Supplementary Material for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 177 _publ_requested_journal OBC loop_ _publ_author_name 'Liam Cox' 'Benson M. Kariuki' 'Keith Reeves' 'Iwan Williams' _publ_contact_author 'Liam R. Cox' _publ_contact_author_address ; School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK ; _publ_contact_author_email l.r.cox@bham.ac.uk _publ_section_title ; Stereoselective Synthesis of 2-Dienyl-Substituted Piperidines using an 4-Dienetricarbonyliron Complex as the Stereocontrolling Element in a Double Reductive Amination Cascade ; _publ_section_references ; PLATON- (a) Spek, A. L. (1990) Acta Cryst. A46, C34. (b) Spek, A. L. (1998) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. SHELXTL, program suite for structure solution and refinement, Bruker AXS, Inc. 5465 East Cheryl Parkway, Madison, Wisconsin 53711-5373, USA SMART, program for instrument control and data aquisition, Bruker AXS, Inc. 5465 East Cheryl Parkway, Madison, Wisconsin 53711-5373, USA SAINTPLUS, program suite for data processing, Bruker AXS, Inc. 5465 East Cheryl Parkway, Madison, Wisconsin 53711-5373, USA ; data_iwfe _database_code_depnum_ccdc_archive 'CCDC 654317' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C10 H11 Fe N O4' _chemical_formula_sum 'C10 H11 Fe N O4' _chemical_formula_weight 265.05 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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' Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _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+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 11.3721(14) _cell_length_b 9.8350(13) _cell_length_c 20.671(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2311.9(5) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1137 _cell_measurement_theta_min 4.28 _cell_measurement_theta_max 69.80 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.523 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1088 _exptl_absorpt_coefficient_mu 10.483 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.1451 _exptl_absorpt_correction_T_max 0.3660 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart 6000 CCD' _diffrn_measurement_method 'CCD scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9881 _diffrn_reflns_av_R_equivalents 0.0701 _diffrn_reflns_av_sigmaI/netI 0.0639 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 4.28 _diffrn_reflns_theta_max 69.80 _reflns_number_total 1940 _reflns_number_gt 1137 _reflns_threshold_expression >2sigma(I) _computing_data_collection SMART _computing_cell_refinement SAINTPLUS _computing_data_reduction