# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Chem.Commun. #==================================================================== # 1. SUBMISSION DETAILS _journal_coden_Cambridge 0182 _publ_contact_author_name 'Malcolm A. Halcrow' _publ_contact_author_address ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; _publ_contact_author_phone '+44 (0)113 3436506' _publ_contact_author_fax '+44 (0)113 3436565' _publ_contact_author_email m.a.halcrow@leeds.ac.uk _publ_contact_letter ; The following set of data is for four structures included in a manuscript we have just submitted to the Chem. Comm. office. Please note that these structures have already been pre-deposited with the CCDC, as numbers 614634-614637. ; #======================================================================= # 2. TITLE AND AUTHOR LIST _publ_section_title ; Iron(II) Complexes With a Terpyridine Embrace Packing Motif Show Remarkably Consistent Cooperative Spin-Transitions ; loop_ _publ_author_name _publ_author_address 'Ruth Pritchard' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Colin A. Kilner' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Malcolm A. Halcrow' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; #=END data_rp23 _database_code_depnum_ccdc_archive 'CCDC 614634' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-di(4-bromopyrazol-1-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ;Bis(2,6-di(4-bromopyrazol-1-yl)pyridine)iron(ii) ditetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety 'C22 H14 Br4 Fe N10, 2[B F4]' _chemical_formula_sum 'C22 H14 B2 Br4 F8 Fe N10' _chemical_formula_weight 967.54 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'P -4 21 c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1/2, -z+1/2' '-y+1/2, -x+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 9.7615(1) _cell_length_b 9.7615(1) _cell_length_c 17.2273(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1641.54(4) _cell_formula_units_Z 2 _cell_measurement_temperature 300(2) _cell_measurement_reflns_used 35262 _cell_measurement_theta_min 3.15 _cell_measurement_theta_max 27.49 _exptl_crystal_description 'Rectangular prism' _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.957 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 928 _exptl_absorpt_coefficient_mu 5.406 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.316 _exptl_absorpt_correction_T_max 0.487 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV. See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 300(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 35262 _diffrn_reflns_av_R_equivalents 0.1043 _diffrn_reflns_av_sigmaI/netI 0.0254 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 3.15 _diffrn_reflns_theta_max 27.49 _reflns_number_total 1884 _reflns_number_gt 1680 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains 1/4 of a complex dication, with Fe1 occupying the crystallographic S4 site [0, 1, 1] and N2 and C5 lying on the C2 axis [0, 1, z]; and, half a BF~4~^-^ anion that is badly disordered about the C~2~ axis [0. 