 C11 115.9(2) . . ? C13 N12 Ag 125.88(18) . 3_545 ? C11 N12 Ag 118.18(17) . 3_545 ? N12 C13 C14 124.6(3) . . ? C9 C14 C13 119.8(3) . . ? F1 B1 F1 180.000(3) . 25_556 ? F1 B1 F2 90.000(2) . . ? F1 B1 F2 90.000(1) 25_556 . ? F1 B1 F2 90.000(1) . 25_556 ? F1 B1 F2 90.000(2) 25_556 25_556 ? F2 B1 F2 180.000(2) . 25_556 ? F1 B1 F3 90.000(1) . 25_556 ? F1 B1 F3 90.000(3) 25_556 25_556 ? F2 B1 F3 85.9(4) . 25_556 ? F2 B1 F3 94.1(4) 25_556 25_556 ? F1 B1 F3 90.000(3) . . ? F1 B1 F3 90.000(1) 25_556 . ? F2 B1 F3 94.1(4) . . ? F2 B1 F3 85.9(4) 25_556 . ? F3 B1 F3 180.000(2) 25_556 . ? _diffrn_measured_fraction_theta_max 0.930 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 2.064 _refine_diff_density_min -0.605 _refine_diff_density_rms 0.093 #===END data_Compound_2b_(sdcpab) _database_code_depnum_ccdc_archive 'CCDC 225251' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene silver tetrafluoroborate' _refine_special_details ; After failing to model regions of diffuse electron density, we resorted to the PLATON SQUEEZE procedure. This removed the contribution of the diffuse regions to the diffraction pattern and gave a new HKL file. The number of electrons thus estimated were included in the final formula, formula weight, calculated density, mu and F(000) is 2056 per unit cell. The residual electron density was assigned to a half of a counteranion, three molecules of acetonitrile solvent, and a molecule of dichloromethane solvent [2056/16 = 128.5 e per ligand molecule. 128.5 - 41*0.5(BF4) - 22*3(MeCN)= 42 e. One molecule of CH2Cl2 would give 42 e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene silver tetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C31 H27 Ag B Cl2 F4 N7 S' _chemical_formula_weight 795.24 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y+1/2, z' 'x, -y, -z' '-x, y+1/2, -z' '-y+1/4, -x+1/4, -z+3/4' 'y+1/4, x+3/4, -z+1/4' 'y+1/4, -x+1/4, z+3/4' '-y+1/4, x+3/4, z+1/4' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1, z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1, -z+1/2' '-y+3/4, -x+3/4, -z+5/4' 'y+3/4, x+5/4, -z+3/4' 'y+3/4, -x+3/4, z+5/4' '-y+3/4, x+5/4, z+3/4' '-x, -y, -z' 'x, y-1/2, -z' '-x, y, z' 'x, -y-1/2, z' 'y-1/4, x-1/4, z-3/4' '-y-1/4, -x-3/4, z-1/4' '-y-1/4, x-1/4, -z-3/4' 'y-1/4, -x-3/4, -z-1/4' '-x+1/2, -y+1/2, -z+1/2' 'x+1/2, y, -z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y, z+1/2' 'y+1/4, x+1/4, z-1/4' '-y+1/4, -x-1/4, z+1/4' '-y+1/4, x+1/4, -z-1/4' 'y+1/4, -x-1/4, -z+1/4' _cell_length_a 22.636(5) _cell_length_b 22.636(5) _cell_length_c 35.393(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 18135(6) _cell_formula_units_Z 16 _cell_measurement_temperature 163(2) _cell_measurement_reflns_used 7413 _cell_measurement_theta_min 2.30 _cell_measurement_theta_max 24.06 _exptl_crystal_description rhomb _exptl_crystal_colour colourless _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.45 _exptl_crystal_size_min 0.24 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.165 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6400 _exptl_absorpt_coefficient_mu 0.650 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8348 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details 'Bruker SADABS, 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 163(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 2 _diffrn_reflns_number 76054 _diffrn_reflns_av_R_equivalents 0.0802 _diffrn_reflns_av_sigmaI/netI 0.0429 _diffrn_reflns_limit_h_min -27 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -44 _diffrn_reflns_limit_l_max 41 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 26.38 _reflns_number_total 4889 _reflns_number_gt 3111 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'OLEX (Oleg V.Dolomanov, 2001)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0784P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4889 _refine_ls_number_parameters 159 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0698 _refine_ls_R_factor_gt 0.0418 _refine_ls_wR_factor_ref 0.1267 _refine_ls_wR_factor_gt 0.1199 _refine_ls_goodness_of_fit_ref 0.962 _refine_ls_restrained_S_all 0.962 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ag Ag 0.336713(10) 0.086713(10) 0.6250 0.03536(13) Uani 1 2 d S . . N1 N 0.23512(12) 0.09194(13) 0.64049(8) 0.0529(8) Uani 1 1 d . . . C2 C 0.21733(15) 0.12485(18) 0.66954(10) 0.0637(11) Uani 1 1 d . . . H2 H 0.2455 0.1473 0.6822 0.076 Uiso 1 1 calc R . . C3 C 0.16035(15) 0.12773(19) 0.68193(10) 0.0600(11) Uani 1 1 d . . . H3 H 0.1505 0.1517 0.7023 0.072 Uiso 1 1 calc R . . C4 C 0.11730(13) 0.09469(14) 0.66391(8) 0.0389(7) Uani 1 1 d . . . C5 C 0.13478(14) 0.06016(16) 0.63380(9) 0.0447(8) Uani 1 1 d . . . H5 H 0.1074 0.0374 0.6208 0.054 Uiso 1 1 calc R . . C6 C 0.19411(14) 0.05989(17) 0.62317(9) 0.0499(8) Uani 1 1 d . . . H6 H 0.2055 0.0361 0.6030 0.060 Uiso 1 1 calc R . . C7 C 0.05478(13) 0.09583(13) 0.67599(8) 0.0373(7) Uani 1 1 d . . . S7 S 0.0000 0.09223(5) 0.64206(3) 0.0414(3) Uani 1 2 d S . . C8 C 0.03144(12) 0.10007(13) 0.71144(8) 0.0348(7) Uani 1 1 d . . . C9 C 0.06519(13) 0.09951(13) 0.74734(8) 