SAINTPLUS _computing_structure_solution SHELXTL _computing_structure_refinement SHELXTL _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0612P)^2^+1.7192P] 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 1940 _refine_ls_number_parameters 147 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1026 _refine_ls_R_factor_gt 0.0559 _refine_ls_wR_factor_ref 0.1444 _refine_ls_wR_factor_gt 0.1264 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.006 _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 C1 C 0.9585(5) 0.2268(6) 0.6352(3) 0.0688(18) Uani 1 1 d . . . H1A H 0.9624 0.2509 0.5902 0.103 Uiso 1 1 calc R . . H1B H 1.0089 0.1504 0.6432 0.103 Uiso 1 1 calc R . . H1C H 0.9837 0.3025 0.6610 0.103 Uiso 1 1 calc R . . C2 C 0.7567(5) 0.2830(5) 0.6649(2) 0.0442(13) Uani 1 1 d . . . C3 C 0.6394(5) 0.2231(5) 0.6780(2) 0.0449(13) Uani 1 1 d . . . H3 H 0.6292 0.1296 0.6740 0.054 Uiso 1 1 calc R . . C4 C 0.5426(5) 0.3049(5) 0.6963(2) 0.0473(14) Uani 1 1 d . . . H4 H 0.5526 0.3950 0.7087 0.057 Uiso 1 1 calc R . . C5 C 0.4316(5) 0.2447(6) 0.6951(3) 0.0563(15) Uani 1 1 d . . . H5 H 0.3658 0.2943 0.7076 0.068 Uiso 1 1 calc R . . C6 C 0.4193(5) 0.1088(6) 0.6749(3) 0.0546(15) Uani 1 1 d . . . H6 H 0.4862 0.0566 0.6676 0.066 Uiso 1 1 calc R . . C7 C 0.3001(5) 0.0464(7) 0.6647(3) 0.089(2) Uani 1 1 d . . . H7A H 0.2759 0.0007 0.7035 0.134 Uiso 1 1 calc R . . H7B H 0.3038 -0.0178 0.6298 0.134 Uiso 1 1 calc R . . H7C H 0.2444 0.1165 0.6544 0.134 Uiso 1 1 calc R . . C8 C 0.3740(6) 0.2599(5) 0.5614(3) 0.0605(16) Uani 1 1 d . . . C9 C 0.5723(5) 0.0968(6) 0.5601(3) 0.0528(14) Uani 1 1 d . . . C10 C 0.5749(5) 0.3745(5) 0.5626(3) 0.0522(15) Uani 1 1 d . . . Fe1 Fe 0.50803(6) 0.23569(7) 0.60511(4) 0.0424(3) Uani 1 1 d . . . N1 N 0.8394(4) 0.1918(4) 0.6518(2) 0.0539(13) Uani 1 1 d . . . H1 H 0.8207 0.1071 0.6534 0.065 Uiso 1 1 calc R . . O1 O 0.7749(3) 0.4061(3) 0.66738(19) 0.0595(11) Uani 1 1 d . . . O2 O 0.2884(4) 0.2709(4) 0.5340(3) 0.0885(15) Uani 1 1 d . . . O3 O 0.6161(4) 0.0125(4) 0.5327(2) 0.0786(13) Uani 1 1 d . . . O4 O 0.6165(4) 0.4603(4) 0.5345(2) 0.0783(13) Uani 1 1 d . . . 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 C1 0.058(4) 0.063(4) 0.085(5) -0.006(4) -0.001(3) 0.000(3) C2 0.055(3) 0.041(3) 0.037(3) 0.001(3) -0.013(2) 0.001(3) C3 0.059(3) 0.031(3) 0.045(3) -0.006(2) -0.013(3) 0.002(3) C4 0.075(4) 0.043(3) 0.023(3) -0.008(2) -0.001(2) 0.008(3) C5 0.060(4) 0.065(4) 0.044(3) 0.000(3) 0.008(3) 0.008(3) C6 0.047(3) 0.057(3) 0.059(4) 0.001(3) 0.018(3) -0.003(3) C7 0.065(4) 0.096(5) 0.106(6) 0.016(5) 0.006(4) -0.022(4) C8 0.059(4) 0.050(3) 