0.5, z]. Three partial environments for this disordered half- anion B12-F16 were refined, labelled 'A' (occupancy 0.35), 'B' (0.05) and 'C' (0.1). These were subject to the refined restraints B---F = 1.37(2)\%A and F...F = 2.24(2)\%A. All non-H atoms except the disordered anion were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. The crystal was refined as a racemic twin. ; _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^)+(0.0376P)^2^+1.6857P] 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 SHELXL _refine_ls_extinction_coef 0.0033(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.199(18) _refine_ls_number_reflns 1884 _refine_ls_number_parameters 148 _refine_ls_number_restraints 30 _refine_ls_R_factor_all 0.0423 _refine_ls_R_factor_gt 0.0360 _refine_ls_wR_factor_ref 0.0916 _refine_ls_wR_factor_gt 0.0878 _refine_ls_goodness_of_fit_ref 1.065 _refine_ls_restrained_S_all 1.063 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.0000 1.0000 1.0000 0.0411(3) Uani 1 4 d S . . N2 N 0.0000 1.0000 0.8766(2) 0.0452(9) Uani 1 2 d S . . C3 C 0.0449(4) 0.8912(4) 0.8369(2) 0.0487(9) Uani 1 1 d . . . C4 C 0.0474(6) 0.8853(5) 0.7571(3) 0.0691(15) Uani 1 1 d . . . H4 H 0.0799 0.8068 0.7302 0.083 Uiso 1 1 calc R . . C5 C 0.0000 1.0000 0.7180(3) 0.079(2) Uani 1 2 d S . . H5 H 0.0000 1.0000 0.6629 0.095 Uiso 1 2 calc SR . . N6 N 0.0889(4) 0.7842(3) 0.88501(18) 0.0480(7) Uani 1 1 d . . . N7 N 0.0720(3) 0.7975(3) 0.96384(18) 0.0447(7) Uani 1 1 d . . . C8 C 0.1167(4) 0.6828(4) 0.9941(3) 0.0496(9) Uani 1 1 d . . . H8 H 0.1175 0.6621 1.0480 0.060 Uiso 1 1 calc R . . C9 C 0.1634(4) 0.5948(4) 0.9350(3) 0.0545(10) Uani 1 1 d . . . C10 C 0.1444(5) 0.6613(4) 0.8672(3) 0.0581(11) Uani 1 1 d . . . H10 H 0.1659 0.6283 0.8168 0.070 Uiso 1 1 calc R . . Br11 Br 0.23906(6) 0.42164(5) 0.94837(4) 0.0826(2) Uani 1 1 d . . . B12A B 0.0337(18) 0.4644(15) 0.6848(9) 0.074(6) Uiso 0.35 1 d PD . 1 F13A F -0.1072(17) 0.456(2) 0.6875(11) 0.161(9) Uiso 0.35 1 d PD . 1 F14A F 0.0831(16) 0.3898(12) 0.6229(6) 0.110(4) Uiso 0.35 1 d PD A 1 F15A F 0.0853(16) 0.4119(14) 0.7543(6) 0.098(3) Uiso 0.35 1 d PD . 1 F16A F 0.0764(18) 0.5958(11) 0.6730(7) 0.098(4) Uiso 0.35 1 d PD . 1 B12B B 0.085(4) 0.484(4) 0.680(2) 0.06(3) Uiso 0.05 1 d PD . 2 F13B F -0.010(6) 0.532(7) 0.627(3) 0.12(3) Uiso 0.05 1 d PD . 2 F14B F 0.150(4) 0.371(4) 0.648(2) 0.048(10) Uiso 0.05 1 d PD . 2 F15B F 0.024(5) 0.451(5) 0.749(2) 0.061(15) Uiso 0.05 1 d PD . 2 F16B F 0.183(5) 0.584(4) 0.691(3) 0.048(13) Uiso 0.05 1 d PD B 2 B12C B 0.060(3) 0.469(3) 0.7020(16) 0.062(17) Uiso 0.10 1 d PD . 3 F13C F -0.052(4) 0.512(4) 0.748(2) 0.12(2) Uiso 0.10 1 d PD . 3 F14C F 0.009(4) 0.398(3) 0.6391(16) 0.069(7) Uiso 0.10 1 d PD . 3 F15C F 0.137(4) 0.383(3) 0.7480(17) 0.095(12) Uiso 0.10 1 d PD . 3 F16C F 0.133(3) 0.583(2) 0.6808(11) 0.027(4) Uiso 0.10 1 d PD . 