# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Prof Mei Wang' _publ_contact_author_address ; School of Chemical Engineering Dalian University of Technology Zhongshan Road 158-46, Dalian 11601 Dalian 116012 CHINA ; _publ_contact_author_email SYMBUENO@DLUT.EDU.CN _publ_section_title ; Spectroscopic and Crystallographic Evidences for the N-Protonated FeIFeI Azadithiolate Complex Related to the Active Site of Fe-Only Hydrogenases ; _publ_contact_author ;Mei Wang Dalian University of technology, Zhongshan Road 158-46, 116012 Dalian, P. R. China, Fax: +86-411-83702185 ; loop_ _publ_author_name 'Mei Wang.' 'Bjorn Akermark' 'Weibing Dong.' 'Kun Jin.' 'Guanghua Li.' ; Xiaoyang Liu ; 'Licheng Sun.' 'Fujiun Wang.' data_o-br _database_code_depnum_ccdc_archive 'CCDC 244661' #------------------------------------------------------------------------------ _audit_creation_date 'Jul 10 10:01:24 2004' _audit_creation_method SHELXL-97 _audit_update_record ? #------------------------------------------------------------------------------ _computing_data_collection 'SMART (Bruker, 1997)' _computing_cell_refinement 'SMART (Bruker, 1997)' _computing_data_reduction 'SAINT (Bruker, 1997)' _computing_structure_solution 'SHELXS97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXP97 (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Bruker, 1997)' #------------------------------------------------------------------------------ _chemical_compound_source ? _chemical_name_common ? _chemical_formula_weight 555.97 _chemical_formula_analytical ? _chemical_formula_sum 'C15 H10 Br Fe2 N O6 S2' _chemical_formula_moiety 'C15 H10 Br Fe2 N O6 S2' _chemical_formula_structural ? _chemical_melting_point ? #------------------------------------------------------------------------------ _cell_length_a 13.3549(9) _cell_length_b 14.8313(10) _cell_length_c 19.7845(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3918.7(4) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? #------------------------------------------------------------------------------ _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'Pbca ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _exptl_crystal_description block _exptl_crystal_colour 'black red' _exptl_crystal_size_max 0.09 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.885 _exptl_crystal_F_000 2192 _exptl_absorpt_coefficient_mu 3.764 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.1928 _exptl_absorpt_correction_T_max 0.3238 _exptl_absorpt_process_details '(SADABS; Sheldrick, 1996)' _exptl_special_details ; ? ; #------------------------------------------------------------------------------ _diffrn_special_details ; ? ; _diffrn_ambient_temperature 293(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 CCD area-detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_decay_% ? _diffrn_reflns_number 