0.072(4) -0.002(3) 0.004(3) 0.000(3) C9 0.053(4) 0.054(3) 0.051(4) -0.003(3) -0.010(3) 0.001(3) C10 0.050(3) 0.044(3) 0.062(4) 0.002(3) -0.007(3) -0.003(3) Fe1 0.0470(5) 0.0383(5) 0.0417(5) -0.0009(4) -0.0023(4) 0.0015(4) N1 0.047(3) 0.038(2) 0.077(4) -0.004(2) -0.013(3) 0.004(2) O1 0.067(3) 0.0288(19) 0.082(3) -0.005(2) -0.006(2) -0.0031(18) O2 0.063(3) 0.087(3) 0.115(4) 0.012(3) -0.030(3) 0.004(3) O3 0.074(3) 0.074(3) 0.087(3) -0.034(3) -0.005(2) 0.013(2) O4 0.075(3) 0.069(3) 0.091(3) 0.031(3) -0.007(2) -0.013(2) _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 C1 N1 1.440(7) . ? C2 O1 1.229(5) . ? C2 N1 1.327(6) . ? C2 C3 1.484(7) . ? C3 C4 1.415(7) . ? C3 Fe1 2.125(5) . ? C4 C5 1.393(8) . ? C4 Fe1 2.043(5) . ? C5 C6 1.408(7) . ? C5 Fe1 2.055(5) . ? C6 C7 1.503(8) . ? C6 Fe1 2.157(5) . ? C8 O2 1.133(6) . ? C8 Fe1 1.787(7) . ? C9 O3 1.121(6) . ? C9 Fe1 1.807(6) . ? C10 O4 1.129(6) . ? C10 Fe1 1.793(6) . ? 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 O1 C2 N1 123.7(5) . . ? O1 C2 C3 122.3(5) . . ? N1 C2 C3 113.9(4) . . ? C4 C3 C2 121.5(4) . . ? C4 C3 Fe1 67.0(3) . . ? C2 C3 Fe1 118.7(3) . . ? C5 C4 C3 117.3(5) . . ? C5 C4 Fe1 70.6(3) . . ? C3 C4 Fe1 73.3(3) . . ? C4 C5 C6 119.9(5) . . ? C4 C5 Fe1 69.6(3) . . ? C6 C5 Fe1 74.5(3) . . ? C5 C6 C7 121.3(5) . . ? C5 C6 Fe1 66.6(3) . . ? C7 C6 Fe1 124.4(4) . . ? O2 C8 Fe1 177.8(5) . . ? O3 C9 Fe1 177.5(5) . . ? O4 C10 Fe1 178.4(5) . . ? C8 Fe1 C10 90.7(3) . . ? C8 Fe1 C9 100.7(3) . . ? C10 Fe1 C9 98.7(2) . . ? C8 Fe1 C4 125.9(2) . . ? C10 Fe1 C4 96.8(2) . . ? C9 Fe1 C4 130.5(2) . . ? C8 Fe1 C5 95.2(3) . . ? C10 Fe1 C5 126.2(2) . . ? C9 Fe1 C5 132.1(2) . . ? C4 Fe1 C5 39.8(2) . . ? C8 Fe1 C3 164.9(2) . . ? C10 Fe1 C3 95.4(2) . . ? C9 Fe1 C3 92.1(2) . . ? C4 Fe1 C3 39.65(19) . . ? C5 Fe1 C3 70.0(2) . . ? C8 Fe1 C6 90.9(2) . . ? C10 Fe1 C6 165.1(2) . . ? C9 Fe1 C6 95.5(2) . . ? C4 Fe1 C6 70.5(2) . . ? C5 Fe1 C6 38.95(19) . . ? C3 Fe1 C6 79.7(2) . . ? C2 N1 C1 123.6(5) . . ? _diffrn_measured_fraction_theta_max 0.891 _diffrn_reflns_theta_full 69.80 _diffrn_measured_fraction_theta_full 0.891 _refine_diff_density_max 0.581 _refine_diff_density_min -0.419 _refine_diff_density_rms 0.065 data_bromopi _database_code_depnum_ccdc_archive 'CCDC 656908' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H22 Br Fe N O3' _chemical_formula_sum 'C17 H22 Br Fe N O3' _chemical_formula_weight 424.12 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 '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 7.6829(3) _cell_length_b 10.9941(4) _cell_length_c 12.0958(4) _cell_angle_alpha 69.757(2) _cell_angle_beta 