# Electronic Supplementary Material for CrystEngComm # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full CrystEngComm _journal_coden_Cambridge 1350 _publ_contact_author_name 'Manuel Almeida' _publ_contact_author_address ; Departamento Quimica Instituto T\'ecnologico e Nuclear / CFMCUL Sacavem Codex P-2686-953 PORTUGAL ; _publ_contact_author_email MALMEIDA@ITN.PT _publ_section_title ; Cation and ligand roles in the coordination of FeIII bisdithiolene complexes; The crystal structures of BrBzPy [Fe(qdt)2] and [Fe(alpha-tpdt)2] salts ; loop_ _publ_author_name 'Manuel Almeida' 'Dulce Belo' 'Isabel Cordeiro Santos' 'Ana Isabel Soares Neves' # end Validation Reply Form # Attachment 'ANeves__n-Bu4N_2[Fe_alpha-tpdt_2]2.cif' data_tbafea _database_code_depnum_ccdc_archive 'CCDC 695832' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '2(C16 H36 N), C16 H8 Fe2 S12' _chemical_formula_sum 'C48 H80 Fe2 N2 S12' _chemical_formula_weight 1181.56 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 12.593(3) _cell_length_b 13.734(3) _cell_length_c 17.690(3) _cell_angle_alpha 90.00 _cell_angle_beta 97.430(11) _cell_angle_gamma 90.00 _cell_volume 3033.8(10) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 2154 _cell_measurement_theta_min 2.59 _cell_measurement_theta_max 19.28 _exptl_crystal_description prism _exptl_crystal_colour brown _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.293 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1252 _exptl_absorpt_coefficient_mu 0.923 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7692 _exptl_absorpt_correction_T_max 0.9133 _exptl_absorpt_process_details '(SADABS; Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker-AXS APEX- CCD area-detector' _diffrn_measurement_method '\f and \w' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18378 _diffrn_reflns_av_R_equivalents 0.1777 _diffrn_reflns_av_sigmaI/netI 0.1942 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.20 _diffrn_reflns_theta_max 23.43 _reflns_number_total 4339 _reflns_number_gt 1637 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART, (Bruker, 2004)' _computing_cell_refinement 'Bruker SMART, (Bruker, 2004)' _computing_data_reduction 'Bruker SAINT, (Bruker, 2004)' _computing_structure_solution 'SIR97 (Altomare, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP3(Farrugia,1997) _computing_publication_material 'WinGX (Farrugia, 1999)' _refine_special_details ; 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. The poor quality of the crystal results in a weak data set which is responsible for the low ratio Observed/Unique reflections (38%), a hight Rint (0.18) and a low resolution data collection (\q-23.43). The terminal thiophenic rings in the anion units showed evidence of disorder in the displacement parameters of C and S atoms. However, this could not be successfully modelled. Due to problems with severe anisotropy and disorder, restraints to anisotropic parameters were used (ISOR and DFIX instructions of SHELX). All non-H atoms were refined ANIS with the exception of the severe disordered carbon atoms of cation which were left isotropic. ; _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^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4339 _refine_ls_number_parameters 264 _refine_ls_number_restraints 19 _refine_ls_R_factor_all 0.3038 _refine_ls_R_factor_gt 0.1322 _refine_ls_wR_factor_ref 0.3878 _refine_ls_wR_factor_gt 0.3258 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.042 _refine_ls_shift/su_max 0.003 _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 Fe1 Fe 0.52455(18) 0.60470(16) 0.03343(11) 0.0532(8) Uani 1 1 d . . . S1 S 0.4392(3) 0.4814(3) 0.0828(2) 0.0543(12) Uani 1 1 d . . . S2 S 0.3667(3) 0.6778(3) -0.0058(2) 0.0581(12) Uani 1 1 d . . . S3 S 0.1414(4) 0.6181(4) 0.0209(3) 0.0896(18) Uani 1 1 d . . . S4 S 0.6004(4) 0.7468(4) 0.0142(4) 0.0917(18) Uani 1 1 d . . . S5 S 0.6687(4) 0.5633(3) 0.1133(2) 0.0660(14) Uani 1 1 d . . . S6 S 0.8956(6) 0.6499(7) 0.1197(4) 0.148(3) Uani 1 1 d D . . N1 N 0.6434(18) 0.2619(16) 0.2538(10) 0.122(7) Uani 1 1 d . . . C1 C 0.2770(13) 0.5996(13) 0.0292(9) 0.061(5) Uani 1 1 d . . . C2 C 0.3069(12) 0.5162(12) 0.0655(8) 0.050(4) Uani 1 1 d . . . C3 C 0.2158(13) 0.4628(13) 0.0865(8) 0.061(5) Uani 1 1 d . . . H3 H 0.2191 0.4026 0.1107 0.073 Uiso 1 1 calc R . . C4 C 0.1280(18) 0.5128(16) 0.0661(9) 0.090(7) Uani 1 1 d . . . H4 H 0.0614 0.4908 0.0762 0.108 Uiso 1 1 calc R . . C5 C 0.7589(14) 0.6471(14) 0.0944(10) 0.070(5) Uani 1 1 d U . . C6 C 0.7368(13) 0.7218(15) 0.0540(11) 0.084(7) Uani 1 1 d . . . C7 C 0.8266(11) 0.7964(11) 0.0376(10) 0.061(5) Uani 1 1 d D . . H7 H 0.8218 0.8534 0.0090 0.074 Uiso 1 1 calc R . . C8 C 0.9106(18) 0.7533(15) 0.0766(14) 0.146(10) Uani 1 1 d DU . . H8 H 0.9780 0.7818 0.0794 0.175 Uiso 1 1 calc R . . C10 C 0.534(3) 0.2796(19) 0.2098(14) 0.159(12) Uani 1 1 d . . . H10A H 0.5376 0.2629 0.1569 0.191 Uiso 1 1 calc R . . H10B H 0.5194 0.3489 0.2115 0.191 Uiso 1 1 calc R . . C11 C 0.435(2) 0.224(2) 0.2357(12) 0.152(12) Uani 1 1 d . . . H11A H 0.4504 0.1551 0.2390 0.183 Uiso 1 1 calc R . . H11B H 0.4234 0.2469 0.2859 0.183 Uiso 1 1 calc R . . C12 C 0.338(2) 0.241(2) 0.1817(19) 0.176(14) Uani 1 1 d . . . H12A H 0.3259 0.3105 0.1764 0.211 Uiso 1 1 calc R . . H12B H 0.3496 0.2158 0.1322 0.211 Uiso 1 1 calc R . . C13 C 0.248(2) 0.198(2) 0.2032(15) 0.146(10) Uani 1 1 d . . . H13A H 0.1871 0.2133 0.1665 0.218 Uiso 1 1 calc R . . H13B H 0.2360 0.2220 0.2523 0.218 Uiso 1 1 calc R . . H13C H 0.2575 0.1286 0.2056 0.218 Uiso 1 1 calc R . . C20 C 0.673(2) 0.159(2) 0.2672(14) 0.164(12) Uani 1 1 d . . . H20A H 0.6292 0.1320 0.3030 0.197 Uiso 1 1 calc R . . H20B H 0.7472 0.1563 0.2907 0.197 Uiso 1 1 calc R . . C21 C 0.661(3) 0.093(2) 0.1920(17) 0.192(15) Uani 1 1 d D . . H21A H 0.5887 0.1046 0.1665 0.230 Uiso 1 1 calc R . . H21B H 0.7092 0.1200 0.1590 0.230 Uiso 1 1 calc R . . C22 C 0.678(3) -0.017(2) 0.194(2) 0.231(17) Uiso 1 1 d D . . H22A H 0.6537 -0.0466 0.2383 0.277 Uiso 1 1 calc R . . H22B H 0.6408 -0.0482 0.1482 0.277 Uiso 1 1 calc R . . C23 C 0.796(3) -0.024(4) 0.196(4) 0.42(4) Uiso 1 1 d D . . H23A H 0.8176 -0.0908 0.2037 0.626 Uiso 1 1 