27109 _reflns_number_observed 1801 _reflns_number_total 4888 _reflns_observed_criterion >2.0sigma(I) _diffrn_reflns_av_R_equivalents 0.1567 _diffrn_reflns_av_sigmaI/netI 0.1484 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.06 _diffrn_reflns_theta_max 28.39 _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 28.39 _diffrn_measured_fraction_theta_full 0.995 #------------------------------------------------------------------------------ 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' Br Br -0.2901 2.4595 '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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #------------------------------------------------------------------------------ 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 0.13622(5) 0.11229(4) 0.58564(3) 0.0422(2) Uani 1 1 d . . . Fe2 Fe 0.31957(5) 0.06864(4) 0.58780(3) 0.0426(2) Uani 1 1 d . . . S1 S 0.19157(10) -0.03126(7) 0.58696(6) 0.0452(3) Uani 1 1 d . . . S2 S 0.23902(10) 0.13301(8) 0.67538(6) 0.0442(3) Uani 1 1 d . . . Br1 Br 0.47761(5) -0.24339(4) 0.77392(3) 0.0694(2) Uani 1 1 d . . . O1 O 0.1223(3) 0.3080(2) 0.56783(19) 0.0869(14) Uani 1 1 d . . . O2 O 0.0813(3) 0.0824(3) 0.44299(19) 0.0881(15) Uani 1 1 d . . . O3 O -0.0566(3) 0.0813(3) 0.6534(2) 0.0822(14) Uani 1 1 d . . . O4 O 0.3662(4) -0.0042(3) 0.4544(2) 0.1068(18) Uani 1 1 d . . . O5 O 0.4898(3) -0.0068(3) 0.6623(2) 0.0831(14) Uani 1 1 d . . . O6 O 0.4072(3) 0.2446(3) 0.55430(17) 0.0751(12) Uani 1 1 d . . . N1 N 0.2244(4) -0.0442(3) 0.7258(2) 0.0603(13) Uani 1 1 d . . . C1 C 0.1297(4) 0.2313(4) 0.5746(2) 0.0554(15) Uani 1 1 d . . . C2 C 0.1025(4) 0.0937(3) 0.4983(3) 0.0570(16) Uani 1 1 d . . . C3 C 0.0189(4) 0.0949(3) 0.6268(3) 0.0511(14) Uani 1 1 d . . . C4 C 0.3478(4) 0.0261(3) 0.5058(3) 0.0637(17) Uani 1 1 d . . . C5 C 0.4234(5) 0.0200(4) 0.6326(3) 0.0580(16) Uani 1 1 d . . . C6 C 0.3728(4) 0.1767(4) 0.5679(2) 0.0492(14) Uani 1 1 d . . . C7 C 0.3540(4) -0.2320(3) 0.8212(2) 0.0442(13) Uani 1 1 d . . . C8 C 0.2866(4) -0.1647(3) 0.8029(2) 0.0400(13) Uani 1 1 d . . . C9 C 0.1967(4) -0.1622(3) 0.8383(2) 0.0561(16) Uani 1 1 d . . . H9 H 0.1490 -0.1191 0.8269 0.080 Uiso 1 1 calc . . . C10 C 0.1766(4) -0.2224(4) 0.8899(2) 0.0563(15) Uani 1 1 d . . . H10 H 0.1165 -0.2187 0.9135 0.080 Uiso 1 1 calc . . . C11 C 0.2436(5) -0.2862(4) 0.9062(3) 0.0679(18) Uani 1 1 d . . . H11 H 0.2293 -0.3270 0.9405 0.080 Uiso 1 1 calc . . . C12 C 0.3338(5) -0.2915(3) 0.8723(3) 0.0591(16) Uani 1 1 d . . . H12 H 0.3805 -0.3353 0.8841 0.080 Uiso 1 1 calc . . . C13 C 0.3118(5) -0.0953(3) 0.7484(2) 0.0583(15) Uani 1 1 d . . . H13A H 0.3614 -0.0537 0.7660 0.080 Uiso 1 1 calc . . . H13B H 0.3411 -0.1260 0.7099 0.080 Uiso 1 1 calc . . . C14 C 0.1662(4) -0.0796(3) 0.6722(3) 0.0561(15) Uani 1 1 d . . . H14A H 0.0961 -0.0701 0.6827 0.080 Uiso 1 1 calc . . . H14B H 0.1773 -0.1442 0.6701 0.080 Uiso 1 1 calc . . . C15 C 0.2114(4) 0.0482(3) 0.7425(2) 0.0574(16) Uani 1 1 d . . . H15A H 0.2538 0.0615 0.7811 0.080 Uiso 1 1 calc . . . H15B H 0.1426 0.0567 0.7568 0.080 Uiso 1 1 calc . . . 