0.0353(7) Uani 1 1 d . . . C10 C 0.08324(17) 0.04764(16) 0.76305(10) 0.0599(10) Uani 1 1 d . . . H10 H 0.0766 0.0121 0.7506 0.072 Uiso 1 1 calc R . . C11 C 0.11162(17) 0.04834(16) 0.79782(10) 0.0614(11) Uani 1 1 d . . . H11 H 0.1228 0.0123 0.8082 0.074 Uiso 1 1 calc R . . N12 N 0.12380(11) 0.09621(11) 0.81705(7) 0.0374(6) Uani 1 1 d . . . C13 C 0.10759(18) 0.14606(15) 0.80130(10) 0.0631(11) Uani 1 1 d . . . H13 H 0.1165 0.1812 0.8137 0.076 Uiso 1 1 calc R . . C14 C 0.07782(19) 0.14906(16) 0.76719(11) 0.0709(13) Uani 1 1 d . . . H14 H 0.0663 0.1857 0.7578 0.085 Uiso 1 1 calc R . . B1 B 0.2500 0.2500 0.7500 0.166(9) Uani 1 4 d S . . F1 F 0.2500 0.1920(3) 0.7500 0.152(4) Uani 0.67 2 d SP . . F2 F 0.2203(5) 0.2500 0.7863(3) 0.197(4) Uani 0.67 2 d SP . . F3 F 0.3069(5) 0.2500 0.7725(3) 0.188(4) Uani 0.67 2 d SP . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ag 0.03757(15) 0.03757(15) 0.03093(19) 0.00016(10) -0.00016(10) 0.00120(15) N1 0.0331(15) 0.075(2) 0.0500(16) -0.0214(15) 0.0065(13) -0.0060(15) C2 0.034(2) 0.094(3) 0.063(2) -0.034(2) 0.0057(17) -0.014(2) C3 0.040(2) 0.084(3) 0.056(2) -0.032(2) 0.0106(17) -0.007(2) C4 0.0292(16) 0.053(2) 0.0345(16) -0.0048(15) 0.0005(13) -0.0039(15) C5 0.0296(17) 0.060(2) 0.045(2) -0.0119(16) 0.0023(14) -0.0012(17) C6 0.0394(19) 0.066(2) 0.0439(18) -0.0178(18) 0.0052(16) -0.0032(17) C7 0.0302(16) 0.0477(19) 0.0339(16) -0.0014(14) -0.0032(13) 0.0031(14) S7 0.0280(6) 0.0596(8) 0.0367(6) -0.0016(6) 0.000 0.000 C8 0.0282(15) 0.0404(18) 0.0359(16) -0.0014(13) -0.0009(13) -0.0004(13) C9 0.0278(14) 0.0446(19) 0.0334(16) 0.0001(13) -0.0008(12) -0.0005(14) C10 0.082(3) 0.046(2) 0.052(2) -0.0083(17) -0.025(2) 0.001(2) C11 0.087(3) 0.048(2) 0.049(2) 0.0036(17) -0.027(2) 0.013(2) N12 0.0374(15) 0.0444(16) 0.0304(13) -0.0007(11) -0.0031(11) 0.0033(12) C13 0.099(3) 0.043(2) 0.048(2) -0.0040(17) -0.031(2) 0.011(2) C14 0.110(3) 0.046(2) 0.057(2) -0.0052(18) -0.045(2) 0.022(2) B1 0.25(3) 0.22(3) 0.033(7) 0.000 -0.021(11) 0.000 F1 0.297(11) 0.058(4) 0.102(5) 0.000 -0.088(6) 0.000 F2 0.202(10) 0.148(8) 0.242(12) 0.000 0.037(9) 0.000 F3 0.241(11) 0.102(6) 0.222(10) 0.000 -0.096(10) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ag N12 2.248(2) 12_546 ? Ag N12 2.248(2) 7_554 ? Ag N1 2.367(3) 6_546 ? Ag N1 2.367(3) . ? N1 C6 1.328(4) . ? N1 C2 1.332(4) . ? C2 C3 1.364(4) . ? C3 C4 1.384(4) . ? C4 C5 1.379(4) . ? C4 C7 1.479(4) . ? C5 C6 1.395(4) . ? C7 C8 1.365(4) . ? C7 S7 1.728(3) . ? S7 C7 1.728(3) 19 ? C8 C8 1.423(5) 19 ? C8 C9 1.483(4) . ? C9 C14 1.354(4) . ? C9 C10 1.362(4) . ? C10 C11 1.388(4) . ? C11 N12 1.309(4) . ? N12 C13 1.311(4) . ? N12 Ag 2.248(2) 12_546 ? C13 C14 1.384(5) . ? B1 F1 1.312(6) . ? B1 F1 1.312(6) 25_556 ? B1 F2 1.448(11) . ? B1 F2 1.448(11) 25_556 ? B1 F3 1.514(10) 25_556 ? B1 F3 1.514(10) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Ag N12 139.16(13) 12_546 7_554 ? N12 Ag N1 106.52(10) 12_546 6_546 ? N12 Ag N1 99.81(10) 7_554 6_546 ? N12 Ag N1 99.81(10) 12_546 . ? N12 Ag N1 106.52(10) 7_554 . ? N1 Ag N1 98.67(14) 6_546 . ? C6 N1 C2 116.8(3) . . ? C6 N1 Ag 123.0(2) . . ? C2 N1 Ag 120.0(2) . . ? N1 C2 C3 124.1(3) . . ? C2 C3 C4 119.5(3) . . ? C5 C4 C3 117.4(3) . . ? C5 C4 C7 120.5(3) . . ? C3 C4 C7 122.1(3) . . ? C4 C5 C6 119.1(3) . . ? N1 C6 C5 123.1(3) . . ? C8 C7 C4 129.6(3) . . ? C8 C7 S7 111.4(2) . . ? C4 C7 S7 119.0(2) . . ? C7 S7 C7 91.7(2) . 19 ? C7 C8 C8 112.78(17) . 19 ? C7 C8 C9 126.0(3) . . ? C8 C8 C9 121.02(16) 19 . ? C14 C9 C10 116.0(3) . . ? C14 C9 C8 123.1(3) . . ? C10 C9 C8 120.8(3) . . ? C9 C10 C11 119.4(3) . . ? N12 C11 C10 124.6(3) . . ? C11 N12 C13 115.6(3) . . ? C11 N12 Ag 118.6(2) . 12_546 ? C13 N12 Ag 125.6(2) . 12_546 ? N12 C13 C14 123.3(3) . . ? C9 C14 C13 121.0(3) . . ? F1 B1 F1 180.000(1) . 25_556 ? F1 B1 F2 90.000(4) . . ? F1 B1 F2 90.000(1) 25_556 . ? F1 B1 F2 90.000(1) . 25_556 ? F1 B1 F2 90.000(4) 25_556 25_556 ? F2 B1 F2 180.000(4) . 25_556 ? F1 B1 F3 90.000(4) . 25_556 ? F1 B1 F3 90.000(1) 25_556 25_556 ? F2 B1 F3 94.1(6) . 25_556 ? F2 B1 F3 85.9(6) 25_556 25_556 ? F1 B1 F3 90.000(1) . . ? F1 B1 F3 90.000(5) 25_556 . ? F2 B1 F3 85.9(6) . . ? F2 B1 F3 94.1(6) 25_556 . ? F3 B1 F3 180.0(7) 25_556 . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 26.38 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.615 _refine_diff_density_min -0.416 _refine_diff_density_rms 0.077 #===END data_Compound_3_(AGTHPY) _database_code_depnum_ccdc_archive 'CCDC 225252' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene silver hexafluoroantimonate' _refine_special_details ; Distance and similarity restraints were applied to Sb-F bonds. The PLATON SQUEEZE procedure was used to treat regions of diffuse solvent which could not be sensibly modelled in terms of atomic sites. Their contribution to the diffraction pattern was removed and modified F(obs)**2 written to a new HKL file. The number of electrons thus located, 1373 per unit cell, are included in the formula, formula weight, calculated density, mu and F(000). This residual electron density was assigned to a molecule of CHCl3, a molecules of MeCN solvents [1373/16 = 86 e per