78.689(2) _cell_angle_gamma 89.592(2) _cell_volume 937.92(6) _cell_formula_units_Z 2 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 2538 _cell_measurement_theta_min 3.98 _cell_measurement_theta_max 70.10 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.502 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 432 _exptl_absorpt_coefficient_mu 9.047 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.2648 _exptl_absorpt_correction_T_max 0.3640 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart 6000 CCD' _diffrn_measurement_method 'CCD scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5900 _diffrn_reflns_av_R_equivalents 0.0226 _diffrn_reflns_av_sigmaI/netI 0.0340 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.98 _diffrn_reflns_theta_max 70.10 _reflns_number_total 3116 _reflns_number_gt 2538 _reflns_threshold_expression >2sigma(I) _computing_data_collection SMART _computing_cell_refinement SAINTPLUS _computing_data_reduction SAINTPLUS _computing_structure_solution SHELXTL _computing_structure_refinement SHELXTL _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0580P)^2^+0.7082P] 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 3116 _refine_ls_number_parameters 210 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0567 _refine_ls_R_factor_gt 0.0433 _refine_ls_wR_factor_ref 0.1167 _refine_ls_wR_factor_gt 0.1091 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0.008 _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 C1 C 0.4144(6) 0.3853(5) 0.4414(4) 0.0624(12) Uani 1 1 d . . . H1A H 0.3938 0.3173 0.5189 0.094 Uiso 1 1 calc R . . H1B H 0.3652 0.4631 0.4493 0.094 Uiso 1 1 calc R . . H1C H 0.5401 0.4014 0.4093 0.094 Uiso 1 1 calc R . . C2 C 0.3273(5) 0.3447(4) 0.3579(4) 0.0462(9) Uani 1 1 d . . . H2 H 0.2790 0.4073 0.3002 0.055 Uiso 1 1 calc R . . C3 C 0.3164(5) 0.2147(4) 0.3644(3) 0.0449(9) Uani 1 1 d . . . H3 H 0.3785 0.1528 0.4129 0.054 Uiso 1 1 calc R . . C4 C 0.2100(5) 0.1798(4) 0.2964(3) 0.0416(8) Uani 1 1 d . . . H4 H 0.2002 0.0943 0.2995 0.050 Uiso 1 1 calc R . . C5 C 0.1179(5) 0.2772(4) 0.2227(3) 0.0372(8) Uani 1 1 d . . . H5 H 0.1377 0.3636 0.2145 0.045 Uiso 1 1 calc R . . C6 C -0.0110(5) 0.2424(4) 0.1580(3) 0.0390(8) Uani 1 1 d . . . H6 H -0.0593 0.1527 0.2027 0.047 Uiso 1 1 calc R . . C7 C -0.1651(5) 0.3323(4) 0.1475(4) 0.0487(9) Uani 1 1 d . . . H7A H -0.2276 0.3253 0.2276 0.058 Uiso 1 1 calc R . . H7B H -0.1176 0.4215 0.1053 0.058 Uiso 1 1 calc R . . C8 C -0.2958(5) 0.2997(5) 0.0808(4) 0.0628(12) Uani 1 1 d . . . H8A H -0.3562 0.2151 0.1281 0.075 Uiso 1 1 calc R . . H8B H -0.3847 0.3635 0.0696 0.075 Uiso 1 1 