3 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 0.0418(4) 0.0418(4) 0.0397(4) 0.000 0.000 0.000 N2 0.054(3) 0.039(2) 0.0429(19) 0.000 0.000 0.008(2) C3 0.055(2) 0.040(2) 0.052(2) -0.0041(16) -0.0027(17) 0.0107(16) C4 0.098(4) 0.061(3) 0.048(2) -0.008(2) 0.000(2) 0.027(3) C5 0.122(7) 0.070(5) 0.045(3) 0.000 0.000 0.027(5) N6 0.0586(19) 0.0395(16) 0.0460(16) -0.0018(13) -0.0049(15) 0.0053(15) N7 0.0421(16) 0.0377(15) 0.0543(17) 0.0006(13) -0.0009(14) 0.0009(12) C8 0.042(2) 0.044(2) 0.063(2) 0.0109(19) -0.0004(19) -0.0005(15) C9 0.0423(19) 0.0352(17) 0.086(3) 0.006(2) -0.006(2) 0.0011(15) C10 0.067(3) 0.037(2) 0.071(3) -0.0082(19) 0.001(2) 0.0081(19) Br11 0.0736(3) 0.0434(2) 0.1309(5) 0.0221(3) 0.0085(3) 0.0160(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 Fe1 N2 2.125(4) . ? Fe1 N7 2.188(3) . ? N2 C3 1.337(4) . ? C3 C4 1.376(6) . ? C3 N6 1.401(5) . ? C4 C5 1.385(5) . ? N6 C10 1.352(5) . ? N6 N7 1.374(5) . ? N7 C8 1.310(5) . ? C8 C9 1.408(6) . ? C9 C10 1.349(6) . ? C9 Br11 1.859(4) . ? B12A F16A 1.363(16) . ? B12A F14A 1.379(15) . ? B12A F13A 1.379(17) . ? B12A F15A 1.396(16) . ? B12B F15B 1.370(19) . ? B12B F14B 1.38(2) . ? B12B F16B 1.39(2) . ? B12B F13B 1.388(19) . ? B12C F16C 1.376(19) . ? B12C F15C 1.380(19) . ? B12C F14C 1.381(19) . ? B12C F13C 1.408(19) . ? 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 N2 Fe1 N2 180.00 2_467 . ? N2 Fe1 N7 106.54(8) . 2_467 ? N2 Fe1 N7 73.46(8) . . ? N7 Fe1 N7 94.65(5) 2_467 . ? N7 Fe1 N7 146.92(16) . 3_575 ? C3 N2 C3 118.4(4) . 3_575 ? C3 N2 Fe1 120.8(2) . . ? N2 C3 C4 123.4(4) . . ? N2 C3 N6 112.9(3) . . ? C4 C3 N6 123.7(4) . . ? C3 C4 C5 116.4(4) . . ? C4 C5 C4 121.9(6) 3_575 . ? C10 N6 N7 110.9(3) . . ? C10 N6 C3 130.6(3) . . ? N7 N6 C3 118.5(3) . . ? C8 N7 N6 105.8(3) . . ? C8 N7 Fe1 140.0(3) . . ? N6 N7 Fe1 113.9(2) . . ? N7 C8 C9 110.0(4) . . ? C10 C9 C8 106.7(4) . . ? C10 C9 Br11 126.8(4) . . ? C8 C9 Br11 126.4(3) . . ? C9 C10 N6 106.6(4) . . ? F16A B12A F14A 105.9(12) . . ? F16A B12A F13A 111.5(13) . . ? F14A B12A F13A 110.0(15) . . ? F16A B12A F15A 111.3(14) . . ? F14A B12A F15A 110.0(12) . . ? F13A B12A F15A 108.1(13) . . ? F15B B12B F14B 111.1(18) . . ? F15B B12B F16B 110.2(18) . . ? F14B B12B F16B 107.8(18) . . ? F15B B12B F13B 110.8(18) . . ? F14B B12B F13B 108.6(18) . . ? F16B B12B F13B 108.4(18) . . ? F16C B12C F15C 111.1(17) . . ? F16C B12C F14C 112.9(18) . . ? F15C B12C F14C 109.7(17) . . ? F16C B12C F13C 108.2(17) . . ? F15C B12C F13C 106.5(17) . . ? F14C B12C F13C 108.1(17) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.681 _refine_diff_density_min -0.424 _refine_diff_density_rms 0.061 #================================================================= data_rp25rt _database_code_depnum_ccdc_archive 'CCDC 614635' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-di(4-chloropyrazol-1-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ;Bis(2,6-di(4-chloropyrazol-1-yl)pyridine)iron(ii) ditetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety 'C22 H14 Cl4 Fe N10, 2[B F4]' _chemical_formula_sum 'C22 H14 B2 Cl4 F8 Fe N10' _chemical_formula_weight 789.70 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'P -4 21 c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1/2, -z+1/2' '-y+1/2, -x+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 9.5613(1) _cell_length_b 9.5613(1) _cell_length_c 17.3177(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1583.16(4) _cell_formula_units_Z 2 _cell_measurement_temperature 300(2) _cell_measurement_reflns_used 24687 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 