calc R . . H23B H 0.8296 0.0149 0.2372 0.626 Uiso 1 1 calc R . . H23C H 0.8161 -0.0011 0.1487 0.626 Uiso 1 1 calc R . . C30 C 0.727(2) 0.3158(19) 0.2133(13) 0.132(9) Uani 1 1 d . . . H30A H 0.7269 0.2874 0.1630 0.158 Uiso 1 1 calc R . . H30B H 0.7048 0.3831 0.2062 0.158 Uiso 1 1 calc R . . C31 C 0.836(2) 0.315(3) 0.2515(13) 0.173(14) Uani 1 1 d D . . H31A H 0.8587 0.2473 0.2594 0.208 Uiso 1 1 calc R . . H31B H 0.8372 0.3444 0.3013 0.208 Uiso 1 1 calc R . . C32 C 0.917(3) 0.367(3) 0.209(3) 0.28(2) Uiso 1 1 d D . . H32A H 0.8839 0.4182 0.1758 0.340 Uiso 1 1 calc R . . H32B H 0.9762 0.3939 0.2429 0.340 Uiso 1 1 calc R . . C33 C 0.952(4) 0.281(4) 0.163(4) 0.40(3) Uiso 1 1 d D . . H33A H 1.0021 0.3031 0.1299 0.601 Uiso 1 1 calc R . . H33B H 0.8906 0.2532 0.1328 0.601 Uiso 1 1 calc R . . H33C H 0.9857 0.2327 0.1972 0.601 Uiso 1 1 calc R . . C40 C 0.654(2) 0.3024(19) 0.3371(12) 0.133(10) Uani 1 1 d . . . H40A H 0.6057 0.2682 0.3660 0.160 Uiso 1 1 calc R . . H40B H 0.7269 0.2922 0.3619 0.160 Uiso 1 1 calc R . . C41 C 0.628(3) 0.411(2) 0.3349(15) 0.196(17) Uani 1 1 d D . . H41A H 0.6841 0.4469 0.3137 0.235 Uiso 1 1 calc R . . H41B H 0.5611 0.4225 0.3029 0.235 Uiso 1 1 calc R . . C42 C 0.621(3) 0.446(2) 0.416(2) 0.230(19) Uani 1 1 d D . . H42A H 0.5966 0.5133 0.4163 0.276 Uiso 1 1 calc R . . H42B H 0.5730 0.4054 0.4409 0.276 Uiso 1 1 calc R . . C43 C 0.733(3) 0.436(3) 0.452(3) 0.27(2) Uiso 1 1 d . . . H43A H 0.7391 0.4577 0.5036 0.412 Uiso 1 1 calc R . . H43B H 0.7786 0.4754 0.4243 0.412 Uiso 1 1 calc R . . H43C H 0.7546 0.3693 0.4500 0.412 Uiso 1 1 calc R . . 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 Fe1 0.0722(17) 0.0550(15) 0.0330(13) -0.0074(11) 0.0093(10) 0.0081(12) S1 0.066(3) 0.070(3) 0.029(2) 0.0013(19) 0.0134(18) 0.013(2) S2 0.061(3) 0.060(3) 0.052(3) -0.007(2) 0.002(2) 0.013(2) S3 0.083(4) 0.116(5) 0.069(3) -0.022(3) 0.008(3) 0.020(3) S4 0.073(4) 0.055(3) 0.148(5) 0.007(3) 0.015(3) 0.007(2) S5 0.077(3) 0.087(3) 0.033(2) -0.016(2) 0.001(2) 0.016(2) S6 0.134(6) 0.179(8) 0.126(6) -0.060(5) 0.004(5) 0.016(5) N1 0.16(2) 0.15(2) 0.051(12) 0.041(12) 0.024(12) 0.014(15) C1 0.081(13) 0.065(12) 0.037(9) -0.033(9) 0.006(8) -0.018(10) C2 0.059(11) 0.052(11) 0.044(9) -0.023(8) 0.024(8) -0.019(9) C3 0.057(12) 0.091(14) 0.032(9) -0.013(8) -0.001(8) 0.030(11) C4 0.125(19) 0.112(18) 0.040(11) -0.031(10) 0.042(11) -0.042(14) C5 0.070(5) 0.070(5) 0.070(5) -0.0006(10) 0.0092(12) 0.0001(10) C6 0.052(12) 0.109(16) 0.100(15) -0.063(13) 0.038(10) -0.057(11) C7 0.034(9) 0.045(10) 0.106(14) -0.011(9) 0.014(9) 0.005(7) C8 0.146(10) 0.146(10) 0.146(10) -0.0003(10) 0.0191(16) -0.0003(10) C10 0.24(3) 0.14(2) 0.086(18) 0.058(17) -0.02(2) -0.04(2) C11 0.13(2) 0.25(3) 0.073(16) 0.089(19) -0.026(15) -0.07(2) C12 0.11(2) 0.22(4) 0.20(3) 0.10(3) 0.03(2) 0.01(2) C13 0.14(3) 0.16(3) 0.14(2) 0.05(2) 0.027(19) 0.01(2) C20 0.29(4) 0.12(2) 0.078(19) 0.072(18) 0.03(2) 0.03(2) C21 0.32(4) 0.17(3) 0.10(2) 0.03(2) 0.09(3) 0.05(3) C30 0.14(2) 0.17(3) 0.082(17) 0.049(17) -0.004(16) -0.028(19) C31 0.12(2) 0.33(5) 0.068(17) 0.00(2) 0.008(16) -0.05(2) C40 0.22(3) 0.12(2) 0.076(18) 0.028(14) 0.045(17) -0.04(2) C41 0.39(5) 0.13(3) 0.074(19) 0.014(17) 0.07(3) -0.01(3) C42 0.25(5) 0.14(3) 0.32(6) 0.09(3) 0.13(4) -0.06(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 Fe1 S4 2.218(5) . ? Fe1 S5 2.226(5) . ? Fe1 S1 2.242(5) . ? Fe1 S2 2.255(4) . ? Fe1 S1 2.466(4) 3_665 ? S1 C2 1.722(16) . ? S1 Fe1 2.466(4) 3_665 ? S2 C1 1.731(17) . ? S3 C4 1.67(2) . ? S3 C1 1.713(17) . ? S4 C6 1.80(2) . ? S5 C5 1.681(19) . ? S6 C8 1.634(16) . ? S6 C5 1.721(18) . ? N1 C20 1.47(3) . ? N1 C10 1.51(3) . ? N1 C30 1.54(3) . ? N1 C40 1.56(3) . ? C1 C2 1.34(2) . ? C2 C3 1.45(2) . ? C3 C4 1.31(2) . ? C5 C6 1.26(2) . ? C6 C7 1.58(2) . ? C7 C8 1.326(16) . ? C10 C11 1.57(3) . ? C11 C12 1.47(3) . ? C12 C13 1.38(3) . ? C20 C21 1.60(3) . ? C21 C22 1.538(18) . ? C22 C23 1.485(19) . ? C30 C31 1.45(3) . ? C31 C32 1.529(19) . ? C32 C33 1.53(2) . ? C40 C41 1.53(3) . ? C41 C42 1.525(19) . ? C42 C43 1.48(4) . ? 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 S4 Fe1 S5 89.4(2) . . ? S4 Fe1 S1 164.1(2) . . ? S5 Fe1 S1 87.26(18) . . ? S4 Fe1 S2 86.64(19) . . ? S5 Fe1 S2 157.44(17) . . ? S1 Fe1 S2 90.47(17) . . ? S4 Fe1 S1 99.5(2) . 3_665 ? S5 Fe1 S1 100.58(16) . 3_665 ? S1 Fe1 S1 96.47(14) . 3_665 ? S2 Fe1 S1 101.98(16) . 3_665 ? C2 S1 Fe1 102.9(6) . . ? C2 S1 Fe1 105.3(5) . 3_665 ? Fe1 S1 Fe1 83.53(14) . 3_665 ? C1 S2 Fe1 101.7(6) . . ? C4 S3 C1 89.5(10) . . ? C6 S4 Fe1 100.4(7) . . ? C5 S5 Fe1 102.4(7) . . ? C8 S6 C5 94.0(11) . . ? C20 N1 C10 116(2) . . ? C20 N1 C30 111(2) . . ? C10 N1 C30 108.5(17) . . ? C20 N1 C40 101.5(18) . . ? C10 N1 C40 113(2) . . ? C30 N1 C40 106.6(19) . . ? C2 C1 S3 112.5(13) . . ? C2 C1 S2 123.0(13) . . ? S3 C1 S2 124.5(12) . . ? C1 C2 C3 111.8(15) . . ? C1 C2 S1 121.8(12) . . ? C3 C2 S1 126.4(14) . . ? C4 C3 C2 109.4(18) . . ? C3 C4 S3 116.8(16) . . ? C6 C5 S5 124.4(15) . . ? C6 C5 S6 105.6(15) . . ? S5 C5 S6 130.0(12) . . ? C5 C6 C7 121.4(18) . . ? C5 C6 S4 120.4(14) . . ? C7 C6 S4 118.2(16) . . ? C8 C7 C6 99.0(17) . . ? C7 C8 S6 119.9(18) . . ? N1 C10 C11 118.3(18) . . ? C12 C11 C10 111(2) . . ? C13 C12 C11 114(3) . . ? N1 C20 C21 114.3(19) . . ? C22 C21 C20 123(3) . . ? C23 C22 C21 102(3) . . ? C31 C30 N1 116(2) . . ? C30 C31 C32 114(3) . . ? C33 C32 C31 99(3) . . ? C41 C40 N1 109.3(19) . . ? C42 C41 C40 109(2) . . ? C43 C42 C41 101(3) . . ? _diffrn_measured_fraction_theta_max 0.975 _diffrn_reflns_theta_full 23.43 _diffrn_measured_fraction_theta_full 0.975 _refine_diff_density_max 1.508 _refine_diff_density_min -0.825 _refine_diff_density_rms 0.178 # start Validation Reply Form _vrf_PLAT242_tbafea ; PROBLEM: Check Low Ueq as Compared to Neighbors for C22 RESPONSE: Due to problems with severe anisotropy and disorder, restraints to anisotropic parameters were used (ISOR and DFIX instructions of SHELX). All non-H atoms were refined ANIS with the exception of the severe disordered carbon atoms of cation which were left isotropic. The poor quality of the crystal results in a weak data set which is responsible for the low ratio Observed/Unique reflections (38%), a hight Rint (0.18) and a low