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 0.0407(5) 0.0366(4) 0.0494(5) 0.0003(3) -0.0019(4) -0.0021(4) Fe2 0.0398(5) 0.0392(4) 0.0487(4) -0.0054(4) 0.0075(4) -0.0011(4) S1 0.0514(10) 0.0348(7) 0.0493(8) -0.0040(6) 0.0000(7) -0.0032(6) S2 0.0462(10) 0.0397(8) 0.0466(8) -0.0067(6) 0.0018(6) -0.0009(7) Br1 0.0486(4) 0.0729(4) 0.0867(4) -0.0154(3) -0.0019(3) 0.0029(3) O1 0.106(4) 0.041(2) 0.114(4) 0.006(2) 0.003(3) 0.002(3) O2 0.116(4) 0.092(3) 0.056(3) 0.002(2) -0.027(3) -0.022(3) O3 0.054(3) 0.081(3) 0.112(4) 0.000(2) 0.024(3) 0.001(3) O4 0.163(5) 0.083(3) 0.074(3) -0.028(2) 0.051(3) -0.010(3) O5 0.049(3) 0.096(3) 0.104(4) 0.036(2) 0.002(2) 0.009(3) O6 0.097(4) 0.056(3) 0.073(3) 0.003(2) -0.008(2) -0.028(2) N1 0.076(4) 0.047(3) 0.058(3) 0.010(2) -0.013(3) 0.003(3) C1 0.053(4) 0.057(4) 0.055(4) 0.002(3) -0.007(3) -0.003(3) C2 0.060(4) 0.041(3) 0.070(4) 0.005(3) -0.006(3) -0.010(3) C3 0.046(4) 0.038(3) 0.068(4) 0.001(3) -0.009(3) 0.002(3) C4 0.064(5) 0.053(4) 0.075(5) -0.003(3) 0.014(3) -0.007(3) C5 0.054(5) 0.061(4) 0.059(4) 0.016(3) 0.016(3) 0.003(3) C6 0.056(4) 0.055(4) 0.036(3) -0.006(3) -0.003(3) 0.002(3) C7 0.046(4) 0.044(3) 0.043(3) -0.008(3) -0.009(2) -0.005(3) C8 0.047(4) 0.040(3) 0.034(3) -0.005(2) -0.002(2) -0.001(3) C9 0.060(5) 0.060(4) 0.048(4) 0.000(3) -0.001(3) 0.008(3) C10 0.064(5) 0.066(4) 0.038(3) 0.004(3) 0.016(3) -0.012(3) C11 0.085(6) 0.070(4) 0.049(4) 0.017(3) -0.006(4) -0.016(4) C12 0.072(5) 0.044(3) 0.062(4) 0.007(3) -0.018(3) 0.000(3) C13 0.068(5) 0.054(4) 0.053(4) 0.008(3) 0.006(3) -0.003(3) C14 0.057(4) 0.037(3) 0.074(4) 0.009(3) -0.001(3) -0.004(3) C15 0.064(5) 0.055(4) 0.053(4) -0.001(3) 0.008(3) 0.008(3) #------------------------------------------------------------------------------ _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^)+(0.0184P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4888 _refine_ls_number_parameters 244 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1522 _refine_ls_R_factor_gt 0.0403 _refine_ls_wR_factor_ref 0.0793 _refine_ls_wR_factor_gt 0.0607 _refine_ls_goodness_of_fit_ref 0.786 _refine_ls_restrained_S_all 0.786 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.445 _refine_diff_density_min -0.519 _refine_diff_density_rms 0.093 #------------------------------------------------------------------------------ _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 C1 1.781(6) . ? Fe1 C3 1.785(6) . ? Fe1 C2 1.806(6) . ? Fe1 S1 2.2539(13) . ? Fe1 S2 2.2652(14) . ? Fe1 Fe2 2.5330(10) . ? Fe2 C4 1.781(6) . ? Fe2 C5 1.797(6) . ? Fe2 C6 1.797(6) . ? Fe2 S2 2.2518(13) . ? Fe2 S1 2.2622(14) . ? S1 C14 1.863(5) . ? S2 C15 