27.46 _exptl_crystal_description 'Rectangular prism' _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.24 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.657 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 784 _exptl_absorpt_coefficient_mu 0.895 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.608 _exptl_absorpt_correction_T_max 0.832 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 300(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24687 _diffrn_reflns_av_R_equivalents 0.0433 _diffrn_reflns_av_sigmaI/netI 0.0237 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.35 _diffrn_reflns_theta_max 27.46 _reflns_number_total 1824 _reflns_number_gt 1693 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains 1/4 of a complex dication, with Fe1 occupying the crystallographic S4 site [0, 1, 1] and N2 and C5 lying on the C2 axis [0, 1, z]; and, half a BF~4~^-^ anion that is badly disordered about the C~2~ axis [0. 0.5, z]. Two partial environments for this disordered half- anion B12-F16 were refined, labelled 'A' (occupancy 0.35) and 'B' (0.15). These were subject to the refined restraints B---F = 1.38(2)\%A and F...F = 2.25(2)\%A. All non-H atoms except the disordered anion were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. ; _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^)+(0.0790P)^2^+0.2717P] 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 SHELXL _refine_ls_extinction_coef 0.037(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00(3) _refine_ls_number_reflns 1824 _refine_ls_number_parameters 127 _refine_ls_number_restraints 20 _refine_ls_R_factor_all 0.0457 _refine_ls_R_factor_gt 0.0424 _refine_ls_wR_factor_ref 0.1209 _refine_ls_wR_factor_gt 0.1166 _refine_ls_goodness_of_fit_ref 1.079 _refine_ls_restrained_S_all 1.098 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.0000 1.0000 1.0000 0.0500(2) Uani 1 4 d S . . N2 N 0.0000 1.0000 0.87671(16) 0.0502(6) Uani 1 2 d S . . C3 C 0.0469(3) 0.8900(3) 0.83715(15) 0.0549(6) Uani 1 1 d . . . C4 C 0.0499(4) 0.8842(4) 0.75750(18) 0.0736(9) Uani 1 1 d . . . H4 H 0.0846 0.8045 0.7309 0.088 Uiso 1 1 calc R . . C5 C 0.0000 1.0000 0.7182(2) 0.0789(13) Uani 1 2 d S . . H5 H 0.0000 1.0000 0.6633 0.095 Uiso 1 2 calc SR . . N6 N 0.0928(2) 0.7807(2) 0.88512(13) 0.0552(5) Uani 1 1 d . . . N7 N 0.0755(2) 0.7947(2) 0.96300(13) 0.0536(5) Uani 1 1 d . . . C8 C 0.1223(3) 0.6763(3) 0.99300(18) 0.0597(6) Uani 1 1 d . . . H8 H 0.1238 0.6551 1.0466 0.072 Uiso 1 1 calc R . . C9 C 0.1694(3) 0.5866(3) 0.9343(2) 0.0642(7) Uani 1 1 d . . . C10 C 0.1504(4) 0.6553(3) 0.86688(19) 0.0666(7) Uani 1 1 d . . . H10 H 0.1730 0.6223 0.8167 0.080 Uiso 1 1 calc R . . Cl11 Cl 0.23932(11) 0.42421(9) 0.94551(8) 0.0957(4) Uani 1 1 d . . . B12A B 0.0368(14) 0.4630(12) 0.6824(7) 0.080(3) Uiso 0.35 1 d PD . 1 F13A F -0.1009(14) 0.4692(16) 0.6859(9) 0.171(6) Uiso 0.35 1 d PD . 1 F14A F 0.0856(8) 0.3814(8) 0.6242(4) 0.0952(18) Uiso 0.35 1 d PD A 1 F15A F 0.0888(11) 0.4078(10) 0.7532(5) 0.102(2) Uiso 0.35 1 d PD . 1 F16A F 0.0946(12) 0.5925(9) 0.6739(5) 0.102(3) Uiso 0.35 1 d PD . 1 B12B B 0.070(2) 0.4642(18) 0.6960(11) 0.067(7) Uiso 0.15 1 d PD . 