resolution data collection (\q-23.43). ; # end Validation Reply Form # end Validation Reply Form # Attachment 'ANeves__BrBzPy]2[Fe_qdt_2]2.cif' data_brfqdt _database_code_depnum_ccdc_archive 'CCDC 695833' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C32 H16 Fe2 N8 S8, 2(C12 H11 Br N)' _chemical_formula_sum 'C56 H38 Br2 Fe2 N10 S8' _chemical_formula_weight 1378.96 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.3129(4) _cell_length_b 11.4865(7) _cell_length_c 17.0461(11) _cell_angle_alpha 100.625(3) _cell_angle_beta 98.672(3) _cell_angle_gamma 106.991(3) _cell_volume 1313.60(14) _cell_formula_units_Z 1 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1662 _cell_measurement_theta_min 2.52 _cell_measurement_theta_max 25.40 _exptl_crystal_description needle _exptl_crystal_colour black _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.743 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 694 _exptl_absorpt_coefficient_mu 2.444 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5691 _exptl_absorpt_correction_T_max 0.9528 _exptl_absorpt_process_details '(SADABS; Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker-AXS APEX- CCD area-detector' _diffrn_measurement_method '\f and \w' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11335 _diffrn_reflns_av_R_equivalents 0.0601 _diffrn_reflns_av_sigmaI/netI 0.0977 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 25.68 _reflns_number_total 4957 _reflns_number_gt 3157 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART, (Bruker, 2004)' _computing_cell_refinement 'Bruker SMART, (Bruker, 2004)' _computing_data_reduction 'Bruker SAINT, (Bruker, 2004)' _computing_structure_solution 'SIR97 (Altomare, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP3(Farrugia,1997) _computing_publication_material 'WinGX (Farrugia, 1999)' _refine_special_details ; 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. ; _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^)+(0.0302P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4957 _refine_ls_number_parameters 352 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0933 _refine_ls_R_factor_gt 0.0424 _refine_ls_wR_factor_ref 0.0812 _refine_ls_wR_factor_gt 0.0723 _refine_ls_goodness_of_fit_ref 0.903 _refine_ls_restrained_S_all 0.903 _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 Br1 Br 0.38841(7) 0.32367(5) 0.13913(3) 0.03094(15) Uani 1 1 d . . . Fe1 Fe 0.71996(8) 0.03868(6) 0.55216(3) 0.01376(15) Uani 1 1 d . . . S1 S 0.93239(14) 0.19923(10) 0.64799(6) 0.0157(2) Uani 1 1 d . . . S2 S 0.65311(15) -0.06762(10) 0.64698(6) 0.0161(2) Uani 1 1 d . . . S3 S 0.87005(14) 0.10426(10) 0.45593(6) 0.0162(2) Uani 1 1 d . . . S4 S 0.54207(14) -0.14081(10) 0.46206(6) 0.0143(2) Uani 1 1 d . . . N1 N 0.9471(5) 0.2585(3) 0.80719(19) 0.0155(8) Uani 1 1 d . . . N2 N 0.7101(5) 0.0140(3) 0.8070(2) 0.0189(8) Uani 1 1 d . . . N3 N 0.8080(5) 0.0015(3) 0.2974(2) 0.0170(8) Uani 1 1 d . . . N4 N 0.5372(5) -0.2259(3) 0.3070(2) 0.0162(8) Uani 1 1 d . . . N5 N 1.2395(4) 0.4482(3) 0.4148(2) 0.0146(8) Uani 1 1 d . . . C1 C 0.8759(5) 0.1684(4) 0.7402(2) 0.0136(10) Uani 1 1 d . . . C2 C 0.7520(5) 0.0447(4) 0.7400(2) 0.0134(9) Uani 1 1 d . . . C3 C 0.9008(6) 0.2280(4) 0.8777(3) 0.0189(10) Uani 1 1 d . . . C4 C 0.7836(6) 0.1070(4) 0.8774(2) 0.0169(10) Uani 1 1 d . . . C5 C 0.9712(6) 0.3218(4) 0.9518(3) 0.0262(11) Uani 1 1 d . . . H5 H 1.0488 0.4043 0.9523 0.031 Uiso 1 1 calc R . . C6 C 0.7427(6) 0.0807(5) 0.9518(3) 0.0284(12) Uani 1 1 d . . . H6 H 0.6665 -0.0015 0.9525 0.034 Uiso 1 1 calc R . . C7 C 0.9277(6) 0.2940(5) 1.0223(3) 0.0280(12) Uani 1 1 d . . . H7 H 0.9762 0.3573 1.0720 0.034 Uiso 1 1 calc R . . C8 C 0.8118(6) 0.1727(5) 1.0228(3) 0.0281(12) Uani 1 1 d . . . H8 H 0.7815 0.1546 1.0724 0.034 Uiso 1 1 calc R . . C9 C 0.7584(5) -0.0146(4) 0.3667(2) 0.0142(9) Uani 1 1 d . . . C10 C 0.6173(5) -0.1291(4) 0.3699(2) 0.0127(9) Uani 1 1 d . . . C11 C 0.7214(6) -0.0941(4) 0.2297(2) 0.0166(10) Uani 1 1 d . . . C12 C 0.5882(6) -0.2088(4) 0.2339(2) 0.0170(10) Uani 1 1 d . . . C13 C 0.7655(6) -0.0799(4) 0.1537(3) 0.0229(11) Uani 1 1 d . . . H13 H 0.8532 -0.0029 0.1497 0.027 Uiso 1 1 calc R . . C14 C 0.5085(6) -0.3073(4) 0.1633(3) 0.0231(11) Uani 1 1 d . . . H14 H 0.4232 -0.3858 0.1661 0.028 Uiso 1 1 calc R . . C15 C 0.6831(7) -0.1757(5) 0.0863(3) 0.0304(12) Uani 1 1 d . . . H15 H 0.7137 -0.1650 0.0353 0.036 Uiso 1 1 calc R . . C16 C 0.5538(6) -0.2901(5) 0.0904(3) 0.0279(12) Uani 1 1 d . . . H16 H 0.4971 -0.3562 0.0424 0.033 Uiso 1 1 calc R . . C17 C 1.2483(5) 0.3654(4) 0.4602(2) 0.0164(10) Uani 1 1 d . . . H17 H 1.2473 0.2840 0.4352 0.020 Uiso 1 1 calc R . . C18 C 1.2587(5) 0.3986(4) 0.5433(3) 0.0202(10) Uani 1 1 d . . . H18 H 1.2651 0.3404 0.5758 0.024 Uiso 1 1 calc R . . C19 C 1.2597(5) 0.5158(4) 0.5785(3) 0.0192(10) Uani 1 1 d . . . H19 H 1.2667 0.5395 0.6356 0.023 Uiso 1 1 calc R . . C20 C 1.2506(6) 0.5992(4) 0.5313(3) 0.0204(10) Uani 1 1 d . . . H20 H 1.2523 0.6810 0.5554 0.024 Uiso 1 1 calc R . . C21 C 1.2391(5) 0.5638(4) 0.4490(3) 0.0186(10) Uani 1 1 d . . . H21 H 1.2308 0.6209 0.4159 0.022 Uiso 1 1 calc R . . C22 C 1.2258(6) 0.4122(4) 0.3248(2) 0.0231(11) Uani 1 1 d . . . H22A H 1.2614 0.3352 0.3112 0.028 Uiso 1 1 calc R . . H22B H 1.3206 0.4800 0.3088 0.028 Uiso 1 1 calc R . . C23 C 1.0243(6) 0.3893(4) 0.2771(2) 0.0155(10) Uani 1 1 d . . . C24 C 0.8758(6) 0.2767(4) 0.2695(2) 0.0231(11) Uani 1 1 d . . . H24 H 0.9042 0.2132 0.2928 0.028 Uiso 1 1 calc R . . C25 C 0.6872(6) 0.2570(4) 0.2282(2) 0.0220(10) Uani 1 1 d . . . H25 H 0.5859 0.1800 0.2223 0.026 Uiso 1 1 calc R . . C26 C 0.6493(6) 0.3503(4) 0.1960(2) 0.0185(10) Uani 1 1 d . . . C27 C 0.7917(6) 0.4630(4) 0.2019(2) 0.0208(10) Uani 1 1 d . . . H27 H 0.7615 0.5258 0.1784 0.025 Uiso 1 1 calc R . . C28 C 0.9803(6) 0.4819(4) 0.2433(2) 0.0196(10) Uani 1 1 d . . . H28 H 1.0808 0.5591 0.2487 0.023 Uiso 1 1 calc R . . 