calc R . . C9 C -0.1980(6) 0.2988(5) -0.0409(4) 0.0643(12) Uani 1 1 d . . . H9A H -0.2795 0.2677 -0.0786 0.077 Uiso 1 1 calc R . . H9B H -0.1541 0.3866 -0.0927 0.077 Uiso 1 1 calc R . . C10 C -0.0435(5) 0.2121(5) -0.0265(4) 0.0550(11) Uani 1 1 d . . . H10A H -0.0886 0.1230 0.0197 0.066 Uiso 1 1 calc R . . H10B H 0.0200 0.2152 -0.1052 0.066 Uiso 1 1 calc R . . C11 C 0.2365(5) 0.1761(4) 0.0339(3) 0.0433(9) Uani 1 1 d . . . H11A H 0.1988 0.0845 0.0717 0.052 Uiso 1 1 calc R . . H11B H 0.3123 0.1972 0.0810 0.052 Uiso 1 1 calc R . . C12 C 0.3412(5) 0.2010(4) -0.0911(3) 0.0405(8) Uani 1 1 d . . . C13 C 0.3928(5) 0.1009(5) -0.1208(4) 0.0529(10) Uani 1 1 d . . . H13 H 0.3574 0.0187 -0.0638 0.063 Uiso 1 1 calc R . . C14 C 0.3861(6) 0.3392(4) -0.1711(5) 0.0672(13) Uani 1 1 d . . . H14A H 0.4952 0.3454 -0.2279 0.101 Uiso 1 1 calc R . . H14B H 0.4000 0.3909 -0.1233 0.101 Uiso 1 1 calc R . . H14C H 0.2922 0.3703 -0.2135 0.101 Uiso 1 1 calc R . . C15 C 0.0562(6) 0.2043(5) 0.5668(4) 0.0568(11) Uani 1 1 d . . . C16 C -0.1433(6) 0.1625(4) 0.4370(3) 0.0493(10) Uani 1 1 d . . . C17 C -0.0212(6) 0.4185(5) 0.3812(4) 0.0534(10) Uani 1 1 d . . . N1 N 0.0792(4) 0.2530(3) 0.0346(3) 0.0400(7) Uani 1 1 d . . . Fe1 Fe 0.05715(7) 0.25992(6) 0.40845(5) 0.03887(18) Uani 1 1 d . . . Br1 Br 0.53385(9) 0.11025(7) -0.27062(5) 0.1001(3) Uani 1 1 d . . . O1 O 0.0526(5) 0.1665(4) 0.6674(3) 0.0878(12) Uani 1 1 d . . . O2 O -0.2726(4) 0.1018(3) 0.4559(3) 0.0709(9) Uani 1 1 d . . . O3 O -0.0668(5) 0.5216(4) 0.3614(4) 0.0869(11) Uani 1 1 d . . . 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 C1 0.066(3) 0.070(3) 0.058(3) -0.025(2) -0.024(2) -0.007(2) C2 0.043(2) 0.054(2) 0.045(2) -0.0177(19) -0.0142(17) -0.0006(17) C3 0.038(2) 0.056(2) 0.042(2) -0.0177(19) -0.0110(17) 0.0110(16) C4 0.0401(19) 0.046(2) 0.045(2) -0.0243(18) -0.0082(17) 0.0106(15) C5 0.0386(18) 0.041(2) 0.0382(19) -0.0208(17) -0.0090(15) 0.0070(14) C6 0.0353(18) 0.046(2) 0.040(2) -0.0192(17) -0.0080(16) 0.0040(15) C7 0.040(2) 0.060(2) 0.054(2) -0.028(2) -0.0125(18) 0.0139(17) C8 0.039(2) 0.088(3) 0.072(3) -0.038(3) -0.019(2) 0.015(2) C9 0.047(2) 0.099(4) 0.064(3) -0.041(3) -0.028(2) 0.015(2) C10 0.042(2) 0.081(3) 0.058(3) -0.040(2) -0.0168(19) 0.006(2) C11 0.040(2) 0.053(2) 0.043(2) -0.0221(19) -0.0132(17) 0.0092(16) C12 0.0339(18) 0.051(2) 0.039(2) -0.0182(18) -0.0098(16) 0.0093(15) C13 0.051(2) 0.068(3) 0.040(2) -0.020(2) -0.0089(18) 0.0166(19) C14 0.056(3) 0.061(3) 0.068(3) -0.007(2) -0.003(2) 0.012(2) C15 0.057(3) 0.069(3) 0.047(3) -0.024(2) -0.011(2) 0.005(2) C16 0.054(2) 0.056(3) 0.037(2) -0.0168(19) -0.0062(18) 0.010(2) C17 