2 F13B F -0.0418(17) 0.518(2) 0.7445(10) 0.121(6) Uiso 0.15 1 d PD . 2 F14B F 0.013(2) 0.3896(17) 0.6383(9) 0.100(5) Uiso 0.15 1 d PD . 2 F15B F 0.137(2) 0.374(2) 0.7460(11) 0.133(8) Uiso 0.15 1 d PD . 2 F16B F 0.1530(12) 0.5784(12) 0.6805(6) 0.054(2) Uiso 0.15 1 d PD . 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 0.0523(3) 0.0523(3) 0.0454(3) 0.000 0.000 0.000 N2 0.0581(15) 0.0443(13) 0.0481(12) 0.000 0.000 0.0066(16) C3 0.0631(14) 0.0490(13) 0.0525(13) -0.0023(10) -0.0011(11) 0.0090(10) C4 0.099(2) 0.0662(18) 0.0560(14) -0.0106(13) 0.0006(14) 0.0199(16) C5 0.111(4) 0.081(3) 0.0449(15) 0.000 0.000 0.023(4) N6 0.0633(12) 0.0464(10) 0.0560(11) -0.0033(9) -0.0035(10) 0.0071(10) N7 0.0536(11) 0.0521(11) 0.0552(11) 0.0035(9) -0.0007(9) 0.0005(9) C8 0.0530(13) 0.0555(13) 0.0706(16) 0.0111(13) -0.0047(13) -0.0005(10) C9 0.0536(14) 0.0464(12) 0.092(2) 0.0055(14) -0.0018(14) 0.0035(10) C10 0.0692(17) 0.0496(14) 0.0810(17) -0.0066(13) 0.0035(15) 0.0086(13) Cl11 0.0959(7) 0.0558(4) 0.1355(9) 0.0223(5) 0.0122(6) 0.0226(4) _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 N2 2.135(3) . ? Fe1 N7 2.188(2) . ? N2 C3 1.333(3) . ? C3 C4 1.381(4) . ? C3 N6 1.406(3) . ? C4 C5 1.384(4) . ? N6 C10 1.357(4) . ? N6 N7 1.365(3) . ? N7 C8 1.323(3) . ? C8 C9 1.404(4) . ? C9 C10 1.353(5) . ? C9 Cl11 1.701(3) . ? B12A F13A 1.320(13) . ? B12A F14A 1.358(12) . ? B12A F16A 1.363(13) . ? B12A F15A 1.424(14) . ? B12B F14B 1.345(17) . ? B12B F15B 1.374(18) . ? B12B F16B 1.374(17) . ? B12B F13B 1.456(17) . ? 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 N2 Fe1 N2 180.00 . 2_467 ? N2 Fe1 N7 72.97(6) . . ? N7 Fe1 N7 145.94(11) 3_575 . ? N2 Fe1 N7 107.03(6) . 2_467 ? N7 Fe1 N7 94.92(3) . 2_467 ? C3 N2 C3 118.1(3) 3_575 . ? C3 N2 Fe1 120.94(15) . . ? N2 C3 C4 123.5(2) . . ? N2 C3 N6 112.8(2) . . ? C4 C3 N6 123.6(2) . . ? C3 C4 C5 116.9(3) . . ? C4 C5 C4 121.1(4) 3_575 . ? C10 N6 N7 111.4(2) . . ? C10 N6 C3 130.3(2) . . ? N7 N6 C3 118.3(2) . . ? C8 N7 N6 105.3(2) . . ? C8 N7 Fe1 139.8(2) . . ? N6 N7 Fe1 114.65(15) . . ? N7 C8 C9 110.3(3) . . ? C10 C9 C8 106.6(2) . . ? C10 C9 Cl11 126.5(3) . . ? C8 C9 Cl11 127.0(2) . . ? C9 C10 N6 106.4(3) . . ? F13A B12A F14A 113.7(13) . . ? F13A B12A F16A 111.6(11) . . ? F14A B12A F16A 107.6(9) . . ? F13A B12A F15A 109.0(12) . . ? F14A B12A F15A 107.9(9) . . ? F16A B12A F15A 106.8(10) . . ? F14B B12B F15B 109.0(14) . . ? F14B B12B F16B 120.7(15) . . ? F15B B12B F16B 110.7(15) . . ? F14B B12B F13B 108.3(15) . . ? F15B B12B F13B 101.4(14) . . ? F16B B12B F13B 104.9(13) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.46 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.312 _refine_diff_density_min -0.243 _refine_diff_density_rms 0.074 #=END data_rp25mt _database_code_depnum_ccdc_archive 'CCDC 614636' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-di(4-chloropyrazol-1-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ;Bis(2,6-di(4-chloropyrazol-1-yl)pyridine)iron(ii) ditetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety 'C22 H14 Cl4 Fe N10, 2[B F4]' _chemical_formula_sum 'C22 H14 B2 Cl4 F8 Fe N10' _chemical_formula_weight 789.70 