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 Br1 0.0239(3) 0.0383(3) 0.0236(3) 0.0007(2) -0.0007(2) 0.0069(2) Fe1 0.0150(3) 0.0129(4) 0.0134(3) 0.0039(3) 0.0027(2) 0.0044(3) S1 0.0160(6) 0.0141(6) 0.0155(5) 0.0047(5) 0.0029(4) 0.0021(5) S2 0.0196(6) 0.0139(6) 0.0136(5) 0.0040(5) 0.0025(4) 0.0038(5) S3 0.0166(6) 0.0145(6) 0.0165(5) 0.0051(5) 0.0040(4) 0.0029(5) S4 0.0155(5) 0.0134(6) 0.0140(5) 0.0040(4) 0.0036(4) 0.0042(4) N1 0.0181(19) 0.013(2) 0.0138(18) 0.0013(16) 0.0019(15) 0.0046(15) N2 0.0192(19) 0.020(2) 0.019(2) 0.0089(17) 0.0072(16) 0.0060(16) N3 0.0205(19) 0.019(2) 0.020(2) 0.0082(17) 0.0099(16) 0.0136(16) N4 0.0142(18) 0.014(2) 0.0206(19) 0.0019(16) 0.0032(15) 0.0060(15) N5 0.0146(18) 0.014(2) 0.0146(18) 0.0047(16) 0.0018(14) 0.0041(15) C1 0.010(2) 0.021(3) 0.014(2) 0.008(2) 0.0032(17) 0.0090(19) C2 0.010(2) 0.011(2) 0.020(2) 0.0047(19) 0.0046(18) 0.0040(18) C3 0.020(2) 0.027(3) 0.017(2) 0.008(2) 0.0082(19) 0.014(2) C4 0.022(2) 0.023(3) 0.011(2) 0.0042(19) 0.0025(18) 0.015(2) C5 0.027(3) 0.028(3) 0.024(3) 0.002(2) 0.004(2) 0.013(2) C6 0.032(3) 0.030(3) 0.024(3) 0.010(2) 0.010(2) 0.008(2) C7 0.033(3) 0.038(3) 0.015(2) -0.003(2) 0.001(2) 0.021(2) C8 0.037(3) 0.039(3) 0.013(2) 0.010(2) 0.011(2) 0.015(3) C9 0.013(2) 0.014(2) 0.017(2) 0.0025(19) 0.0023(17) 0.0080(18) C10 0.012(2) 0.013(2) 0.017(2) 0.0045(19) 0.0013(17) 0.0099(18) C11 0.022(2) 0.017(3) 0.016(2) 0.0043(19) 0.0035(18) 0.013(2) C12 0.021(2) 0.021(3) 0.013(2) 0.002(2) 0.0003(18) 0.015(2) C13 0.028(3) 0.028(3) 0.020(2) 0.011(2) 0.007(2) 0.016(2) C14 0.023(2) 0.024(3) 0.024(3) 0.000(2) 0.004(2) 0.012(2) C15 0.045(3) 0.041(4) 0.016(2) 0.007(2) 0.012(2) 0.029(3) C16 0.032(3) 0.037(3) 0.015(2) -0.006(2) -0.001(2) 0.022(2) C17 0.014(2) 0.012(2) 0.022(2) 0.003(2) 0.0027(18) 0.0039(18) C18 0.015(2) 0.025(3) 0.025(2) 0.011(2) 0.0089(19) 0.009(2) C19 0.013(2) 0.025(3) 0.018(2) 0.001(2) 0.0039(18) 0.007(2) C20 0.016(2) 0.015(3) 0.028(3) 0.000(2) 0.0024(19) 0.0065(19) C21 0.012(2) 0.015(3) 0.028(3) 0.011(2) 0.0013(18) 0.0008(19) C22 0.027(3) 0.030(3) 0.016(2) 0.007(2) 0.0090(19) 0.012(2) C23 0.017(2) 0.019(3) 0.010(2) 0.0052(19) 0.0058(17) 0.0045(19) C24 0.035(3) 0.016(3) 0.019(2) 0.006(2) 0.007(2) 0.007(2) C25 0.030(3) 0.013(3) 0.020(2) 0.003(2) 0.007(2) 0.002(2) C26 0.011(2) 0.023(3) 0.011(2) -0.007(2) -0.0018(17) -0.0010(19) C27 0.027(3) 0.018(3) 0.018(2) 0.005(2) 0.0030(19) 0.009(2) C28 0.023(2) 0.015(3) 0.018(2) 0.005(2) 0.0097(19) -0.0009(19) _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 Br1 C26 1.914(4) . ? Fe1 S1 2.2208(11) . ? Fe1 S2 2.2271(12) . ? Fe1 S4 2.2280(12) . ? Fe1 S3 2.2312(12) . ? Fe1 S4 2.5270(12) 2_656 ? S1 C1 1.755(4) . ? S2 C2 1.748(4) . ? S3 C9 1.747(4) . ? S4 C10 1.756(4) . ? S4 Fe1 2.5270(12) 2_656 ? N1 C1 1.310(5) . ? N1 C3 1.376(5) . ? N2 C2 1.309(5) . ? N2 C4 1.367(5) . ? N3 C9 1.317(5) . ? N3 C11 1.357(5) . ? N4 C10 1.311(5) . ? N4 C12 1.385(5) . ? N5 C17 1.342(5) . ? N5 C21 1.350(5) . ? N5 C22 1.494(5) . ? C1 C2 1.444(5) . ? C3 C4 1.402(6) . ? C3 C5 1.415(6) . ? C4 C6 1.411(6) . ? C5 C7 1.358(6) . ? C5 H5 0.9500 . ? C6 C8 1.366(6) . ? C6 H6 0.9500 . ? C7 C8 1.406(6) . ? C7 H7 0.9500 . ? C8 H8 0.9500 . ? C9 C10 1.431(5) . ? C11 C13 1.409(6) . ? C11 C12 1.413(6) . ? C12 C14 1.403(5) . ? C13 C15 1.353(6) . ? C13 H13 0.9500 . ? C14 C16 1.366(6) . ? C14 H14 0.9500 . ? C15 C16 1.399(6) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 C18 1.382(5) . ? C17 H17 0.9500 . ? C18 C19 1.367(5) . ? C18 H18 0.9500 . ? C19 C20 1.369(6) . ? C19 H19 0.9500 . ? C20 C21 1.368(6) . ? C20 H20 0.9500 . ? C21 H21 0.9500 . ? C22 C23 1.494(5) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 C28 1.392(6) . ? C23 C24 1.395(6) . ? C24 C25 1.384(6) . ? C24 H24 0.9500 . ? C25 C26 1.369(6) . ? C25 H25 0.9500 . ? C26 C27 1.380(6) . ? C27 C28 1.387(5) . ? C27 H27 0.9500 . ? C28 H28 0.9500 . ? 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 S1 Fe1 S2 89.92(4) . . ? S1 Fe1 S4 169.91(5) . . ? S2 Fe1 S4 85.55(4) . . ? S1 Fe1 S3 90.86(4) . . ? S2 Fe1 S3 157.50(5) . . ? S4 Fe1 S3 89.91(4) . . ? S1 Fe1 S4 94.61(4) . 2_656 ? S2 Fe1 S4 103.97(4) . 2_656 ? S4 Fe1 S4 95.23(4) . 2_656 ? S3 Fe1 S4 98.38(4) . 2_656 ? C1 S1 Fe1 104.29(14) . . ? C2 S2 Fe1 104.73(14) . . ? C9 S3 Fe1 105.40(15) . . ? C10 S4 Fe1 105.76(14) . . ? C10 S4 Fe1 99.30(12) . 2_656 ? Fe1 S4 Fe1 84.77(4) . 2_656 ? C1 N1 C3 116.3(4) . . ? C2 N2 C4 116.4(4) . . ? C9 N3 C11 117.7(4) . . ? C10 N4 C12 115.7(4) . . ? C17 N5 C21 120.9(4) . . ? C17 N5 C22 120.1(3) . . ? C21 N5 C22 119.0(3) . . ? N1 C1 C2 121.9(4) . . ? N1 C1 S1 119.0(3) . . ? C2 C1 S1 119.1(3) . . ? N2 C2 C1 122.3(4) . . ? N2 C2 S2 118.9(3) . . ? C1 C2 S2 118.8(3) . . ? N1 C3 C4 121.6(4) . . ? N1 C3 C5 118.9(4) . . ? C4 C3 C5 119.6(4) . . ? N2 C4 C3 121.5(4) . . ? N2 C4 C6 119.4(4) . . ? C3 C4 C6 119.0(4) . . ? C7 C5 C3 120.0(5) . . ? C7 C5 H5 120.0 . . ? C3 C5 H5 120.0 . . ? C8 C6 C4 120.5(5) . . ? C8 C6 H6 119.7 . . ? C4 C6 H6 119.7 . . ? C5 C7 C8 120.8(4) . . ? C5 C7 H7 119.6 . . ? C8 C7 H7 119.6 . . ? C6 C8 C7 120.0(4) . . ? C6 C8 H8 120.0 . . ? C7 C8 H8 120.0 . . ? N3 C9 C10 120.7(4) . . ? N3 C9 S3 119.4(3) . . ? C10 C9 S3 119.9(3) . . ? N4 C10 C9 123.6(4) . . ? N4 C10 S4 117.7(3) . . ? C9 C10 S4 118.7(3) . . ? N3 C11 C13 119.8(4) . . ? N3 C11 C12 121.3(4) . . ? C13 C11 C12 118.9(4) . . ? N4 C12 C14 119.6(4) . . ? N4 C12 C11 120.8(4) . . ? C14 C12 C11 119.5(4) . . ? C15 C13 C11 120.2(4) . . ? C15 C13 H13 119.9 . . ? C11 C13 H13 119.9 . . ? C16 C14 C12 120.0(4) . . ? C16 C14 H14 120.0 . . ? C12 C14 H14 120.0 . . ? C13 C15 C16 121.1(4) . . ? C13 C15 H15 119.4 . . ? C16 C15 H15 119.4 . . ? C14 C16 C15 120.3(4) . . ? C14 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? N5 C17 C18 119.9(4) . . ? N5 C17 H17 120.1 . . ? C18 C17 H17 120.1 . . ? C19 C18 C17 119.5(4) . . ? C19 C18 H18 120.3 . . ? C17 C18 H18 120.3 . . ? C18 C19 C20 119.9(4) . . ? C18 C19 H19 120.1 . . ? C20 C19 H19 120.1 . . ? C21 C20 C19 119.6(4) . . ? C21 C20 H20 120.2 . . ? C19 C20 H20 120.2 . . ? N5 C21 C20 120.3(4) . . ? N5 C21 H21 119.9 . . ? C20 C21 H21 119.9 . . ? N5 C22 C23 111.8(3) . . ? N5 C22 H22A 109.3 . . ? C23 C22 H22A 109.3 . . ? N5 C22 H22B 109.3 . . ? C23 C22 H22B 109.3 . . ? H22A C22 H22B 107.9 . . ? C28 C23 C24 119.3(4) . . ? C28 C23 C22 120.6(4) . . ? C24 C23 C22 120.0(4) . . ? C25 C24 C23 120.3(4) . . ? C25 C24 H24 119.9 . . ? C23 C24 H24 119.9 . . ? C26 C25 C24 118.8(4) . . ? C26 C25 H25 120.6 . . ? C24 C25 H25 120.6 . . ? C25 C26 C27 122.8(4) . . ? C25 C26 Br1 118.9(3) . . ? C27 C26 Br1 118.2(3) . . ? C26 C27 C28 117.9(4) . . ? C26 C27 H27 121.0 . . ? C28 C27 H27 121.0 . . ? C27 C28 C23 120.8(4) . . ? C27 C28 H28 119.6 . . ? C23 C28 H28 119.6 . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.68 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.628 _refine_diff_density_min -0.609 _refine_diff_density_rms 0.109 # Attachment 'ANeves__Et4]2[Fe_alpha-tpdt_2]2.cif' data_featpdt _database_code_depnum_ccdc_archive 'CCDC 695834' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H8 Fe2 S12, 2(C8 H20 N)' _chemical_formula_sum 'C32 H48 Fe2 N2 S12' _chemical_formula_weight 957.14 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.5925(6) _cell_length_b 11.0890(5) _cell_length_c 16.2457(8) _cell_angle_alpha 90.00 _cell_angle_beta 106.464(3) _cell_angle_gamma 90.00 _cell_volume 2175.51(18) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1935 _cell_measurement_theta_min 2.49 _cell_measurement_theta_max 21.88 _exptl_crystal_description plate _exptl_crystal_colour black _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.461 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 996 _exptl_absorpt_coefficient_mu 1.269 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7854 _exptl_absorpt_correction_T_max 0.9751 _exptl_absorpt_process_details 'SADABS - Sheldrick 2004' _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker-AXS APEX- CCD area-detector' _diffrn_measurement_method '\f and \w' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15151 _diffrn_reflns_av_R_equivalents 0.0851 _diffrn_reflns_av_sigmaI/netI 0.1007 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.03 _diffrn_reflns_theta_max 25.73 _reflns_number_total 4132 _reflns_number_gt 2219 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR97 (Altomare, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SCHAKAL(Keller,1989),Ortep3(Farrugia,1997) _computing_publication_material 'WinGX (Farrugia, 1999)' _refine_special_details ; 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. The crystals obtained were of poor quality, which results in a weak data set. Due to slight anisotropy in the CH3 atoms of TEA cation, restraints to anisotropic parameters were used (ISOR instructions in SHELX97 (Sheldrick,1997). The terminal thiophenic rings in the anion units showed evidence of disorder in the displacement parameters of C and S atoms. They were successfully modelled over two positions with sof 70:30 for S3-C3-C4, and sof 61:39 for S6-C7-C8 and restraints were used (ISOR and DFIX instructions in SHELX97 (Sheldrick,1997). ; _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^)+(0.0949P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4132 _refine_ls_number_parameters 273 _refine_ls_number_restraints 67 _refine_ls_R_factor_all 0.1424 _refine_ls_R_factor_gt 0.0627 _refine_ls_wR_factor_ref 0.1794 _refine_ls_wR_factor_gt 0.1547 _refine_ls_goodness_of_fit_ref 0.970 _refine_ls_restrained_S_all 0.997 _refine_ls_shift/su_max 0.003 _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 Fe1 Fe 0.47083(6) 0.05928(8) 0.57955(5) 0.0325(3) Uani 1 1 d . . . S1 S 0.63433(12) 0.04907(14) 0.54983(10) 0.0368(4) Uani 1 1 d . . . S2 S 0.45372(15) 0.25288(15) 0.53984(11) 0.0474(5) Uani 1 1 d . A . S4 S 0.53214(16) -0.08883(15) 0.67414(11) 0.0512(5) Uani 1 1 d . B . S5 S 0.32970(14) 0.09429(19) 0.63391(11) 0.0553(5) Uani 1 1 d . . . C1 C 0.5701(7) 0.2768(6) 0.5047(4) 0.054(2) Uani 1 1 d D . . C2 C 0.6496(6) 0.1899(6) 0.5088(4) 0.0479(17) Uani 1 1 d D A . S3 S 0.5993(5) 0.4030(4) 0.4541(3) 0.092(2) Uani 0.698(10) 1 d PD A 1 C3 C 0.739(2) 0.226(2) 0.4752(19) 0.084(11) Uani 0.698(10) 1 d PDU A 1 H3 H 0.8016 0.1782 0.4758 0.101 Uiso 0.698(10) 1 calc PR A 1 C4 C 0.7203(15) 0.3364(13) 0.4435(12) 0.110(8) Uani 0.698(10) 1 d PD A 1 H4 H 0.7690 0.3762 0.4171 0.132 Uiso 0.698(10) 1 calc PR A 1 C3A C 0.616(2) 0.389(2) 0.473(2) 0.032(8) Uani 0.302(10) 1 d PDU A 2 H3A H 0.5821 0.4649 0.4762 0.038 Uiso 0.302(10) 1 calc PR A 2 S3A S 0.7459(12) 0.2449(14) 0.4649(10) 0.078(6) Uani 0.302(10) 1 d PD A 2 C4A C 0.703(3) 0.383(2) 0.441(3) 0.0742(2) Uani 0.302(10) 1 d PDU A 2 H4A H 0.7320 0.4440 0.4128 0.089 Uiso 0.302(10) 1 calc PR A 2 C5 C 0.4243(7) -0.1003(7) 0.7229(4) 0.066(2) Uani 1 1 d D . . C6 C 0.3375(7) -0.0203(8) 0.7068(5) 0.062(2) Uani 1 1 d D B . C7 C 0.254(2) -0.0300(18) 0.7497(17) 0.051(6) Uani 0.609(14) 1 d PD B 1 H7 H 0.1904 0.0186 0.7427 0.062 Uiso 0.609(14) 1 calc PR B 1 S6 S 0.3992(5) -0.2017(5) 0.7961(3) 0.064(2) Uani 0.609(14) 1 d P B 1 C8 C 0.2884(15) -0.1259(14) 0.8034(10) 0.054(6) Uani 0.609(14) 1 d PDU B 1 H8 H 0.2500 -0.1486 0.8436 0.065 Uiso 0.609(14) 1 calc PR B 1 S6A S 0.2688(8) -0.0822(14) 0.7717(8) 0.106(7) Uani 0.391(14) 1 d PD B 2 C7A C 0.451(2) -0.204(2) 0.7896(18) 0.058(10) Uani 0.391(14) 1 d PD B 2 H7A H 0.5113 -0.2594 0.8058 0.070 Uiso 0.391(14) 1 calc PR B 2 C8A C 0.3606(19) -0.188(2) 0.8164(16) 0.055(9) Uani 0.391(14) 1 d PDU B 2 H8A H 0.3489 -0.2376 0.8609 0.066 Uiso 0.391(14) 1 calc PR B 2 N1 N 0.6095(4) 0.2642(5) 0.8511(3) 0.0448(14) Uani 1 1 d . . . C10 C 0.5507(7) 0.1451(7) 0.8458(5) 0.066(2) Uani 1 1 d . . . H10A H 0.5373 0.1123 0.7870 0.079 Uiso 1 1 calc R . . H10B H 0.4778 0.1583 0.8561 0.079 Uiso 1 1 calc R . . C11 C 0.6161(10) 0.0516(12) 0.9106(9) 0.149(5) Uani 1 1 d U . . H11A H 0.6955 0.0690 0.9240 0.223 Uiso 1 1 calc R . . H11B H 0.6014 -0.0293 0.8858 0.223 Uiso 1 1 calc R . . H11C H 0.5930 0.0557 0.9633 0.223 Uiso 1 1 calc R . . C20 C 0.7217(6) 0.2557(9) 0.8407(6) 0.091(3) Uani 1 1 d . . . H20A H 0.7672 0.2028 0.8862 0.109 Uiso 1 1 calc R . . H20B H 0.7558 0.3369 0.8488 0.109 Uiso 1 1 calc R . . C21 C 0.7251(8) 0.2065(9) 0.7527(6) 0.102(3) Uani 1 1 d U . . H21A H 0.6898 0.1269 0.7433 0.153 Uiso 1 1 calc R . . H21B H 0.8023 0.1994 0.7516 0.153 Uiso 1 1 calc R . . H21C H 0.6854 0.2618 0.7073 0.153 Uiso 1 1 calc R . . C30 C 0.5329(7) 0.3380(8) 0.7823(5) 0.076(3) Uani 1 1 d . . . H30A H 0.4589 0.3383 0.7923 0.091 Uiso 1 1 calc R . . H30B H 0.5252 0.2981 0.7264 0.091 Uiso 1 1 calc R . . C31 C 0.5695(9) 0.4706(11) 0.7761(8) 0.125(4) Uani 1 1 d U . . H31A H 0.5860 0.5085 0.8328 0.188 Uiso 1 1 calc R . . H31B H 0.5096 0.5150 0.7357 0.188 Uiso 1 1 calc R . . H31C H 0.6358 0.4721 0.7559 0.188 Uiso 1 1 calc R . . C40 C 0.6279(6) 0.3252(8) 0.9351(5) 0.066(2) Uani 1 1 d . . . H40A H 0.6551 0.4079 0.9303 0.079 Uiso 1 1 calc R . . H40B H 0.6870 0.2816 0.9781 0.079 Uiso 1 1 calc R . . C41 C 0.5278(8) 0.3332(9) 0.9678(7) 0.101(3) Uani 1 1 d U . . H41A H 0.4734 0.3879 0.9311 0.152 Uiso 1 1 calc R . . H41B H 0.5497 0.3640 1.0268 0.152 Uiso 1 1 calc R . . H41C H 0.4949 0.2529 0.9668 0.152 Uiso 1 1 calc R . . 