ligand; 86 - 22*1(MeCN)) = 64 e. A molecule of CHCl3 would give 58e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene silver hexafluoroantimonate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C27 H20 Ag Cl3 F6 N5 S Sb' _chemical_formula_weight 896.51 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Sb Sb -0.5866 1.5461 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+1/4, x+3/4, z+1/4' 'y+1/4, -x+1/4, z+3/4' '-x+1/2, y, -z+1/2' 'x, -y, -z' 'y+1/4, x+3/4, -z+1/4' '-y+1/4, -x+1/4, -z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+3/4, x+5/4, z+3/4' 'y+3/4, -x+3/4, z+5/4' '-x+1, y+1/2, -z+1' 'x+1/2, -y+1/2, -z+1/2' 'y+3/4, x+5/4, -z+3/4' '-y+3/4, -x+3/4, -z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-1/4, -x-3/4, -z-1/4' '-y-1/4, x-1/4, -z-3/4' 'x-1/2, -y, z-1/2' '-x, y, z' '-y-1/4, -x-3/4, z-1/4' 'y-1/4, x-1/4, z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y+1/4, -x-1/4, -z+1/4' '-y+1/4, x+1/4, -z-1/4' 'x, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' '-y+1/4, -x-1/4, z+1/4' 'y+1/4, x+1/4, z-1/4' _cell_length_a 22.975(5) _cell_length_b 22.975(5) _cell_length_c 34.298(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 18104(11) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1646 _cell_measurement_theta_min 2.7 _cell_measurement_theta_max 18.1 _exptl_crystal_description tablet _exptl_crystal_colour colourless _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.316 _exptl_crystal_density_method ? _exptl_crystal_F_000 6976 _exptl_absorpt_coefficient_mu 1.297 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.750 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'Bruker SADABS, 1996' _exptl_special_details ? _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD area detector' _diffrn_measurement_method omega _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 43790 _diffrn_reflns_av_R_equivalents 0.212 _diffrn_reflns_av_sigmaI/netI 0.160 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 31 _diffrn_reflns_limit_l_min -45 _diffrn_reflns_limit_l_max 41 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 28.93 _reflns_number_total 6205 _reflns_number_gt 1961 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART version 5.624 (Bruker, 2001)' _computing_cell_refinement 'Bruker SAINT version 6.02a (Bruker, 2000)' _computing_data_reduction 'Bruker SAINT; Bruker SHELXTL (Bruker, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'OLEX (Dolomanov, 2001)' _computing_publication_material 'enCIFer (CCDC, 2003); PLATON (Spek, 2003)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1195P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00016(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5919 _refine_ls_number_parameters 204 _refine_ls_number_restraints 54 _refine_ls_R_factor_all 0.1747 _refine_ls_R_factor_gt 0.0665 _refine_ls_wR_factor_ref 0.2063 _refine_ls_wR_factor_gt 0.1748 _refine_ls_goodness_of_fit_ref 0.746 _refine_ls_restrained_S_all 0.744 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ag Ag 0.33474(2) 0.08474(2) 0.6250 0.0534(3) Uani 1 2 d SU . . N1 N 0.2326(2) 0.0877(3) 0.63622(17) 0.0642(17) Uani 1 1 d U . . C2 C 0.2143(3) 0.1207(4) 0.6653(2) 0.081(3) Uani 1 1 d U . . H2 H 0.2425 0.1436 0.6785 0.098 Uiso 1 1 calc R . . C3 C 0.1585(3) 0.1245(4) 0.6779(2) 0.082(3) Uani 1 1 d U . . H3 H 0.1486 0.1490 0.6992 0.098 Uiso 1 1 calc R . . C4 C 0.1158(3) 0.0917(3) 0.6589(2) 0.0545(16) Uani 1 1 d U . . C5 C 0.1347(3) 0.0559(3) 0.6289(2) 0.0636(19) Uani 1 1 d U . . H5 H 0.1077 0.0319 0.6155 0.076 Uiso 1 1 calc R . . C6 C 0.1927(3) 0.0551(3) 0.6187(2) 0.070(2) Uani 1 1 d U . . H6 H 0.2048 0.0301 0.5982 0.084 Uiso 1 1 calc R . . C7 C 0.0548(3) 0.0937(3) 0.67088(18) 0.0507(16) Uani 1 1 d U . . S7 S 0.0000 0.08912(12) 0.63623(8) 0.0599(7) Uani 1 2 d SU . . C8 C 0.0321(3) 0.0987(3) 0.70768(19) 0.0537(16) Uani 1 1 d U . . C9 C 0.0658(3) 0.0989(3) 0.74514(18) 0.0477(15) Uani 1 1 d U . . C10 C 0.0888(4) 0.0490(4) 0.7586(2) 0.096(3) Uani 1 1 d U . . H10 H 0.0848 0.0140 0.7442 0.115 Uiso 1 1 calc R . . C11 C 0.1177(4) 0.0492(4) 0.7931(2) 0.099(3) Uani 1 1 d U . . H11 H 0.1338 0.0134 0.8018 0.119 Uiso 1 1 calc R . . N12 N 0.1254(2) 0.0965(2) 0.81602(15) 0.0547(14) Uani 1 1 d U . . C13 C 0.1036(3) 0.1451(3) 0.80152(19) 0.0601(18) Uani 1 1 d U . . H13 H 0.1087 0.1801 0.8159 0.072 Uiso 1 1 calc R . . C14 C 0.0738(3) 0.1478(3) 0.7668(2) 0.064(2) Uani 1 1 d U . . H14 H 0.0589 0.1840 0.7578 0.077 Uiso 1 1 calc R . . Sb1 Sb 0.2500 0.2500 0.7500 0.0622(3) Uani 1 4 d SU . . F1 F 0.2500 0.3309(2) 0.7500 0.092(2) Uani 1 2 d SU . . F2 F 0.2155(4) 0.2500 0.79849(18) 0.113(2) Uani 1 2 d SU . . F3 F 0.3216(3) 0.2500 0.7750(2) 0.113(2) Uani 1 2 d SU . . Sb2 Sb 0.0000 0.2500 0.8750 0.0657(4) Uani 1 8 d SU . . F4 F 0.0822(2) 0.2500 0.87487(17) 0.0769(16) Uani 1 2 d SU . . F5 F 0.0000 0.2500 0.9291(2) 0.074(2) Uani 1 4 d SU . . Sb3 Sb 0.2500 0.58339(19) 0.7500 0.1313(18) Uani 0.25 2 d SPU . . F6 F 0.1718(13) 0.5905(10) 0.7655(8) 0.107(7) Uani 0.19 1 d PU . . F7 F 0.2699(10) 0.5192(11) 0.7778(6) 0.258(15) Uani 0.38 1 d PU . . F8 F 0.2615(19) 0.637(2) 0.7819(12) 0.240(19) Uani 0.19 1 d PU . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ag 0.0533(3) 0.0533(3) 0.0538(5) 0.0023(3) -0.0023(3) -0.0011(3) N1 0.042(3) 0.086(5) 0.065(4) -0.022(3) 0.000(3) -0.006(3) C2 0.056(4) 0.115(7) 0.072(5) -0.036(5) 0.013(4) -0.019(5) C3 0.057(4) 0.097(6) 0.092(6) -0.046(5) 0.009(4) -0.010(4) C4 0.043(3) 0.058(4) 0.062(4) -0.001(3) 0.007(3) -0.003(3) C5 0.049(4) 0.077(5) 0.065(5) -0.020(4) 0.002(4) -0.013(4) C6 0.051(4) 0.075(5) 0.084(5) -0.023(4) 0.008(4) 0.000(4) C7 0.045(3) 0.056(4) 0.051(4) -0.007(3) 0.004(3) 0.001(3) S7 0.0455(14) 0.0782(18) 0.0559(16) -0.0080(13) 0.000 0.000 C8 0.048(4) 0.058(4) 0.055(4) -0.004(3) 0.003(3) 0.002(3) C9 0.047(4) 0.053(4) 0.044(3) -0.008(3) -0.004(3) -0.003(3) C10 0.162(9) 0.052(4) 0.074(6) -0.016(4) -0.054(6) 0.010(5) C11 0.156(9) 0.054(5) 0.089(6) -0.008(4) -0.052(6) 0.024(5) N12 0.062(4) 0.051(3) 0.052(3) 0.001(3) -0.002(3) 0.007(3) C13 0.059(5) 0.060(4) 0.062(4) -0.014(4) -0.014(3) 0.007(3) C14 0.077(5) 0.052(4) 0.064(4) 0.003(3) -0.020(4) 0.010(4) Sb1 0.0881(8) 0.0424(6) 0.0561(6) 0.000 -0.0124(5) 0.000 F1 0.167(7) 0.034(3) 0.075(4) 0.000 -0.021(4) 0.000 F2 0.188(7) 0.078(5) 0.072(4) 0.000 0.007(4) 0.000 F3 0.130(5) 0.068(4) 0.140(7) 0.000 -0.061(5) 0.000 Sb2 0.0689(6) 0.0689(6) 0.0593(9) 0.000 0.000 0.000 F4 0.057(3) 0.099(4) 0.074(4) 0.000 0.004(3) 0.000 F5 0.092(6) 0.074(6) 0.058(4) 0.000 0.000 0.000 Sb3 0.179(5) 0.108(3) 0.107(3) 0.000 0.061(3) 0.000 F6 0.176(13) 0.057(14) 0.087(18) 0.024(12) 0.051(15) 0.005(11) F7 0.26(2) 0.32(2) 0.202(19) 0.169(17) 0.18(2) 0.17(2) F8 0.23(3) 0.30(2) 0.19(4) -0.14(2) 0.17(3) -0.13(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ag N12 2.237(5) 5_556 ? Ag N12 2.237(5) 4_554 ? Ag N1 2.379(5) 7_546 ? Ag N1 2.379(5) . ? N1 C2 1.321(9) . ? N1 C6 1.326(8) . ? C2 C3 1.355(9) . ? C3 C4 1.398(9) . ? C4 C5 1.387(9) . ? C4 C7 1.461(9) . ? C5 C6 1.379(9) . ? C7 C8 1.371(8) . ? C7 S7 1.735(7) . ? S7 C7 1.735(7) 22 ? C8 C8 1.474(12) 22 ? C8 C9 1.500(8) . ? C9 C10 1.343(10) . ? C9 C14 1.359(8) . ? C10 C11 1.357(10) . ? C11 N12 1.354(9) . ? N12 C13 1.321(8) . ? N12 Ag 2.237(5) 3_545 ? C13 C14 1.375(8) . ? Sb1 F2 1.842(7) . ? Sb1 F2 1.842(7) 25_556 ? Sb1 F3 1.854(7) 25_556 ? Sb1 F3 1.854(7) . ? Sb1 F1 1.859(5) 25_556 ? Sb1 F1 1.859(5) . ? Sb2 F5 1.857(8) 19_567 ? Sb2 F5 1.857(8) . ? Sb2 F4 1.888(5) 19_567 ? Sb2 F4 1.888(5) 10_454 ? Sb2 F4 1.888(5) . ? Sb2 F4 1.888(5) 28_557 ? Sb3 F8 1.67(4) . ? Sb3 F8 1.67(4) 5_556 ? Sb3 F7 1.815(18) 5_556 ? Sb3 F7 1.815(18) . ? Sb3 F6 1.88(3) 5_556 ? Sb3 F6 1.88(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Ag N12 135.9(3) 5_556 4_554 ? N12 Ag N1 104.7(2) 5_556 7_546 ? N12 Ag N1 104.7(2) 4_554 7_546 ? N12 Ag N1 104.7(2) 5_556 . ? N12 Ag N1 104.7(2) 4_554 . ? N1 Ag N1 94.8(3) 7_546 . ? C2 N1 C6 116.5(6) . . ? C2 N1 Ag 116.9(5) . . ? C6 N1 Ag 126.2(5) . . ? N1 C2 C3 125.4(7) . . ? C2 C3 C4 118.6(7) . . ? C5 C4 C3 116.5(6) . . ? C5 C4 C7 121.8(6) . . ? C3 C4 C7 121.6(6) . . ? C6 C5 C4 119.9(6) . . ? N1 C6 C5 123.0(7) . . ? C8 C7 C4 128.8(6) . . ? C8 C7 S7 111.0(5) . . ? C4 C7 S7 120.1(5) . . ? C7 S7 C7 93.1(4) . 22 ? C7 C8 C8 112.4(4) . 22 ? C7 C8 C9 126.3(6) . . ? C8 C8 C9 121.1(3) 22 . ? C10 C9 C14 117.6(6) . . ? C10 C9 C8 119.7(6) . . ? C14 C9 C8 122.7(6) . . ? C9 C10 C11 119.4(7) . . ? N12 C11 C10 124.8(7) . . ? C13 N12 C11 114.3(6) . . ? C13 N12 Ag 126.8(4) . 3_545 ? C11 N12 Ag 118.7(5) . 3_545 ? N12 C13 C14 123.6(6) . . ? C9 C14 C13 120.2(7) . . ? F2 Sb1 F2 180.000(1) . 25_556 ? F2 Sb1 F3 92.0(4) . 25_556 ? F2 Sb1 F3 88.0(4) 25_556 25_556 ? F2 Sb1 F3 88.0(4) . . ? F2 Sb1 F3 92.0(4) 25_556 . ? F3 Sb1 F3 180.0(4) 25_556 . ? F2 Sb1 F1 90.000(2) . 25_556 ? F2 Sb1 F1 90.000(1) 25_556 25_556 ? F3 Sb1 F1 90.000(2) 25_556 25_556 ? F3 Sb1 F1 90.000(1) . 25_556 ? F2 Sb1 F1 90.000(1) . . ? F2 Sb1 F1 90.000(2) 25_556 . ? F3 Sb1 F1 90.000(1) 25_556 . ? F3 Sb1 F1 90.000(2) . . ? F1 Sb1 F1 180.000(1) 25_556 . ? F5 Sb2 F5 180.000(3) 19_567 . ? F5 Sb2 F4 90.13(18) 19_567 19_567 ? F5 Sb2 F4 89.87(18) . 19_567 ? F5 Sb2 F4 89.87(18) 19_567 10_454 ? F5 Sb2 F4 90.13(18) . 10_454 ? F4 Sb2 F4 90.000(4) 19_567 10_454 ? F5 Sb2 F4 89.87(18) 19_567 . ? F5 Sb2 F4 90.13(18) . . ? F4 Sb2 F4 90.000(2) 19_567 . ? F4 Sb2 F4 179.7(4) 10_454 . ? F5 Sb2 F4 90.13(18) 19_567 28_557 ? F5 Sb2 F4 89.87(18) . 28_557 ? F4 Sb2 F4 179.7(4) 19_567 28_557 ? F4 Sb2 F4 90.000(2) 10_454 28_557 ? F4 Sb2 F4 90.000(3) . 28_557 ? F8 Sb3 F8 84(4) . 5_556 ? F8 Sb3 F7 170.0(13) . 5_556 ? F8 Sb3 F7 103(2) 5_556 5_556 ? F8 Sb3 F7 103(2) . . ? F8 Sb3 F7 170.0(13) 5_556 . ? F7 Sb3 F7 71.3(19) 5_556 . ? F8 Sb3 F6 88.3(14) . 5_556 ? F8 Sb3 F6 84.4(16) 5_556 5_556 ? F7 Sb3 F6 99.3(9) 5_556 5_556 ? F7 Sb3 F6 88.8(11) . 