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'P -4 21 c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x+1/2, -y+1/2, -z+1/2' '-x+1/2, y+1/2, -z+1/2' '-y+1/2, -x+1/2, z+1/2' 'y+1/2, x+1/2, z+1/2' _cell_length_a 9.5410(3) _cell_length_b 9.5410(3) _cell_length_c 17.1024(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1556.84(9) _cell_formula_units_Z 2 _cell_measurement_temperature 220(2) _cell_measurement_reflns_used 22329 _cell_measurement_theta_min 2.38 _cell_measurement_theta_max 27.62 _exptl_crystal_description 'Rectangular prism' _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.685 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 784 _exptl_absorpt_coefficient_mu 0.910 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.471 _exptl_absorpt_correction_T_max 0.746 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 220(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 22329 _diffrn_reflns_av_R_equivalents 0.1081 _diffrn_reflns_av_sigmaI/netI 0.0356 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.38 _diffrn_reflns_theta_max 27.62 _reflns_number_total 1814 _reflns_number_gt 1646 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains 1/4 of a complex dication, with Fe1 occupying the crystallographic S4 site [0, 1, 1] and N2 and C5 lying on the C2 axis [0, 1, z]; and, half a BF~4~^-^ anion that is badly disordered about the C~2~ axis [0. 0.5, z]. Two partial environments for this disordered half- anion B12-F16 were refined, labelled 'A' (occupancy 0.40) and 'B' (0.10). These were subject to the refined restraints B---F = 1.38(2)\%A and F...F = 2.25(2)\%A. All non-H atoms except the disordered anion were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. ; _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^)+(0.0584P)^2^+2.0085P] 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 SHELXL _refine_ls_extinction_coef 0.035(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.03(5) _refine_ls_number_reflns 1814 _refine_ls_number_parameters 127 _refine_ls_number_restraints 20 _refine_ls_R_factor_all 0.0691 _refine_ls_R_factor_gt 0.0574 _refine_ls_wR_factor_ref 0.1612 _refine_ls_wR_factor_gt 0.1545 _refine_ls_goodness_of_fit_ref 1.187 _refine_ls_restrained_S_all 1.185 _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 Fe1 Fe 0.0000 1.0000 1.0000 0.0467(4) Uani 1 4 d S . . N2 N 0.0000 1.0000 1.1253(3) 0.0438(10) Uani 1 2 d S . . C3 C 0.0473(5) 0.8880(5) 1.1646(3) 0.0463(11) Uani 1 1 d . . . C4 C 0.0505(6) 0.8831(6) 1.2449(3) 0.0599(15) Uani 1 1 d . . . H4 H 0.0857 0.8035 1.2720 0.072 Uiso 1 1 calc R . . C5 C 0.0000 1.0000 1.2851(4) 0.067(2) Uani 1 2 d S . . H5 H 0.0000 1.0000 1.3406 0.080 Uiso 1 2 calc SR . . N6 N 0.0921(4) 0.7808(4) 1.1161(2) 0.0474(9) Uani 1 1 d . . . N7 N 0.0746(4) 0.7944(4) 1.0368(2) 0.0461(9) Uani 1 1 d . . . C8 C 0.1201(5) 0.6759(5) 1.0065(3) 0.0506(11) Uani 1 1 d . . . H8 H 0.1197 0.6540 0.9523 0.061 Uiso 1 1 calc R . . C9 C 0.1695(5) 0.5866(5) 1.0657(3) 0.0523(11) Uani 1 1 d . . . C10 C 0.1484(6) 0.6554(5) 1.1346(3) 0.0556(12) Uani 1 1 d . . . H10 H 0.1692 0.6216 1.1855 0.067 Uiso 1 1 calc R . . Cl11 Cl 0.23812(17) 0.42228(15) 1.05410(11) 0.0757(5) Uani 1 1 d . . . B12A B 0.0518(16) 0.4563(14) 1.3155(8) 0.057(4) Uiso 0.40 1 d PD . 