1.866(5) . ? Br1 C7 1.905(5) . ? O1 C1 1.150(5) . ? O2 C2 1.143(5) . ? O3 C3 1.155(6) . ? O4 C4 1.139(5) . ? O5 C5 1.135(6) . ? O6 C6 1.139(5) . ? N1 C14 1.416(6) . ? N1 C15 1.420(5) . ? N1 C13 1.462(6) . ? C7 C12 1.369(6) . ? C7 C8 1.392(6) . ? C8 C9 1.391(7) . ? C8 C13 1.528(6) . ? C9 C10 1.384(6) . ? C9 H9 0.9300 . ? C10 C11 1.341(7) . ? C10 H10 0.9300 . ? C11 C12 1.380(7) . ? C11 H11 0.9300 . ? C12 H12 0.9300 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? #------------------------------------------------------------------------------ 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 C1 Fe1 C3 99.0(2) . . ? C1 Fe1 C2 91.3(2) . . ? C3 Fe1 C2 101.3(2) . . ? C1 Fe1 S1 162.54(18) . . ? C3 Fe1 S1 98.40(15) . . ? C2 Fe1 S1 87.06(16) . . ? C1 Fe1 S2 89.48(16) . . ? C3 Fe1 S2 101.19(17) . . ? C2 Fe1 S2 157.12(18) . . ? S1 Fe1 S2 85.43(5) . . ? C1 Fe1 Fe2 107.63(18) . . ? C3 Fe1 Fe2 143.52(16) . . ? C2 Fe1 Fe2 102.60(18) . . ? S1 Fe1 Fe2 56.04(4) . . ? S2 Fe1 Fe2 55.64(4) . . ? C4 Fe2 C5 98.3(3) . . ? C4 Fe2 C6 91.9(2) . . ? C5 Fe2 C6 99.2(2) . . ? C4 Fe2 S2 162.2(2) . . ? C5 Fe2 S2 99.15(18) . . ? C6 Fe2 S2 88.84(15) . . ? C4 Fe2 S1 85.48(18) . . ? C5 Fe2 S1 108.89(18) . . ? C6 Fe2 S1 151.83(17) . . ? S2 Fe2 S1 85.54(5) . . ? C4 Fe2 Fe1 106.25(19) . . ? C5 Fe2 Fe1 148.95(18) . . ? C6 Fe2 Fe1 98.69(17) . . ? S2 Fe2 Fe1 56.14(4) . . ? S1 Fe2 Fe1 55.73(4) . . ? C14 S1 Fe1 108.34(16) . . ? C14 S1 Fe2 112.51(18) . . ? Fe1 S1 Fe2 68.23(4) . . ? C15 S2 Fe2 110.87(16) . . ? C15 S2 Fe1 110.29(17) . . ? Fe2 S2 Fe1 68.22(4) . . ? C14 N1 C15 117.8(4) . . ? C14 N1 C13 118.3(4) . . ? C15 N1 C13 121.7(4) . . ? O1 C1 Fe1 177.9(5) . . ? O2 C2 Fe1 179.7(5) . . ? O3 C3 Fe1 178.2(5) . . ? O4 C4 Fe2 177.5(5) . . ? O5 C5 Fe2 176.7(6) . . ? O6 C6 Fe2 178.9(5) . . ? C12 C7 C8 121.8(5) . . ? C12 C7 Br1 118.5(4) . . ? C8 C7 Br1 119.7(4) . . ? C9 C8 C7 116.5(4) . . ? C9 C8 C13 121.8(5) . . ? C7 C8 C13 121.7(5) . . ? C10 C9 C8 121.4(5) . . ? C10 C9 H9 119.3 . . ? C8 C9 H9 119.3 . . ? C11 C10 C9 120.2(5) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C10 C11 C12 120.4(5) . . ? C10 C11 H11 119.8 . . ? C12 C11 H11 119.8 . . ? C7 C12 C11 119.6(5) . . ? C7 C12 H12 120.2 . . ? C11 C12 H12 120.2 . . ? N1 C13 C8 112.9(5) . . ? N1 C13 H13A 109.0 . . ? C8 C13 H13A 109.0 . . ? N1 C13 H13B 109.0 . . ? C8 C13 H13B 109.0 . . ? H13A C13 H13B 107.8 . . ? N1 C14 S1 115.8(4) . . ? N1 C14 H14A 108.3 . . ? S1 C14 H14A 108.3 . . ? N1 C14 H14B 108.3 . . ? S1 C14 H14B 108.3 . . ? H14A C14 H14B 107.4 . . ? N1 C15 S2 117.4(3) . . ? N1 C15 H15A 107.9 . . ? S2 C15 H15A 107.9 . . ? N1 C15 H15B 107.9 . . ? S2 C15 H15B 107.9 . . ? H15A C15 H15B 107.2 . . ? #===END # Copyright The Royal Society of Chemistry, 2004 # CCDC Number: 258455 data_o-br+H _database_code_depnum_ccdc_archive 'CCDC 258455' #------------------------------------------------------------------------------ _audit_creation_date 'Aug 15 14:01:24 2004' _audit_creation_method SHELXL-97 _audit_update_record ? #------------------------------------------------------------------------------ _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SHELXP-97 _computing_publication_material SHELXTL #------------------------------------------------------------------------------ _chemical_compound_source ? _chemical_name_common ? _chemical_formula_weight 656.43 _chemical_formula_analytical ? _chemical_formula_sum 'C15 H11 Br Cl Fe2 N O10 S2' _chemical_formula_moiety 'C15 H11 Br Cl Fe2 N O10 S2' _chemical_formula_structural ? _chemical_melting_point ? #------------------------------------------------------------------------------ _cell_length_a 22.953(10) _cell_length_b 6.611(3) _cell_length_c 15.033(6) _cell_angle_alpha 90.00 _cell_angle_beta 104.63(3) _cell_angle_gamma 90.00 _cell_volume 2207.2(16) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? #------------------------------------------------------------------------------ _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/c _symmetry_Int_Tables_number 9 _symmetry_space_group_name_Hall ? 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' _exptl_crystal_description block _exptl_crystal_colour 'black red' _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.975 _exptl_crystal_F_000 1296 _exptl_absorpt_coefficient_mu 3.488 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.2474 _exptl_absorpt_correction_T_max 0.4437 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; #------------------------------------------------------------------------------ _diffrn_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_radiation_detector 'Imaging Plate' _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_decay_% 0.00 _diffrn_reflns_number 14151 _reflns_number_observed 2403 _reflns_number_total 5515 _reflns_observed_criterion >2.0sigma(I) _diffrn_reflns_av_R_equivalents 0.2544 _diffrn_reflns_av_sigmaI/netI 0.2231 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.72 _diffrn_reflns_theta_max 28.82 _diffrn_measured_fraction_theta_max 0.958 _diffrn_reflns_theta_full 28.82 _diffrn_measured_fraction_theta_full 0.958 #------------------------------------------------------------------------------ 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' 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' 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' #------------------------------------------------------------------------------ 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 N1 N 0.2035(2) 0.0113(11) 0.3208(4) 0.0267(16) Uani 1 1 d . . . H1 H 0.2093 0.0631 0.3785 0.080 Uiso 1 1 calc . . . Cl1 Cl 0.16705(9) -0.3377(4) 0.06221(15) 0.0388(6) Uani 1 1 d . . . Fe1 Fe 0.36801(5) -0.0032(2) 0.30550(9) 0.0344(4) Uani 1 1 d . . . Fe2 Fe 0.34667(5) 0.12214(19) 0.45080(9) 0.0303(3) Uani 1 1 d . . . Br1 Br 0.12671(5) 0.35784(19) 0.40548(8) 0.0577(4) Uani 1 1 d . . . S1 S 0.31625(8) -0.1801(3) 0.38682(15) 0.0297(5) Uani 1 1 d . . . S2 S 0.30221(8) 0.2453(3) 0.31000(16) 0.0298(5) Uani 1 1 d . . . O1 O 0.4448(4) 0.3079(16) 0.2569(8) 0.100(4) Uani 1 1 d . . . O2 O 0.4729(3) -0.2608(14) 0.3712(7) 0.092(3) Uani 1 1 d . . . O3 O 0.3265(3) -0.1967(17) 0.1243(6) 0.094(3) Uani 1 1 d . . . O4 O 0.4389(3) -0.0983(12) 0.5854(6) 0.075(3) Uani 1 1 d . . . O5 O 0.2742(3) 0.2562(15) 0.5736(6) 0.080(3) Uani 1 1 d . . . O6 O 0.4246(3) 0.4750(12) 0.4880(6) 0.072(3) Uani 1 1 d . . . O7 O 0.1052(3) -0.3471(14) 0.0164(6) 0.081(3) Uani 1 1 d . . . O8 O 0.2012(3) -0.3919(13) 0.0003(5) 0.065(2) Uani 1 1 d . . . O9 O 0.1812(4) -0.4649(14) 0.1395(5) 0.082(3) Uani 1 1 d . . . O10 O 0.1825(3) -0.1337(11) 0.0940(6) 0.066(2) Uani 1 1 d . . . C1 C 0.4166(4) 0.193(2) 0.2765(8) 0.059(3) Uani 1 1 d . . . C2 C 0.4312(4) -0.1616(18) 0.3458(8) 0.053(3) Uani 1 1 d . . . C3 C 0.3420(4) -0.1157(16) 0.1949(7) 0.044(3) Uani 1 1 d . . . C4 C 0.4021(4) -0.0141(18) 0.5336(8) 0.054(3) Uani 1 1 d . . . C5 C 0.3002(4) 0.1989(17) 0.5258(7) 0.045(3) Uani 1 1 d . . . C6 C 0.3936(4) 0.3416(18) 0.4712(7) 0.048(3) Uani 1 1 d . . . C7 C 0.0867(4) 0.3059(16) 0.2809(7) 0.044(3) Uani 1 1 d . . . C8 C 0.0971(3) 0.1317(14) 0.2396(6) 0.032(2) Uani 1 1 d . . . C9 C 0.0662(3) 0.1067(15) 0.1413(8) 0.047(3) Uani 1 1 d . . . H9 H 0.0726 -0.0080 0.1092 0.080 Uiso 1 1 calc . . . C10 C 0.0282(4) 0.255(2) 0.0987(7) 0.056(3) Uani 1 1 d . . . H8 H 0.0089 0.2427 0.0367 0.080 Uiso 1 1 calc . . . C11 C 0.0180(4) 0.4219(17) 0.1457(8) 0.051(3) Uani 1 1 d . . . H7 H -0.0093 0.5188 0.1156 0.080 Uiso 1 1 calc . . . C12 C 0.0469(4) 0.4500(15) 0.2359(8) 0.049(3) Uani 1 1 d . . . H6 H 0.0397 0.5657 0.2667 0.080 Uiso 1 1 calc . . . C13 C 0.1361(3) -0.0394(13) 0.2847(6) 0.031(2) Uani 1 1 d . . . H3A H 0.1321 -0.1493 0.2408 0.080 Uiso 1 1 calc . . . H3B H 0.1212 -0.0876 0.3357 0.080 Uiso 1 1 calc . . . C14 C 0.2366(3) -0.1905(12) 0.3284(6) 0.0245(18) Uani 1 1 d . . . H1A H 0.2325 -0.2435 0.2670 0.080 Uiso 1 1 calc . . . H1B H 0.2171 -0.2851 0.3609 0.080 Uiso 1 1 calc . . . C15 C 0.2254(3) 0.1588(15) 0.2650(6) 0.034(2) Uani 1 1 d . . . H2A H 0.1991 0.2757 0.2567 0.080 Uiso 1 1 calc . . . H2B H 0.2222 0.1003 0.2048 0.080 Uiso 1 1 calc . . . 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 N1 0.017(3) 0.039(5) 0.023(4) 0.002(3) 0.003(3) 0.001(3) Cl1 0.0406(11) 0.0469(16) 0.0282(12) -0.0001(11) 0.0072(9) 0.0052(10) Fe1 0.0260(6) 0.0435(9) 0.0346(7) 0.0049(7) 0.0094(5) 0.0027(5) Fe2 0.0294(6) 0.0300(8) 0.0277(7) 0.0028(6) 0.0004(5) -0.0071(5) Br1 0.0653(7) 0.0597(8) 0.0475(7) -0.0161(6) 0.0129(5) 0.0012(5) S1 0.0247(9) 0.0282(12) 0.0325(12) 0.0017(10) 0.0006(8) -0.0008(8) S2 0.0286(10) 0.0285(13) 0.0312(12) 