0.058(3) 0.063(3) 0.049(2) -0.030(2) -0.014(2) 0.015(2) N1 0.0331(15) 0.0539(19) 0.0409(17) -0.0236(15) -0.0132(13) 0.0084(13) Fe1 0.0401(3) 0.0438(3) 0.0354(3) -0.0171(3) -0.0083(2) 0.0060(2) Br1 0.1092(5) 0.1331(6) 0.0570(3) -0.0398(4) -0.0052(3) 0.0702(4) O1 0.102(3) 0.114(3) 0.0406(19) -0.017(2) -0.0180(18) 0.000(2) O2 0.0522(18) 0.079(2) 0.071(2) -0.0182(18) -0.0039(16) -0.0157(16) O3 0.111(3) 0.067(2) 0.098(3) -0.040(2) -0.037(2) 0.040(2) _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 C1 C2 1.499(5) . ? C2 C3 1.406(5) . ? C2 Fe1 2.165(4) . ? C3 C4 1.407(5) . ? C3 Fe1 2.062(4) . ? C4 C5 1.421(5) . ? C4 Fe1 2.045(4) . ? C5 C6 1.503(5) . ? C5 Fe1 2.144(3) . ? C6 N1 1.482(4) . ? C6 C7 1.533(5) . ? C7 C8 1.520(6) . ? C8 C9 1.519(6) . ? C9 C10 1.516(6) . ? C10 N1 1.465(5) . ? C11 N1 1.471(4) . ? C11 C12 1.500(5) . ? C12 C13 1.307(6) . ? C12 C14 1.491(6) . ? C13 Br1 1.890(4) . ? C15 O1 1.136(5) . ? C15 Fe1 1.796(5) . ? C16 O2 1.140(5) . ? C16 Fe1 1.788(4) . ? C17 O3 1.142(5) . ? C17 Fe1 1.782(5) . ? 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 C3 C2 C1 122.0(4) . . ? C3 C2 Fe1 66.7(2) . . ? C1 C2 Fe1 122.9(3) . . ? C2 C3 C4 119.0(4) . . ? C2 C3 Fe1 74.6(2) . . ? C4 C3 Fe1 69.3(2) . . ? C3 C4 C5 118.9(3) . . ? C3 C4 Fe1 70.6(2) . . ? C5 C4 Fe1 74.0(2) . . ? C4 C5 C6 120.8(3) . . ? C4 C5 Fe1 66.5(2) . . ? C6 C5 Fe1 124.6(2) . . ? N1 C6 C5 110.6(3) . . ? N1 C6 C7 107.9(3) . . ? C5 C6 C7 111.6(3) . . ? C8 C7 C6 112.3(3) . . ? C9 C8 C7 110.0(3) . . ? C10 C9 C8 110.5(4) . . ? N1 C10 C9 111.2(3) . . ? N1 C11 C12 112.2(3) . . ? C13 C12 C14 124.6(4) . . ? C13 C12 C11 118.1(4) . . ? C14 C12 C11 117.3(4) . . ? C12 C13 Br1 125.1(4) . . ? O1 C15 Fe1 178.2(4) . . ? O2 C16 Fe1 178.9(4) . . ? O3 C17 Fe1 178.0(4) . . ? C10 N1 C11 109.2(3) . . ? C10 N1 C6 110.9(3) . . ? C11 N1 C6 112.4(3) . . ? C17 Fe1 C16 102.3(2) . . ? C17 Fe1 C15 102.5(2) . . ? C16 Fe1 C15 90.49(19) . . ? C17 Fe1 C4 131.42(18) . . ? C16 Fe1 C4 97.00(17) . . ? C15 Fe1 C4 121.61(18) . . ? C17 Fe1 C3 126.65(18) . . ? C16 Fe1 C3 128.50(17) . . ? C15 Fe1 C3 93.22(18) . . ? C4 Fe1 C3 40.07(15) . . ? C17 Fe1 C5 95.18(17) . . ? C16 Fe1 C5 92.08(16) . . ? C15 Fe1 C5 161.17(18) . . ? C4 Fe1 C5 39.56(14) . . ? C3 Fe1 C5 70.72(14) . . ? C17 Fe1 C2 89.09(18) . . ? C16 Fe1 C2 166.82(17) . . ? C15 Fe1 C2 93.49(18) . . ? C4 Fe1 C2 70.24(15) . . ? C3 Fe1 C2 38.76(15) . . ? C5 Fe1 C2 80.19(14) . . ? _diffrn_measured_fraction_theta_max 0.874 _diffrn_reflns_theta_full 70.10 _diffrn_measured_fraction_theta_full 0.874 _refine_diff_density_max 0.748 _refine_diff_density_min -0.844 _refine_diff_density_rms 0.062