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 Fe1 0.0303(5) 0.0334(5) 0.0278(5) -0.0039(4) -0.0015(3) 0.0052(4) S1 0.0294(8) 0.0430(9) 0.0328(8) -0.0065(7) 0.0001(6) 0.0032(7) S2 0.0569(11) 0.0304(8) 0.0444(10) -0.0027(8) -0.0027(8) 0.0112(8) S4 0.0717(12) 0.0400(10) 0.0349(9) 0.0046(8) 0.0040(8) 0.0112(9) S5 0.0396(9) 0.0839(15) 0.0400(10) -0.0116(9) 0.0075(8) 0.0070(10) C1 0.087(5) 0.036(4) 0.028(4) -0.006(3) -0.002(4) -0.020(4) C2 0.049(4) 0.048(4) 0.043(4) -0.009(3) 0.008(3) -0.015(4) S3 0.164(5) 0.040(2) 0.051(3) 0.0080(17) -0.002(3) -0.029(3) C3 0.084(11) 0.084(11) 0.084(11) -0.0001(11) 0.024(3) -0.0002(11) C4 0.20(2) 0.031 0.104(12) -0.011(10) 0.045(13) -0.053(11) C3A 0.031(8) 0.032(8) 0.032(8) 0.0000(11) 0.009(3) 0.0002(11) S3A 0.085(8) 0.094(11) 0.063(7) -0.042(6) 0.034(6) -0.055(8) C4A 0.081 0.080 0.062 0.0001(11) 0.0205(10) -0.0003(11) C5 0.118(7) 0.048(5) 0.031(4) -0.011(3) 0.019(4) -0.041(5) C6 0.068(5) 0.072(6) 0.047(5) -0.016(4) 0.016(4) -0.033(5) C7 0.063(10) 0.051(10) 0.046(14) 0.000(7) 0.025(9) -0.017(8) S6 0.085(5) 0.056(3) 0.056(3) 0.003(2) 0.029(3) -0.004(3) C8 0.054(6) 0.054(6) 0.055(6) -0.0001(11) 0.0152(19) -0.0001(11) S6A 0.064(7) 0.202(19) 0.059(9) -0.024(11) 0.028(7) -0.064(10) C7A 0.10(3) 0.041(12) 0.058(14) -0.017(10) 0.064(18) -0.041(17) C8A 0.055(9) 0.055(9) 0.055(9) 0.0003(11) 0.016(3) -0.0002(11) N1 0.026(3) 0.061(4) 0.041(3) -0.008(3) -0.001(2) -0.004(3) C10 0.081(6) 0.052(5) 0.049(5) 0.001(4) -0.008(4) -0.011(4) C11 0.149(5) 0.148(5) 0.148(5) 0.0002(11) 0.0412(17) -0.0005(11) C20 0.052(5) 0.124(8) 0.089(7) -0.069(6) 0.007(5) -0.021(5) C21 0.101(3) 0.102(3) 0.102(3) -0.0018(10) 0.0289(14) -0.0001(10) C30 0.078(6) 0.071(6) 0.065(6) 0.004(5) -0.002(5) -0.012(5) C31 0.126(4) 0.125(4) 0.125(4) 0.0008(11) 0.0348(15) -0.0006(11) C40 0.048(4) 0.087(6) 0.065(5) -0.030(5) 0.018(4) -0.024(4) C41 0.102(3) 0.102(3) 0.101(3) -0.0006(10) 0.0288(13) -0.0003(10) _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 Fe1 S5 2.2313(19) . ? Fe1 S4 2.2322(19) . ? Fe1 S2 2.2344(19) . ? Fe1 S1 2.2469(17) . ? Fe1 S1 2.4570(17) 3_656 ? S1 C2 1.730(7) . ? S1 Fe1 2.4570(17) 3_656 ? S2 C1 1.738(8) . ? S4 C5 1.760(8) . ? S5 C6 1.720(8) . ? C1 C2 1.377(10) . ? C1 C3A 1.520(18) . ? C1 S3 1.715(8) . ? C2 C3 1.44(3) . ? C2 S3A 1.686(15) . ? S3 C4 1.745(15) . ? C3 C4 1.321(18) . ? C3A C4A 1.34(2) . ? S3A C4A 1.637(19) . ? C5 C6 1.375(11) . ? C5 C7A 1.550(18) . ? C5 S6 1.730(9) . ? C6 C7 1.42(3) . ? C6 S6A 1.689(13) . ? C7 C8 1.366(17) . ? S6 C8 1.660(18) . ? S6A C8A 1.665(17) . ? C7A C8A 1.35(2) . ? N1 C20 1.473(9) . ? N1 C40 1.481(8) . ? N1 C30 1.496(9) . ? N1 C10 1.505(9) . ? C10 C11 1.539(14) . ? C20 C21 1.541(12) . ? C30 C31 1.553(13) . ? C40 C41 1.503(11) . ? 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 S5 Fe1 S4 90.82(8) . . ? S5 Fe1 S2 85.68(8) . . ? S4 Fe1 S2 153.12(7) . . ? S5 Fe1 S1 167.15(7) . . ? S4 Fe1 S1 87.23(7) . . ? S2 Fe1 S1 90.32(7) . . ? S5 Fe1 S1 97.30(6) . 3_656 ? S4 Fe1 S1 103.09(7) . 3_656 ? S2 Fe1 S1 103.79(6) . 3_656 ? S1 Fe1 S1 95.51(6) . 3_656 ? C2 S1 Fe1 104.2(2) . . ? C2 S1 Fe1 101.7(2) . 3_656 ? Fe1 S1 Fe1 84.49(6) . 3_656 ? C1 S2 Fe1 102.7(2) . . ? C5 S4 Fe1 101.7(3) . . ? C6 S5 Fe1 104.3(3) . . ? C2 C1 C3A 104.5(12) . . ? C2 C1 S3 110.0(6) . . ? C3A C1 S3 10.6(14) . . ? C2 C1 S2 123.1(5) . . ? C3A C1 S2 132.2(12) . . ? S3 C1 S2 126.7(5) . . ? C1 C2 C3 114.9(11) . . ? C1 C2 S3A 109.0(8) . . ? C3 C2 S3A 6.0(14) . . ? C1 C2 S1 119.5(5) . . ? C3 C2 S1 125.6(11) . . ? S3A C2 S1 131.4(8) . . ? C1 S3 C4 90.8(6) . . ? C4 C3 C2 110(2) . . ? C3 C4 S3 114.6(17) . . ? C4A C3A C1 121(2) . . ? C4A S3A C2 101.9(14) . . ? C3A C4A S3A 102(2) . . ? C6 C5 C7A 128.2(11) . . ? C6 C5 S6 105.1(6) . . ? C7A C5 S6 23.7(8) . . ? C6 C5 S4 122.7(6) . . ? C7A C5 S4 108.8(10) . . ? S6 C5 S4 132.2(6) . . ? C5 C6 C7 121.0(9) . . ? C5 C6 S6A 98.0(7) . . ? C7 C6 S6A 23.2(8) . . ? C5 C6 S5 119.7(6) . . ? C7 C6 S5 119.3(9) . . ? S6A C6 S5 142.3(8) . . ? C8 C7 C6 103(2) . . ? C8 S6 C5 92.4(6) . . ? C7 C8 S6 117.7(18) . . ? C8A S6A C6 98.3(11) . . ? C8A C7A C5 95.2(18) . . ? C7A C8A S6A 120(2) . . ? C20 N1 C40 103.3(5) . . ? C20 N1 C30 112.6(7) . . ? C40 N1 C30 109.8(6) . . ? C20 N1 C10 114.2(6) . . ? C40 N1 C10 113.6(6) . . ? C30 N1 C10 103.5(5) . . ? N1 C10 C11 113.1(7) . . ? N1 C20 C21 114.1(6) . . ? N1 C30 C31 115.2(7) . . ? N1 C40 C41 115.1(6) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.73 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.654 _refine_diff_density_min -0.679 _refine_diff_density_rms 0.105 # start Validation Reply Form _vrf_PLAT860_featpdt ; PROBLEM: Number of Least-Squares Restraints ....... 67 RESPONSE: The crystals obtained were of poor quality, which results in a weak data set. Due to slight anisotropy in the CH3 atoms of TEA cation, restraints to anisotropic parameters were used (ISOR instructions in SHELX97 (Sheldrick,1997). The terminal thiophenic rings in the anion units showed evidence of disorder in the displacement parameters of C and S atoms. They were successfully modelled over two positions with sof 70:30 for S3-C3-C4, and sof 61:39 for S6-C7-C8 and restraints were used (ISOR and DFIX instructions in SHELX97 (Sheldrick,1997). ; _vrf_PLAT241_featpdt ; PROBLEM: Check High Ueq as Compared to Neighbors for S6A RESPONSE: The crystals obtained were of poor quality, which results in a weak data set. The terminal thiophenic rings in the anion units showed evidence of disorder in the displacement parameters of C and S atoms. They were successfully modelled over two positions with sof 70:30 for S3-C3-C4, and sof 61:39 for S6-C7-C8 and restraints were used (ISOR and DFIX instructions in SHELX97 (Sheldrick,1997). ; _vrf_PLAT242_featpdt ; PROBLEM: Check Low Ueq as Compared to Neighbors for C3A RESPONSE:The crystals obtained were of poor quality, which results in a weak data set. The terminal thiophenic rings in the anion units showed evidence of disorder in the displacement parameters of C and S atoms. They were successfully modelled over two positions with sof 70:30 for S3-C3-C4, and sof 61:39 for S6-C7-C8 and restraints were used (ISOR and DFIX instructions in SHELX97 (Sheldrick,1997). ; # Attachment 'ANeves__BrBzPy]2[Fe_alpha-tpdt_2]2.cif' data_brbzfe _database_code_depnum_ccdc_archive 'CCDC 695835' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H8 Fe2 S12, 2(C12 H11 Br N)' _chemical_formula_sum 'C40 H30 Br2 Fe2 N2 S12' _chemical_formula_weight 1194.90 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.3573(5) _cell_length_b 25.3284(15) _cell_length_c 10.0811(6) _cell_angle_alpha 90.00 _cell_angle_beta 100.854(3) _cell_angle_gamma 90.00 _cell_volume 2346.5(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 2076 _cell_measurement_theta_min 2.21 _cell_measurement_theta_max 19.25 _exptl_crystal_description plate _exptl_crystal_colour black _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.691 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1196 _exptl_absorpt_coefficient_mu 2.888 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.2996 _exptl_absorpt_correction_T_max 0.9445 _exptl_absorpt_process_details '(SADABS; Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker-AXS APEX- CCD area-detector' _diffrn_measurement_method '\f and \w' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 19152 _diffrn_reflns_av_R_equivalents 0.1195 _diffrn_reflns_av_sigmaI/netI 0.1151 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 30 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.74 _diffrn_reflns_theta_max 25.03 _reflns_number_total 4116 _reflns_number_gt 1904 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART, (Bruker, 2004)' _computing_cell_refinement 'Bruker SMART, (Bruker, 2004)' _computing_data_reduction 'Bruker SAINT, (Bruker, 2004)' _computing_structure_solution 'SIR97 (Altomare, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP3(Farrugia,1997) _computing_publication_material 'WinGX (Farrugia, 1999)' _refine_special_details ; 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. The poor quality of the crystal results in a weak data set with great value of Rint (0.12%) which is responsible for the low ratio Unique/expected reflections (46 %). The two terminal thiophenic rings showed evidence of disorder in the displacement parameters of C and S atoms, witch were successfully modelled over two positions in the case of C7, C8 and S6 with sof 55:45. Restraints for displacement parameters were applied for atoms C6, C7 and C8 using DFIX and ISOR instructions in SHELXL97 (Sheldrick,1997). For the C3, C4 and S3 atoms these could not be successfully modelled. ; _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^)+(0.0851P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4116 _refine_ls_number_parameters 290 _refine_ls_number_restraints 16 _refine_ls_R_factor_all 0.1621 _refine_ls_R_factor_gt 0.0583 _refine_ls_wR_factor_ref 0.1604 _refine_ls_wR_factor_gt 0.1346 _refine_ls_goodness_of_fit_ref 0.867 _refine_ls_restrained_S_all 0.866 _refine_ls_shift/su_max 0.007 _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 Fe1 Fe 0.04612(10) 0.50854(4) 0.35762(10) 0.0461(3) Uani 1 1 d . . . Br1 Br 0.43160(13) 0.24010(4) -0.09711(12) 0.1082(5) Uani 1 1 d . . . S5 S 0.2368(2) 0.56187(8) 0.42594(19) 0.0571(5) Uani 1 1 d . . . S1 S -0.0552(2) 0.43787(8) 0.2423(2) 0.0603(6) Uani 1 1 d . . . S2 S 0.14338(19) 0.45583(7) 0.52976(18) 0.0494(5) Uani 1 1 d . . . S4 S -0.0167(2) 0.55577(8) 0.16759(19) 0.0578(5) Uani 1 1 d . A . N1 N 0.4200(6) 0.4746(2) 0.2229(6) 0.0494(15) Uani 1 1 d . . . C5 C 0.1018(8) 0.6091(3) 0.1945(8) 0.0522(19) Uani 1 1 d D . . C6 C 0.2091(9) 0.6115(3) 0.3056(8) 0.059(2) Uani 1 1 d D A . C14 C 0.3954(8) 0.4229(3) 0.2906(8) 0.060(2) Uani 1 1 d . . . H14A H 0.4685 0.4190 0.3749 0.072 Uiso 1 1 calc R . . H14B H 0.2977 0.4231 0.3148 0.072 Uiso 1 1 calc R . . C12 C 0.5711(9) 0.5452(4) 0.1905(9) 0.076(3) Uani 1 1 d . . . H12 H 0.6625 0.5626 0.2114 0.091 Uiso 1 1 calc R . . C10 C 0.3309(10) 0.5410(4) 0.0680(8) 0.069(2) Uani 1 1 d . . . H10 H 0.2538 0.5558 0.0039 0.083 Uiso 1 1 calc R . . C11 C 0.4625(10) 0.5657(3) 0.0993(8) 0.069(2) Uani 1 1 d . . . H11 H 0.4774 0.5980 0.0557 0.083 Uiso 1 1 calc R . . C9 C 0.3128(8) 0.4944(3) 0.1313(8) 0.060(2) Uani 1 1 d . . . H9 H 0.2229 0.4761 0.1095 0.071 Uiso 1 1 calc R . . C13 C 0.5483(9) 0.4985(3) 0.2535(8) 0.067(2) Uani 1 1 d . . . H13 H 0.6240 0.4835 0.3185 0.080 Uiso 1 1 calc R . . C17 C 0.5457(9) 0.3121(3) 0.1124(8) 0.065(2) Uani 1 1 d . . . H17 H 0.6364 0.2953 0.1120 0.078 Uiso 1 1 calc R . . C15 C 0.4071(8) 0.3773(3) 0.1996(7) 0.0502(18) Uani 1 1 d . . . C18 C 0.4227(10) 0.2955(3) 0.0244(9) 0.067(2) Uani 1 1 d . . . C16 C 0.5373(9) 0.3527(3) 0.2006(8) 0.060(2) Uani 1 1 d . . . H16 H 0.6217 0.3638 0.2622 0.072 Uiso 1 1 calc R . . C20 C 0.2860(9) 0.3609(3) 0.1150(9) 0.076(3) Uani 1 1 d . . . H20 H 0.1951 0.3770 0.1186 0.091 Uiso 1 1 calc R . . C19 C 0.2925(9) 0.3206(3) 0.0225(11) 0.085(3) Uani 1 1 d . . . H19 H 0.2083 0.3106 -0.0408 0.102 Uiso 1 1 calc R . . C1 C -0.0056(7) 0.3868(3) 0.3536(8) 0.058(2) Uani 1 1 d . . . C2 C 0.0801(7) 0.3920(3) 0.4770(8) 0.056(2) Uani 1 1 d . . . S3 S -0.0565(3) 0.32188(11) 0.3276(3) 0.1074(10) Uani 1 1 d . . . C3 C 0.1113(7) 0.3425(2) 0.5627(7) 0.0391(17) Uani 1 1 d . . . H3 H 0.1686 0.3388 0.6506 0.047 Uiso 1 1 calc R . . C4 C 0.0388(12) 0.3061(5) 0.4844(14) 0.127(5) Uani 1 1 d U . . H4 H 0.0393 0.2707 0.5154 0.152 Uiso 1 1 calc R . . S6 S 0.1061(10) 0.6603(5) 0.0927(8) 0.078(3) Uani 0.547(14) 1 d P A 1 C8 C 0.248(3) 0.6872(10) 0.191(2) 0.063(7) Uani 0.547(14) 1 d PD A 1 H8 H 0.2897 0.7195 0.1697 0.075 Uiso 0.547(14) 1 calc PR A 1 C7 C 0.301(4) 0.6597(15) 0.306(3) 0.080(18) Uani 0.547(14) 1 d PD A 1 H7 H 0.3821 0.6694 0.3734 0.095 Uiso 0.547(14) 1 calc PR A 1 S6A S 0.3121(18) 0.6671(6) 0.2996(16) 0.086(6) Uani 0.453(14) 1 d P A 