0.0054(10) 0.0056(9) -0.0013(8) O1 0.086(6) 0.098(8) 0.137(9) 0.035(7) 0.065(6) -0.022(5) O2 0.044(4) 0.078(7) 0.156(10) 0.061(6) 0.028(5) 0.023(4) O3 0.082(5) 0.128(9) 0.069(6) -0.056(6) 0.018(5) 0.024(5) O4 0.087(5) 0.038(5) 0.068(6) 0.014(4) -0.041(4) -0.008(4) O5 0.080(5) 0.097(8) 0.076(6) -0.036(5) 0.045(5) -0.031(5) O6 0.046(4) 0.054(6) 0.100(6) 0.016(5) -0.013(4) -0.023(4) O7 0.037(4) 0.099(8) 0.099(7) -0.007(6) 0.003(4) -0.014(4) O8 0.081(5) 0.084(7) 0.040(4) -0.011(4) 0.034(4) 0.007(4) O9 0.117(6) 0.084(7) 0.043(5) 0.035(5) 0.018(5) 0.019(5) O10 0.076(5) 0.048(5) 0.073(6) -0.032(4) 0.016(4) -0.005(4) C1 0.047(6) 0.080(9) 0.059(8) 0.008(7) 0.029(5) 0.012(6) C2 0.039(5) 0.071(9) 0.054(7) 0.003(6) 0.020(5) -0.009(5) C3 0.038(5) 0.056(7) 0.044(6) -0.014(5) 0.019(4) 0.010(4) C4 0.039(5) 0.055(8) 0.058(7) -0.007(6) -0.008(5) -0.013(5) C5 0.050(5) 0.056(7) 0.028(5) -0.006(5) 0.009(5) -0.022(5) C6 0.030(5) 0.062(8) 0.045(6) 0.015(6) -0.008(4) -0.002(5) C7 0.037(5) 0.050(7) 0.047(6) -0.013(5) 0.014(4) -0.007(4) C8 0.019(4) 0.048(6) 0.028(5) 0.005(5) 0.005(3) 0.006(4) C9 0.025(4) 0.043(6) 0.074(8) 0.009(6) 0.016(5) 0.009(4) C10 0.043(5) 0.081(9) 0.037(6) 0.008(6) -0.003(5) 0.009(5) C11 0.048(6) 0.044(7) 0.058(7) 0.020(6) 0.008(5) 0.013(5) C12 0.026(4) 0.041(6) 0.083(8) 0.005(6) 0.020(5) 0.009(4) C13 0.019(4) 0.032(5) 0.037(5) -0.001(4) 0.000(3) -0.006(3) C14 0.018(3) 0.020(4) 0.030(5) 0.001(4) -0.004(3) 0.002(3) C15 0.028(4) 0.046(6) 0.024(5) 0.008(4) 0.001(3) -0.003(4) #------------------------------------------------------------------------------ _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^)+(0.0699P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0022(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5515 _refine_ls_number_parameters 290 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.2075 _refine_ls_R_factor_gt 0.0865 _refine_ls_wR_factor_ref 0.1947 _refine_ls_wR_factor_gt 0.1479 _refine_ls_goodness_of_fit_ref 0.961 _refine_ls_restrained_S_all 0.961 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_min -0.87 _refine_diff_density_max 0.85 #------------------------------------------------------------------------------ _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 N1 C15 1.456(11) . ? N1 C14 1.525(10) . ? N1 C13 1.542(9) . ? N1 H1 0.9100 . ? Cl1 O9 1.404(8) . ? Cl1 O8 1.405(7) . ? Cl1 O7 1.414(6) . ? Cl1 O10 1.445(7) . ? Fe1 C2 1.767(11) . ? Fe1 C3 1.781(10) . ? Fe1 C1 1.831(13) . ? Fe1 S1 2.237(3) . ? Fe1 S2 2.244(3) . ? Fe1 Fe2 2.498(2) . ? Fe2 C4 1.782(11) . ? Fe2 C6 1.787(11) . ? Fe2 C5 1.810(11) . ? Fe2 S1 2.251(3) . ? Fe2 S2 2.257(3) . ? Br1 C7 1.897(10) . ? S1 C14 1.819(7) . ? S2 C15 1.813(8) . ? O1 C1 1.089(13) . ? O2 C2 1.144(11) . ? O3 C3 1.162(11) . ? O4 C4 1.140(11) . ? O5 C5 1.110(12) . ? O6 C6 1.120(11) . ? C7 C8 1.358(13) . ? C7 C12 1.375(13) . ? C8 C9 