1 F13A F -0.0908(15) 0.4688(17) 1.3146(9) 0.126(5) Uiso 0.40 1 d PD . 1 F14A F 0.0959(10) 0.3747(9) 1.3757(5) 0.073(2) Uiso 0.40 1 d PD A 1 F15A F 0.0952(12) 0.4001(11) 1.2447(6) 0.075(3) Uiso 0.40 1 d PD . 1 F16A F 0.1043(12) 0.5906(10) 1.3225(6) 0.069(3) Uiso 0.40 1 d PD . 1 B12B B 0.074(3) 0.468(3) 1.3009(17) 0.040(14) Uiso 0.10 1 d PD . 2 F13B F -0.039(3) 0.522(5) 1.259(3) 0.16(2) Uiso 0.10 1 d PD . 2 F14B F 0.023(4) 0.400(3) 1.3661(19) 0.087(11) Uiso 0.10 1 d PD . 2 F15B F 0.138(4) 0.369(3) 1.2543(17) 0.067(9) Uiso 0.10 1 d PD . 2 F16B F 0.164(2) 0.5746(19) 1.3191(10) 0.020(4) Uiso 0.10 1 d PD B 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 0.0507(5) 0.0507(5) 0.0386(6) 0.000 0.000 0.000 N2 0.054(3) 0.035(2) 0.042(2) 0.000 0.000 0.006(3) C3 0.050(2) 0.042(2) 0.047(2) 0.0023(19) 0.0011(19) 0.0036(18) C4 0.081(4) 0.052(3) 0.046(3) 0.006(2) 0.001(2) 0.012(3) C5 0.096(6) 0.062(5) 0.042(3) 0.000 0.000 0.020(5) N6 0.052(2) 0.043(2) 0.047(2) 0.0004(16) -0.0032(18) 0.0006(17) N7 0.048(2) 0.048(2) 0.0421(19) -0.0035(16) 0.0035(16) -0.0034(17) C8 0.045(2) 0.047(2) 0.060(3) -0.009(2) 0.002(2) 0.0002(17) C9 0.045(2) 0.041(2) 0.071(3) -0.003(2) 0.000(2) 0.0030(19) C10 0.058(3) 0.041(2) 0.068(3) -0.001(2) 0.000(3) 0.004(2) Cl11 0.0752(10) 0.0483(7) 0.1036(12) -0.0186(8) -0.0092(9) 0.0154(6) _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 N2 2.143(5) . ? Fe1 N7 2.180(4) . ? N2 C3 1.340(5) . ? C3 C4 1.375(7) . ? C3 N6 1.385(6) . ? C4 C5 1.395(6) . ? N6 C10 1.349(7) . ? N6 N7 1.373(6) . ? N7 C8 1.317(6) . ? C8 C9 1.404(7) . ? C9 C10 1.364(7) . ? C9 Cl11 1.710(5) . ? B12A F14A 1.357(14) . ? B12A F13A 1.366(15) . ? B12A F16A 1.380(15) . ? B12A F15A 1.388(15) . ? B12B F16B 1.371(19) . ? B12B F14B 1.378(19) . ? B12B F15B 1.380(19) . ? B12B F13B 1.390(19) . ? 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 N2 Fe1 N2 180 2_467 . ? N2 Fe1 N7 106.77(10) . 2_467 ? N2 Fe1 N7 73.23(10) . . ? N7 Fe1 N7 146.46(19) 3_575 . ? N7 Fe1 N7 94.77(5) 2_467 . ? C3 N2 C3 119.8(5) 3_575 . ? C3 N2 Fe1 120.1(3) . . ? N2 C3 C4 122.4(4) . . ? N2 C3 N6 113.1(4) . . ? C4 C3 N6 124.5(4) . . ? C3 C4 C5 117.2(5) . . ? C4 C5 C4 121.0(6) 3_575 . ? C10 N6 N7 111.3(4) . . ? C10 N6 C3 129.6(4) . . ? N7 N6 C3 119.0(4) . . ? C8 N7 N6 105.5(4) . . ? C8 N7 Fe1 140.1(4) . . ? N6 N7 Fe1 114.2(3) . . ? N7 C8 C9 110.4(5) . . ? C10 C9 C8 106.3(4) . . ? C10 C9 Cl11 126.7(4) . . ? C8 C9 Cl11 127.0(4) . . ? N6 C10 C9 106.5(5) . . ? F14A B12A F13A 111.5(14) . . ? F14A B12A F16A 110.8(11) . . ? F13A B12A F16A 106.3(12) . . ? F14A B12A F15A 110.4(11) . . ? F13A B12A F15A 108.7(12) . . ? F16A B12A F15A 109.0(12) . . ? F16B B12B F14B 112.7(17) . . ? F16B B12B F15B 110.8(17) . . ? F14B B12B F15B 107.6(17) . . ? F16B B12B F13B 109.4(17) . . ? F14B B12B F13B 108.5(17) . . ? F15B B12B F13B 107.7(17) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.62 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.536 _refine_diff_density_min -0.752 _refine_diff_density_rms 0.202 #=END data_rp25lt _database_code_depnum_ccdc_archive 'CCDC 