2 C8A C 0.204(4) 0.6868(14) 0.133(3) 0.076(10) Uani 0.453(14) 1 d PD A 2 H8A H 0.2206 0.7180 0.0854 0.091 Uiso 0.453(14) 1 calc PR A 2 C7A C 0.097(6) 0.6510(17) 0.086(4) 0.10(2) Uani 0.453(14) 1 d PDU A 2 H7A H 0.0325 0.6520 0.0016 0.124 Uiso 0.453(14) 1 calc PR A 2 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 Fe1 0.0399(6) 0.0630(7) 0.0340(6) -0.0034(5) 0.0034(4) -0.0022(5) Br1 0.1280(10) 0.0946(8) 0.1077(9) -0.0381(7) 0.0367(7) -0.0064(7) S5 0.0499(11) 0.0733(14) 0.0449(11) -0.0013(10) 0.0010(9) -0.0110(10) S1 0.0605(12) 0.0705(14) 0.0446(12) -0.0085(10) -0.0036(10) -0.0043(10) S2 0.0443(10) 0.0606(12) 0.0414(11) -0.0011(9) 0.0030(8) -0.0006(9) S4 0.0525(12) 0.0734(14) 0.0445(11) 0.0087(10) 0.0014(9) -0.0069(10) N1 0.049(4) 0.060(4) 0.041(4) -0.006(3) 0.015(3) 0.003(3) C5 0.048(4) 0.056(5) 0.054(5) 0.000(4) 0.012(4) 0.006(4) C6 0.053(5) 0.058(5) 0.069(6) -0.007(4) 0.019(5) -0.006(4) C14 0.057(5) 0.075(6) 0.047(5) -0.001(4) 0.012(4) 0.001(4) C12 0.060(5) 0.088(7) 0.070(6) -0.005(5) -0.011(5) -0.016(5) C10 0.076(6) 0.083(7) 0.043(5) -0.004(5) -0.002(4) 0.035(5) C11 0.089(7) 0.065(6) 0.052(5) 0.008(4) 0.012(5) 0.010(5) C9 0.044(4) 0.081(6) 0.051(5) 0.000(5) 0.000(4) 0.013(4) C13 0.064(5) 0.074(6) 0.055(5) 0.008(5) -0.008(4) -0.002(5) C17 0.061(5) 0.074(6) 0.063(6) 0.016(5) 0.022(5) 0.005(5) C15 0.058(5) 0.051(5) 0.042(4) -0.004(4) 0.011(4) -0.008(4) C18 0.074(6) 0.061(5) 0.070(6) -0.002(4) 0.022(5) -0.001(5) C16 0.057(5) 0.065(5) 0.055(5) 0.009(4) 0.003(4) 0.008(4) C20 0.057(5) 0.086(7) 0.086(7) -0.024(6) 0.016(5) 0.003(5) C19 0.054(5) 0.083(7) 0.114(8) -0.015(6) 0.008(5) -0.003(5) C1 0.046(4) 0.060(5) 0.064(5) -0.025(4) 0.003(4) -0.004(4) C2 0.041(4) 0.062(5) 0.066(6) -0.004(4) 0.014(4) 0.002(4) S3 0.109(2) 0.0835(19) 0.127(3) -0.0203(17) 0.0148(19) -0.0063(16) C3 0.050(4) 0.024(4) 0.040(4) -0.004(3) -0.001(3) -0.002(3) C4 0.118(10) 0.114(10) 0.159(13) 0.070(9) 0.051(9) 0.066(8) S6 0.075(5) 0.069(5) 0.089(5) 0.013(3) 0.016(3) -0.007(3) C8 0.084(17) 0.063(12) 0.039(16) 0.027(14) 0.004(13) -0.001(11) C7 0.09(3) 0.12(4) 0.027(17) 0.000(17) 0.001(17) 0.05(2) S6A 0.081(9) 0.073(7) 0.104(13) -0.018(7) 0.019(8) -0.038(6) C8A 0.11(3) 0.089(19) 0.023(16) 0.009(18) 0.008(17) 0.03(2) C7A 0.10(2) 0.10(2) 0.10(2) 0.0000(10) 0.019(5) 0.0000(10) _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 Fe1 S5 2.241(2) . ? Fe1 S4 2.241(2) . ? Fe1 S2 2.242(2) . ? Fe1 S1 2.245(2) . ? Fe1 S2 2.451(2) 3_566 ? Br1 C18 1.874(8) . ? S5 C6 1.733(9) . ? S1 C1 1.718(8) . ? S2 C2 1.769(7) . ? S2 Fe1 2.451(2) 3_566 ? S4 C5 1.736(7) . ? N1 C9 1.327(9) . ? N1 C13 1.328(9) . ? N1 C14 1.515(9) . ? C5 C6 1.358(10) . ? C5 C7A 1.517(17) . ? C5 S6 1.659(10) . ? C6 C7 1.49(4) . ? C6 S6A 1.714(13) . ? C14 C15 1.492(10) . ? C12 C11 1.340(11) . ? C12 C13 1.378(10) . ? C10 C11 1.364(11) . ? C10 C9 1.367(10) . ? C17 C16 1.372(10) . ? C17 C18 1.380(11) . ? C15 C20 1.350(10) . ? C15 C16 1.366(9) . ? C18 C19 1.371(11) . ? C20 C19 1.392(11) . ? C1 C2 1.354(10) . ? C1 S3 1.718(7) . ? C2 C3 1.519(9) . ? S3 C4 1.710(12) . ? C3 C4 1.316(14) . ? S6 C8 1.65(3) . ? C8 C7 1.359(19) . ? S6A C8A 1.86(3) . ? C8A C7A 1.36(2) . ? 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 S5 Fe1 S4 90.38(8) . . ? S5 Fe1 S2 86.41(8) . . ? S4 Fe1 S2 169.22(8) . . ? S5 Fe1 S1 150.94(9) . . ? S4 Fe1 S1 88.04(8) . . ? S2 Fe1 S1 89.78(8) . . ? S5 Fe1 S2 103.86(8) . 3_566 ? S4 Fe1 S2 95.92(8) . 3_566 ? S2 Fe1 S2 94.84(7) . 3_566 ? S1 Fe1 S2 105.17(8) . 3_566 ? C6 S5 Fe1 102.5(3) . . ? C1 S1 Fe1 103.1(2) . . ? C2 S2 Fe1 104.3(3) . . ? C2 S2 Fe1 104.2(2) . 3_566 ? Fe1 S2 Fe1 85.16(7) . 3_566 ? C5 S4 Fe1 103.0(3) . . ? C9 N1 C13 121.4(7) . . ? C9 N1 C14 118.8(6) . . ? C13 N1 C14 119.8(6) . . ? C6 C5 C7A 118.5(14) . . ? C6 C5 S6 112.0(6) . . ? C7A C5 S6 7.6(19) . . ? C6 C5 S4 121.0(6) . . ? C7A C5 S4 120.1(14) . . ? S6 C5 S4 127.0(6) . . ? C5 C6 C7 112.0(11) . . ? C5 C6 S6A 109.9(8) . . ? C7 C6 S6A 2.2(13) . . ? C5 C6 S5 122.3(7) . . ? C7 C6 S5 125.6(10) . . ? S6A C6 S5 127.6(7) . . ? C15 C14 N1 110.9(6) . . ? C11 C12 C13 119.0(8) . . ? C11 C10 C9 118.3(7) . . ? C12 C11 C10 121.0(8) . . ? N1 C9 C10 120.5(7) . . ? N1 C13 C12 119.8(7) . . ? C16 C17 C18 120.2(8) . . ? C20 C15 C16 120.4(7) . . ? C20 C15 C14 118.5(7) . . ? C16 C15 C14 121.1(7) . . ? C19 C18 C17 119.9(8) . . ? C19 C18 Br1 119.1(7) . . ? C17 C18 Br1 120.9(7) . . ? C15 C16 C17 119.8(7) . . ? C15 C20 C19 120.8(8) . . ? C18 C19 C20 118.8(8) . . ? C2 C1 S3 109.4(6) . . ? C2 C1 S1 124.5(6) . . ? S3 C1 S1 126.0(5) . . ? C1 C2 C3 117.4(6) . . ? C1 C2 S2 118.2(6) . . ? C3 C2 S2 124.4(6) . . ? C4 S3 C1 90.1(5) . . ? C4 C3 C2 102.4(7) . . ? C3 C4 S3 120.7(8) . . ? C8 S6 C5 93.5(8) . . ? C7 C8 S6 115(2) . . ? C8 C7 C6 107(3) . . ? C6 S6A C8A 92.2(13) . . ? C7A C8A S6A 112(2) . . ? C8A C7A C5 107(2) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.543 _refine_diff_density_min -0.715 _refine_diff_density_rms 0.100 # start Validation Reply Form _vrf_PLAT241_brbzfe ; PROBLEM: Check High Ueq as Compared to Neighbors for C4 RESPONSE: The two terminal thiophenic rings showed evidence of disorder in the displacement parameters of C and S atoms, witch were successfully modelled over two positions in the case of C7, C8 and S6 with sof 55:45. For the C3, C4 and S3 atoms these could not be successfully modelled. ; _vrf_PLAT242_brbzfe ; PROBLEM: Check Low Ueq as Compared to Neighbors for C3 RESPONSE: The two terminal thiophenic rings showed evidence of disorder in the displacement parameters of C and S atoms, witch were successfully modelled over two positions in the case of C7, C8 and S6 with sof 55:45. For the C3, C4 and S3 atoms these could not be successfully modelled. ; _vrf_PLAT860_brbzfe ; PROBLEM: Number of Least-Squares Restraints ....... 16 RESPONSE: The two terminal thiophenic rings showed evidence of disorder in the displacement parameters of C and S atoms, witch were successfully modelled over two positions in the case of C7, C8 and S6 with sof 55:45. Restraints for displacement parameters were applied for atoms C6, C7 and C8 using DFIX and ISOR instructions in SHELXL97 (Sheldrick,1997). For the C3, C4 and S3 atoms these could not be successfully modelled. ;