5_556 ? F8 Sb3 F6 84.4(16) . . ? F8 Sb3 F6 88.3(14) 5_556 . ? F7 Sb3 F6 88.8(11) 5_556 . ? F7 Sb3 F6 99.3(9) . . ? F6 Sb3 F6 170.0(14) 5_556 . ? _diffrn_measured_fraction_theta_max 0.944 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.896 _refine_diff_density_min -0.615 _refine_diff_density_rms 0.140 #===END data_Compound_4_(sdcpat) _database_code_depnum_ccdc_archive 'CCDC 225253' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene silver triflate' _refine_special_details ; In the counterion the C and S atoms share the same position as do F and O atoms. After failing to model regions of diffuse electron density, we resorted to the PLATON SQUEEZE procedure. This removed the contribution of the diffuse regions to the diffraction pattern and gave a new HKL file. The number of electrons thus estimated were included in the final formula, formula weight, calculated density, mu and F(000) is 1937 per unit cell. The residual electron density was assigned to a half of a counteranion, two molecules of acetonitrile solvent, and a molecule of dichloromethane solvent [1937/16 = 121.1 e per ligand molecule. 121.1 - 73*0.5(CF3SO3) - 22*2(MeCN)= 40.6 e. One molecule of CH2Cl2 would give 42 e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene silver triflate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H24 Ag Cl2 F3 N6 O3 S2' _chemical_formula_weight 816.44 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y+1/2, z' 'x, -y, -z' '-x, y+1/2, -z' '-y+1/4, -x+1/4, -z+3/4' 'y+1/4, x+3/4, -z+1/4' 'y+1/4, -x+1/4, z+3/4' '-y+1/4, x+3/4, z+1/4' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1, z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1, -z+1/2' '-y+3/4, -x+3/4, -z+5/4' 'y+3/4, x+5/4, -z+3/4' 'y+3/4, -x+3/4, z+5/4' '-y+3/4, x+5/4, z+3/4' '-x, -y, -z' 'x, y-1/2, -z' '-x, y, z' 'x, -y-1/2, z' 'y-1/4, x-1/4, z-3/4' '-y-1/4, -x-3/4, z-1/4' '-y-1/4, x-1/4, -z-3/4' 'y-1/4, -x-3/4, -z-1/4' '-x+1/2, -y+1/2, -z+1/2' 'x+1/2, y, -z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y, z+1/2' 'y+1/4, x+1/4, z-1/4' '-y+1/4, -x-1/4, z+1/4' '-y+1/4, x+1/4, -z-1/4' 'y+1/4, -x-1/4, -z+1/4' _cell_length_a 23.166(5) _cell_length_b 23.166(5) _cell_length_c 34.931(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 18746(6) _cell_formula_units_Z 16 _cell_measurement_temperature 163(2) _cell_measurement_reflns_used 9877 _cell_measurement_theta_min 2.49 _cell_measurement_theta_max 23.83 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.50 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.157 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6560 _exptl_absorpt_coefficient_mu 0.675 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8013 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details 'Bruker SADABS, 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 163(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 85947 _diffrn_reflns_av_R_equivalents 0.0747 _diffrn_reflns_av_sigmaI/netI 0.0332 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -43 _diffrn_reflns_limit_l_max 39 _diffrn_reflns_theta_min 1.70 _diffrn_reflns_theta_max 26.40 _reflns_number_total 5047 _reflns_number_gt 3331 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'OLEX (Oleg V.Dolomanov, 2001)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1189P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5047 _refine_ls_number_parameters 161 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0815 _refine_ls_R_factor_gt 0.0589 _refine_ls_wR_factor_ref 0.1908 _refine_ls_wR_factor_gt 0.1800 _refine_ls_goodness_of_fit_ref 1.082 _refine_ls_restrained_S_all 1.132 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ag Ag 0.330503(13) 0.080503(13) 0.6250 0.0453(2) Uani 1 2 d S . . N1 N 0.23046(15) 0.08597(16) 0.63974(11) 0.0570(10) Uani 1 1 d . . . C2 C 0.2134(2) 0.1192(2) 0.66856(14) 0.0726(15) Uani 1 1 d . . . H2 H 0.2411 0.1411 0.6813 0.087 Uiso 1 1 calc R . . C3 C 0.1567(2) 0.1232(2) 0.68069(15) 0.0719(15) Uani 1 1 d . . . H3 H 0.1468 0.1480 0.7006 0.086 Uiso 1 1 calc R . . C4 C 0.11487(16) 0.09006(19) 0.66313(12) 0.0497(10) Uani 1 1 d . . . C5 C 0.13302(19) 0.0556(2) 0.63295(13) 0.0643(13) Uani 1 1 d . . . H5 H 0.1066 0.0326 0.6199 0.077 Uiso 1 1 calc R . . C6 C 0.1903(2) 0.0556(2) 0.62231(14) 0.0636(13) Uani 1 1 d . . . H6 H 0.2012 0.0328 0.6016 0.076 Uiso 1 1 calc R . . C7 C 0.05376(17) 0.09157(18) 0.67541(12) 0.0500(10) Uani 1 1 d . . . S7 S 0.0000 0.08796(7) 0.64076(5) 0.0559(4) Uani 1 2 d S . . C8 C 0.03083(16) 0.09648(18) 0.71143(11) 0.0453(9) Uani 1 1 d . . . C9 C 0.06440(17) 0.09457(19) 0.74782(11) 0.0471(10) Uani 1 1 d . . . C10 C 0.0850(2) 0.0445(2) 0.76174(14) 0.0795(17) Uani 1 1 d . . . H10 H 0.0788 0.0102 0.7486 0.095 Uiso 1 1 calc R . . C11 C 0.1159(2) 0.0446(2) 0.79628(15) 0.0879(18) Uani 1 1 d . . . H11 H 0.1314 0.0098 0.8046 0.105 Uiso 1 1 calc R . . N12 N 0.12440(15) 0.09043(14) 0.81781(10) 0.0488(9) Uani 1 1 d . . . C13 C 0.1036(2) 0.1380(2) 0.80423(14) 0.0779(16) Uani 1 1 d . . . H13 H 0.1089 0.1714 0.8185 0.093 Uiso 1 1 calc R . . C14 C 0.0739(3) 0.1428(2) 0.76959(15) 0.0859(18) Uani 1 1 d . . . H14 H 0.0606 0.1786 0.7614 0.103 Uiso 1 1 calc R . . C15 C 0.22158(19) 0.2500 0.75358(14) 0.157(2) Uani 0.50 2 d SPD . . F1 O 0.1781(3) 0.2500 0.7268(2) 0.143(3) Uani 0.50 2 d SP . . F2 O 0.2090(4) 0.2500 0.7950(2) 0.165(3) Uani 0.50 2 d SP . . F3 O 0.2500 0.1774(3) 0.7500 0.319(10) Uani 0.50 2 d SPD . . S2 S 0.22158(19) 0.2500 0.75358(14) 0.157(2) Uani 0.50 2 d SPD . . O1 O 0.1781(3) 0.2500 0.7268(2) 0.143(3) Uani 0.50 2 d SP . . O2 O 0.2090(4) 0.2500 0.7950(2) 0.165(3) Uani 0.50 2 d SP . . O3 O 0.2500 0.1774(3) 0.7500 0.319(10) Uani 0.50 2 d SPD . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ag 0.0457(2) 0.0457(2) 0.0446(3) -0.00004(13) 0.00004(13) 0.00059(18) N1 0.041(2) 0.076(3) 0.054(2) -0.0121(19) 0.0028(17) -0.0035(17) C2 0.049(3) 0.094(4) 0.075(3) -0.030(3) 0.007(2) -0.019(3) C3 0.057(3) 0.090(4) 0.069(3) -0.035(3) 0.009(2) -0.010(3) C4 0.031(2) 0.071(3) 0.047(2) -0.003(2) 0.0036(18) 0.0008(19) C5 0.046(3) 0.079(3) 0.067(3) -0.020(3) 0.005(2) -0.014(2) C6 0.049(2) 0.083(3) 0.059(3) -0.029(3) 0.010(2) -0.004(3) C7 0.040(2) 0.063(3) 0.047(2) -0.0035(19) -0.0019(18) -0.0006(19) S7 0.0358(8) 0.0780(12) 0.0539(9) -0.0031(8) 0.000 0.000 C8 0.042(2) 0.050(2) 0.044(2) -0.0026(18) 0.0027(18) 0.0000(18) C9 0.034(2) 0.062(3) 0.046(2) -0.0010(19) 0.0037(17) 0.0014(18) C10 0.116(5) 0.050(3) 0.073(3) -0.012(2) -0.039(3) 0.005(3) C11 0.120(5) 0.064(3) 0.080(4) -0.010(3) -0.045(3) 0.024(3) N12 0.046(2) 0.051(2) 0.050(2) -0.0022(16) -0.0048(16) 0.0014(15) C13 0.113(4) 0.052(3) 0.068(3) -0.008(2) -0.035(3) 0.009(3) C14 0.139(5) 0.053(3) 0.065(3) -0.007(2) -0.042(3) 0.025(3) C15 0.108(3) 0.278(8) 0.084(3) 0.000 -0.015(3) 0.000 F1 0.164(6) 0.050(3) 0.215(8) 0.000 -0.132(6) 0.000 F2 0.264(10) 0.131(6) 0.100(5) 0.000 0.040(6) 0.000 F3 0.72(3) 0.049(4) 0.192(9) 0.000 -0.272(13) 0.000 S2 0.108(3) 0.278(8) 0.084(3) 0.000 -0.015(3) 0.000 O1 0.164(6) 0.050(3) 0.215(8) 0.000 -0.132(6) 0.000 O2 0.264(10) 0.131(6) 0.100(5) 0.000 0.040(6) 0.000 O3 0.72(3) 0.049(4) 0.192(9) 0.000 -0.272(13) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ag N12 2.266(3) 12_546 ? Ag N12 2.266(3) 7_554 ? Ag N1 2.377(4) . ? Ag N1 2.377(4) 6_546 ? N1 C6 1.315(6) . ? N1 C2 1.328(6) . ? C2 C3 1.384(6) . ? C3 C4 1.379(6) . ? C4 C5 1.388(6) . ? C4 C7 1.480(5) . ? C5 C6 1.379(6) . ? C7 C8 1.370(5) . ? C7 S7 1.739(4) . ? S7 C7 1.739(4) 19 ? C8 C8 1.428(7) 19 ? C8 C9 1.491(5) . ? C9 C10 1.344(6) . ? C9 C14 1.369(6) . ? C10 C11 1.403(6) . ? C11 N12 1.316(6) . ? N12 C13 1.292(6) . ? N12 Ag 2.266(3) 12_546 ? C13 C14 1.397(6) . ? C15 S2 1.340(9) 25_556 ? C15 C15 1.340(9) 25_556 ? C15 F1 1.374(6) . ? C15 F2 1.476(8) . ? C15 O3 1.810(6) 25_556 ? C15 F3 1.810(6) 25_556 ? C15 F3 1.810(6) . ? F3 S2 1.810(6) 25_556 ? F3 C15 1.810(6) 25_556 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Ag N12 133.12(17) 12_546 7_554 ? N12 Ag N1 104.66(13) 12_546 . ? N12 Ag N1 105.39(13) 7_554 . ? N12 Ag N1 105.39(13) 12_546 6_546 ? N12 Ag N1 104.66(13) 7_554 6_546 ? N1 Ag N1 98.67(18) . 6_546 ? C6 N1 C2 116.8(4) . . ? C6 N1 Ag 124.1(3) . . ? C2 N1 Ag 119.0(3) . . ? N1 C2 C3 123.5(4) . . ? C4 C3 C2 119.6(4) . . ? C3 C4 C5 116.4(4) . . ? C3 C4 C7 122.0(4) . . ? C5 C4 C7 121.6(4) . . ? C6 C5 C4 119.8(4) . . ? N1 C6 C5 123.8(4) . . ? C8 C7 C4 129.7(4) . . ? C8 C7 S7 111.4(3) . . ? C4 C7 S7 118.8(3) . . ? C7 S7 C7 91.5(3) . 19 ? C7 C8 C8 112.8(2) . 19 ? C7 C8 C9 125.3(4) . . ? C8 C8 C9 121.4(2) 19 . ? C10 C9 C14 116.5(4) . . ? C10 C9 C8 121.3(4) . . ? C14 C9 C8 122.2(4) . . ? C9 C10 C11 119.4(5) . . ? N12 C11 C10 124.7(5) . . ? C13 N12 C11 114.9(4) . . ? C13 N12 Ag 125.6(3) . 12_546 ? C11 N12 Ag 119.4(3) . 12_546 ? N12 C13 C14 124.8(4) . . ? C9 C14 C13 119.6(4) . . ? S2 C15 C15 0.0(4) 25_556 25_556 ? S2 C15 F1 126.3(7) 25_556 . ? C15 C15 F1 126.3(7) 25_556 . ? S2 C15 F2 112.2(6) 25_556 . ? C15 C15 F2 112.2(6) 25_556 . ? F1 C15 F2 121.5(7) . . ? S2 C15 O3 68.27(16) 25_556 25_556 ? C15 C15 O3 68.27(16) 25_556 25_556 ? F1 C15 O3 102.7(2) . 25_556 ? F2 C15 O3 98.0(2) . 25_556 ? S2 C15 F3 68.27(16) 25_556 25_556 ? C15 C15 F3 68.27(16) 25_556 25_556 ? F1 C15 F3 102.7(2) . 25_556 ? F2 C15 F3 98.0(2) . 25_556 ? O3 C15 F3 0.00(15) 25_556 25_556 ? S2 C15 F3 68.27(16) 25_556 . ? C15 C15 F3 68.27(16) 25_556 . ? F1 C15 F3 102.7(2) . . ? F2 C15 F3 98.0(2) . . ? O3 C15 F3 136.5(3) 25_556 . ? F3 C15 F3 136.5(3) 25_556 . ? S2 F3 C15 0.0(3) 25_556 25_556 ? S2 F3 C15 43.5(3) 25_556 . ? C15 F3 C15 43.5(3) 25_556 . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.40 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 1.222 _refine_diff_density_min -0.577 _refine_diff_density_rms 0.094 #===END data_Compound_5_(sdcpap) _database_code_depnum_ccdc_archive 'CCDC 225254' _chemical_name_common '2,3,4,5-tetra(4-pyridyl)thiophene silver hexafluorophosphate' _refine_special_details ; After failing to model regions of diffuse electron density, we resorted to the PLATON SQUEEZE procedure. This removed the contribution of the diffuse regions to the diffraction pattern and gave a new HKL file. The number of electrons thus estimated were included in the final formula, formula weight, calculated density, mu and F(000) is 1264 per unit cell. The residual electron density was assigned to a quarter of a counteranion, one molecule of acetonitrile solvent, and one molecule of dichloromethane solvent [1264/16 = 79.0 e per ligand molecule. 