1.478(13) . ? C8 C13 1.495(11) . ? C9 C10 1.362(13) . ? C9 H9 0.9300 . ? C10 C11 1.360(16) . ? C10 H8 0.9300 . ? C11 C12 1.363(14) . ? C11 H7 0.9300 . ? C12 H6 0.9300 . ? C13 H3A 0.9700 . ? C13 H3B 0.9700 . ? C14 H1A 0.9700 . ? C14 H1B 0.9700 . ? C15 H2A 0.9700 . ? C15 H2B 0.9700 . ? #------------------------------------------------------------------------------ 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 C15 N1 C14 113.1(6) . . ? C15 N1 C13 113.8(6) . . ? C14 N1 C13 105.8(6) . . ? C15 N1 H1 108.0 . . ? C14 N1 H1 108.0 . . ? C13 N1 H1 108.0 . . ? O9 Cl1 O8 110.1(5) . . ? O9 Cl1 O7 111.8(5) . . ? O8 Cl1 O7 109.0(5) . . ? O9 Cl1 O10 107.4(5) . . ? O8 Cl1 O10 109.0(5) . . ? O7 Cl1 O10 109.5(5) . . ? C2 Fe1 C3 97.2(5) . . ? C2 Fe1 C1 90.3(5) . . ? C3 Fe1 C1 98.8(5) . . ? C2 Fe1 S1 90.3(3) . . ? C3 Fe1 S1 101.1(3) . . ? C1 Fe1 S1 159.8(4) . . ? C2 Fe1 S2 157.5(4) . . ? C3 Fe1 S2 105.3(3) . . ? C1 Fe1 S2 86.8(4) . . ? S1 Fe1 S2 84.95(9) . . ? C2 Fe1 Fe2 102.8(4) . . ? C3 Fe1 Fe2 149.4(3) . . ? C1 Fe1 Fe2 103.8(4) . . ? S1 Fe1 Fe2 56.44(7) . . ? S2 Fe1 Fe2 56.54(7) . . ? C4 Fe2 C6 89.8(4) . . ? C4 Fe2 C5 97.8(5) . . ? C6 Fe2 C5 95.2(5) . . ? C4 Fe2 S1 86.5(3) . . ? C6 Fe2 S1 154.5(4) . . ? C5 Fe2 S1 110.3(3) . . ? C4 Fe2 S2 155.6(4) . . ? C6 Fe2 S2 88.8(3) . . ? C5 Fe2 S2 106.6(3) . . ? S1 Fe2 S2 84.35(9) . . ? C4 Fe2 Fe1 100.4(4) . . ? C6 Fe2 Fe1 100.2(4) . . ? C5 Fe2 Fe1 156.2(3) . . ? S1 Fe2 Fe1 55.93(7) . . ? S2 Fe2 Fe1 56.06(7) . . ? C14 S1 Fe1 111.3(3) . . ? C14 S1 Fe2 113.9(3) . . ? Fe1 S1 Fe2 67.63(8) . . ? C15 S2 Fe1 110.9(3) . . ? C15 S2 Fe2 113.7(3) . . ? Fe1 S2 Fe2 67.41(8) . . ? O1 C1 Fe1 178.2(12) . . ? O2 C2 Fe1 178.4(10) . . ? O3 C3 Fe1 176.9(10) . . ? O4 C4 Fe2 177.8(10) . . ? O5 C5 Fe2 175.4(10) . . ? O6 C6 Fe2 176.5(9) . . ? C8 C7 C12 122.3(9) . . ? C8 C7 Br1 120.5(7) . . ? C12 C7 Br1 117.2(8) . . ? C7 C8 C9 117.2(8) . . ? C7 C8 C13 126.1(8) . . ? C9 C8 C13 116.7(8) . . ? C10 C9 C8 118.5(10) . . ? C10 C9 H9 120.7 . . ? C8 C9 H9 120.7 . . ? C11 C10 C9 121.0(10) . . ? C11 C10 H8 119.5 . . ? C9 C10 H8 119.5 . . ? C10 C11 C12 121.5(9) . . ? C10 C11 H7 119.3 . . ? C12 C11 H7 119.3 . . ? C11 C12 C7 119.5(10) . . ? C11 C12 H6 120.3 . . ? C7 C12 H6 120.3 . . ? C8 C13 N1 115.4(7) . . ? C8 C13 H3A 108.4 . . ? N1 C13 H3A 108.4 . . ? C8 C13 H3B 108.4 . . ? N1 C13 H3B 108.4 . . ? H3A C13 H3B 107.5 . . ? N1 C14 S1 115.1(5) . . ? N1 C14 H1A 108.5 . . ? S1 C14 H1A 108.5 . . ? N1 C14 H1B 108.5 . . ? S1 C14 H1B 108.5 . . ? H1A C14 H1B 107.5 . . ? N1 C15 S2 116.2(5) . . ? N1 C15 H2A 108.2 . . ? S2 C15 H2A 108.2 . . ? N1 C15 H2B 108.2 . . ? S2 C15 H2B 108.2 . . ? H2A C15 H2B 107.4 . . ? #------------------------------------------------------------------------------ loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1 O8 0.91 2.20 2.826(9) 125.2 4_556 N1 H1 Br1 0.91 2.82 3.334(7) 117.2 . #===END