79.0 - 69*0.25(PF6) - 22*1(MeCN)= 39.75 e. One molecule of CH2Cl2 would give 42 e.] As a result of the large fraction of disordered electron density in the unit cell, each reciprocal lattice point has, in addition to the Bragg peak (elastic scattering), a significant contribution from thermally diffuse scattering (inelastic scattering). This leads to the appearance of a significantly large number of systematic absence violations for the I4(1)/amd space group that characterises the coordination framework. Moreover, it appears from the significant deviations, in some cases, of unit cell parameters from tetragonality (angles differing by more than 0.1 deg from 90 deg and unit cell lengths differing by more than 0.03 A, and from rather poor averaging statisitics, in all but one case, for tetragonal 4/mmm symmetry that the disordered electron density may not be ordered according to I4(1)/amd symmetry, a loss of symmetry that may have occured on cooling crystals prepared at room temperature to ~150 K for data collection. Refinements have been carried out in lower symmetry space groups (C2/c or, for a beta angle closer to 90 deg, I2/a), both with SQUEEZEd and unSQUEEZEd data, for selected members of this group of compounds. R1 and wR2 are significantly lower, even when allowing for the much larger number of parameters, but metrical details of the chemically interesting part of the crystal structure, the coordination framework polymer, are identical to those obtained from refinements conducted in space group I4(1)/amd. Refinements of the coordination framework in I4(1)/amd were judged to be prudent and accurate. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,3,4,5-tetra(4-pyridyl)thiophene silver hexafluorophosphate ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C27 H21 Ag Cl2 F6 N5 P S' _chemical_formula_weight 771.29 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I4(1)/amd loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+1/4, x+3/4, z+1/4' 'y+1/4, -x+1/4, z+3/4' '-x+1/2, y, -z+1/2' 'x, -y, -z' 'y+1/4, x+3/4, -z+1/4' '-y+1/4, -x+1/4, -z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+3/4, x+5/4, z+3/4' 'y+3/4, -x+3/4, z+5/4' '-x+1, y+1/2, -z+1' 'x+1/2, -y+1/2, -z+1/2' 'y+3/4, x+5/4, -z+3/4' '-y+3/4, -x+3/4, -z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-1/4, -x-3/4, -z-1/4' '-y-1/4, x-1/4, -z-3/4' 'x-1/2, -y, z-1/2' '-x, y, z' '-y-1/4, -x-3/4, z-1/4' 'y-1/4, x-1/4, z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y+1/4, -x-1/4, -z+1/4' '-y+1/4, x+1/4, -z-1/4' 'x, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' '-y+1/4, -x-1/4, z+1/4' 'y+1/4, x+1/4, z-1/4' _cell_length_a 22.963(5) _cell_length_b 22.963(5) _cell_length_c 34.546(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 18216(9) _cell_formula_units_Z 16 _cell_measurement_temperature 163(2) _cell_measurement_reflns_used 6915 _cell_measurement_theta_min 2.36 _cell_measurement_theta_max 26.38 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.62 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.125 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6144 _exptl_absorpt_coefficient_mu 0.684 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6014 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details 'Bruker SADABS, 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 163(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 110345 _diffrn_reflns_av_R_equivalents 0.1340 _diffrn_reflns_av_sigmaI/netI 0.0306 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -43 _diffrn_reflns_limit_l_max 43 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 26.54 _reflns_number_total 4980 _reflns_number_gt 3942 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'OLEX (Oleg V.Dolomanov, 2001)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1100P)^2^+51.4700P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens 'geometrically placed' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4980 _refine_ls_number_parameters 171 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0838 _refine_ls_R_factor_gt 0.0723 _refine_ls_wR_factor_ref 0.2175 _refine_ls_wR_factor_gt 0.2056 _refine_ls_goodness_of_fit_ref 1.150 _refine_ls_restrained_S_all 1.150 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ag Ag 0.333978(13) 0.083978(13) 0.6250 0.0431(2) Uani 1 2 d S . . N1 N 0.23307(16) 0.08930(18) 0.63810(14) 0.0565(10) Uani 1 1 d . . . C2 C 0.2155(2) 0.1227(3) 0.66703(17) 0.0700(16) Uani 1 1 d . . . H2 H 0.2433 0.1448 0.6800 0.084 Uiso 1 1 calc R . . C3 C 0.1588(2) 0.1267(3) 0.67894(17) 0.0652(15) Uani 1 1 d . . . H3 H 0.1491 0.1510 0.6995 0.078 Uiso 1 1 calc R . . C4 C 0.11565(18) 0.0943(2) 0.66027(14) 0.0470(10) Uani 1 1 d . . . C5 C 0.1343(2) 0.0603(2) 0.62941(16) 0.0610(13) Uani 1 1 d . . . H5 H 0.1078 0.0385 0.6152 0.073 Uiso 1 1 calc R . . C6 C 0.1926(2) 0.0593(3) 0.62018(17) 0.0613(14) Uani 1 1 d . . . H6 H 0.2042 0.0356 0.5997 0.074 Uiso 1 1 calc R . . C7 C 0.05417(17) 0.09645(19) 0.67219(14) 0.0462(10) Uani 1 1 d . . . S7 S 0.0000 0.09255(8) 0.63801(5) 0.0500(4) Uani 1 2 d S . . C8 C 0.03119(17) 0.10155(18) 0.70862(13) 0.0436(9) Uani 1 1 d . . . C9 C 0.06515(17) 0.10040(19) 0.74531(13) 0.0434(9) Uani 1 1 d . . . C10 C 0.0880(3) 0.0501(2) 0.75954(19) 0.0795(18) Uani 1 1 d . . . H10 H 0.0846 0.0160 0.7452 0.095 Uiso 1 1 calc R . . C11 C 0.1156(3) 0.0487(2) 0.79415(18) 0.0822(19) Uani 1 1 d . . . H11 H 0.1300 0.0131 0.8027 0.099 Uiso 1 1 calc R . . N12 N 0.12341(16) 0.09535(16) 0.81701(11) 0.0479(9) Uani 1 1 d . . . C13 C 0.1021(2) 0.1454(2) 0.80312(16) 0.0564(12) Uani 1 1 d . . . H13 H 0.1071 0.1791 0.8177 0.068 Uiso 1 1 calc R . . C14 C 0.0733(2) 0.1495(2) 0.76832(17) 0.0616(13) Uani 1 1 d . . . H14 H 0.0590 0.1853 0.7601 0.074 Uiso 1 1 calc R . . P1 P 0.2500 0.2500 0.7500 0.0545(6) Uani 1 4 d S . . F1 F 0.2500 0.1819(2) 0.7500 0.146(3) Uani 1 2 d S . . F2 F 0.2163(5) 0.2500 0.7890(3) 0.162(4) Uani 1 2 d S . . F3 F 0.3014(4) 0.2500 0.7790(3) 0.173(5) Uani 1 2 d S . . P2 P 0.0000 0.2500 0.8750 0.0652(10) Uani 1 8 d S . . F4 F 0.0694(2) 0.2500 0.87491(15) 0.0833(15) Uani 1 2 d S . . F5 F 0.0000 0.2500 0.9215(2) 0.0778(19) Uani 1 4 d S . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ag 0.0396(2) 0.0396(2) 0.0501(3) -0.00030(12) 0.00030(12) 0.00191(16) N1 0.0350(19) 0.071(3) 0.063(3) -0.017(2) 0.0044(18) -0.0035(16) C2 0.042(2) 0.088(4) 0.080(4) -0.030(3) 0.006(2) -0.016(2) C3 0.046(2) 0.080(4) 0.069(3) -0.027(3) 0.015(2) -0.012(2) C4 0.032(2) 0.057(2) 0.053(3) 0.000(2) 0.0025(18) -0.0017(17) C5 0.039(2) 0.066(3) 0.078(4) -0.019(3) 0.004(2) -0.005(2) C6 0.039(2) 0.073(3) 0.072(3) -0.026(3) 0.009(2) -0.003(2) C7 0.032(2) 0.053(2) 0.054(3) -0.0075(19) -0.0064(18) -0.0021(17) S7 0.0316(7) 0.0682(10) 0.0502(9) -0.0050(8) 0.000 0.000 C8 0.035(2) 0.042(2) 0.054(3) 0.0012(18) 0.0004(18) -0.0022(16) C9 0.0298(18) 0.051(2) 0.049(2) -0.0031(19) 0.0011(16) -0.0037(17) C10 0.107(5) 0.049(3) 0.083(4) -0.016(3) -0.026(4) 0.016(3) C11 0.120(5) 0.049(3) 0.077(4) -0.016(3) -0.033(4) 0.023(3) N12 0.0448(19) 0.0495(19) 0.049(2) 0.0008(16) -0.0064(17) 0.0019(15) C13 0.065(3) 0.041(2) 0.063(3) -0.003(2) -0.016(2) 0.005(2) C14 0.065(3) 0.047(2) 0.073(3) 0.001(2) -0.025(3) 0.012(2) P1 0.0700(16) 0.0366(11) 0.0570(15) 0.000 -0.0069(12) 0.000 F1 0.284(9) 0.041(2) 0.112(5) 0.000 -0.089(6) 0.000 F2 0.221(10) 0.125(6) 0.141(7) 0.000 0.071(7) 0.000 F3 0.195(8) 0.056(3) 0.267(10) 0.000 -0.170(8) 0.000 P2 0.0620(14) 0.0620(14) 0.072(3) 0.000 0.000 0.000 F4 0.056(3) 0.099(4) 0.095(4) 0.000 0.000(2) 0.000 F5 0.080(4) 0.080(4) 0.073(5) 0.000 0.000 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ag N12 2.245(4) 5_556 ? Ag N12 2.245(4) 4_554 ? Ag N1 2.364(4) 7_546 ? Ag N1 2.364(4) . ? N1 C6 1.312(6) . ? N1 C2 1.323(7) . ? C2 C3 1.367(6) . ? C3 C4 1.398(7) . ? C4 C5 1.389(7) . ? C4 C7 1.471(6) . ? C5 C6 1.376(7) . ? C7 C8 1.370(6) . ? C7 S7 1.717(4) . ? S7 C7 1.717(4) 22 ? C8 C8 1.432(8) 22 ? C8 C9 1.488(6) . ? C9 C10 1.361(7) . ? C9 C14 1.392(6) . ? C10 C11 1.353(8) . ? C11 N12 1.343(6) . ? N12 C13 1.339(6) . ? N12 Ag 2.245(4) 3_545 ? C13 C14 1.376(7) . ? P1 F3 1.547(6) . ? P1 F3 1.547(6) 25_556 ? P1 F2 1.553(8) 25_556 ? P1 F2 1.553(8) . ? P1 F1 1.564(5) . ? P1 F1 1.564(5) 25_556 ? P2 F4 1.594(5) 19_567 ? P2 F4 1.594(5) . ? P2 F4 1.594(5) 28_557 ? P2 F4 1.594(5) 10_454 ? P2 F5 1.605(8) 19_567 ? P2 F5 1.605(8) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N12 Ag N12 134.0(2) 5_556 4_554 ? N12 Ag N1 105.21(15) 5_556 7_546 ? N12 Ag N1 104.50(15) 4_554 7_546 ? N12 Ag N1 104.50(15) 5_556 . ? N12 Ag N1 105.21(15) 4_554 . ? N1 Ag N1 97.9(2) 7_546 . ? C6 N1 C2 116.4(4) . . ? C6 N1 Ag 125.2(3) . . ? C2 N1 Ag 118.3(3) . . ? N1 C2 C3 123.8(5) . . ? C2 C3 C4 120.0(5) . . ? C5 C4 C3 115.7(4) . . ? C5 C4 C7 122.0(4) . . ? C3 C4 C7 122.3(4) . . ? C6 C5 C4 119.1(5) . . ? N1 C6 C5 124.8(5) . . ? C8 C7 C4 129.0(4) . . ? C8 C7 S7 110.9(3) . . ? C4 C7 S7 120.1(4) . . ? C7 S7 C7 92.8(3) 22 . ? C7 C8 C8 112.7(2) . 22 ? C7 C8 C9 125.4(4) . . ? C8 C8 C9 121.6(2) 22 . ? C10 C9 C14 115.4(4) . . ? C10 C9 C8 121.6(4) . . ? C14 C9 C8 122.8(4) . . ? C11 C10 C9 121.3(5) . . ? N12 C11 C10 124.3(5) . . ? C13 N12 C11 115.2(4) . . ? C13 N12 Ag 125.4(3) . 3_545 ? C11 N12 Ag 119.4(3) . 3_545 ? N12 C13 C14 123.2(4) . . ? C13 C14 C9 120.6(4) . . ? F3 P1 F3 180.000(2) . 25_556 ? F3 P1 F2 100.4(6) . 25_556 ? F3 P1 F2 79.6(6) 25_556 25_556 ? F3 P1 F2 79.6(6) . . ? F3 P1 F2 100.4(6) 25_556 . ? F2 P1 F2 180.000(3) 25_556 . ? F3 P1 F1 90.000(1) . . ? F3 P1 F1 90.000(2) 25_556 . ? F2 P1 F1 90.000(1) 25_556 . ? F2 P1 F1 90.000(2) . . ? F3 P1 F1 90.000(2) . 25_556 ? F3 P1 F1 90.000(1) 25_556 25_556 ? F2 P1 F1 90.000(2) 25_556 25_556 ? F2 P1 F1 90.000(2) . 25_556 ? F1 P1 F1 180.000(1) . 25_556 ? F4 P2 F4 90.000(2) 19_567 . ? F4 P2 F4 179.8(4) 19_567 28_557 ? F4 P2 F4 90.000(3) . 28_557 ? F4 P2 F4 90.000(4) 19_567 10_454 ? F4 P2 F4 179.8(4) . 10_454 ? F4 P2 F4 90.000(2) 28_557 10_454 ? F4 P2 F5 90.11(18) 19_567 19_567 ? F4 P2 F5 89.89(18) . 19_567 ? F4 P2 F5 90.11(18) 28_557 19_567 ? F4 P2 F5 89.89(18) 10_454 19_567 ? F4 P2 F5 89.89(18) 19_567 . ? F4 P2 F5 90.11(18) . . ? F4 P2 F5 89.89(18) 28_557 . ? F4 P2 F5 90.11(18) 10_454 . ? F5 P2 F5 180.000(4) 19_567 . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 26.54 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 1.214 _refine_diff_density_min -1.003 _refine_diff_density_rms 0.112 #===END