614637' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-di(4-chloropyrazol-1-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ;Bis(2,6-di(4-chloropyrazol-1-yl)pyridine)iron(ii) ditetrafluoroborate ; _chemical_melting_point ? _chemical_formula_moiety 'C22 H14 Cl4 Fe N10, 2[B F4]' _chemical_formula_sum 'C22 H14 B2 Cl4 F8 Fe N10' _chemical_formula_weight 789.70 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 9.6268(3) _cell_length_b 9.6508(3) _cell_length_c 16.5051(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.7285(12) _cell_angle_gamma 90.00 _cell_volume 1533.30(8) _cell_formula_units_Z 2 _cell_measurement_temperature 202(2) _cell_measurement_reflns_used 21495 _cell_measurement_theta_min 2.12 _cell_measurement_theta_max 27.54 _exptl_crystal_description 'Rectangular prism' _exptl_crystal_colour Brown _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.710 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 784 _exptl_absorpt_coefficient_mu 0.924 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.649 _exptl_absorpt_correction_T_max 0.888 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings The crystal undergoes a phase change at 204 K. Further cooling of the crystals causes them to crack. However, this dataset of the low-temperature phase was successfully obtained at a temperature just below the phase change. ; _diffrn_ambient_temperature 202(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 21495 _diffrn_reflns_av_R_equivalents 0.0680 _diffrn_reflns_av_sigmaI/netI 0.0583 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 27.54 _reflns_number_total 6726 _reflns_number_gt 6265 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 crystal was refined as a racemic twin. Both BF~4~^-^ anions are disordered over three equally occupied sites labelled 'A', 'B' and 'C'. All B---F distances were restrained to 1.39(2)\%A, and non-bonded F...F contacts within each disorder orientation to 2.27(2)\%A. All wholly occupied non-H atoms were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. ; _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^)+(0.0886P)^2^+3.5882P] 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 SHELXL _refine_ls_extinction_coef 0.046(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.13(3) _refine_ls_number_reflns 6726 _refine_ls_number_parameters 457 _refine_ls_number_restraints 61 _refine_ls_R_factor_all 0.0791 _refine_ls_R_factor_gt 0.0742 _refine_ls_wR_factor_ref 0.2069 _refine_ls_wR_factor_gt 0.2038 _refine_ls_goodness_of_fit_ref 1.128 _refine_ls_restrained_S_all 1.127 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.23115(8) 0.23799(9) 0.74796(5) 0.0378(2) Uani 1 1 d . . . N2 N 0.2409(5) 0.2377(7) 0.8629(3) 0.0421(10) Uani 1 1 d . . . C3 C 0.1360(7) 0.1902(7) 0.9065(4) 0.0466(15) Uani 1 1 d . . . C4 C 0.1425(9) 0.1810(9) 0.9903(5) 0.0587(19) Uani 1 1 d . . . H4 H 0.0684 0.1421 1.0203 0.070 Uiso 1 1 calc R . . C5 C 0.2610(9) 0.2306(12) 1.0283(4) 0.0655(19) Uani 1 1 d . . . H5 H 0.2659 0.2305 1.0859 0.079 Uiso 1 1 calc R . . C6 C 0.3712(8) 0.2797(9) 0.9858(5) 0.0569(18) Uani 1 1 d . . . H6 H 0.4535 0.3106 1.0126 0.068 Uiso 1 1 calc R . . C7 C 0.3584(7) 0.2829(7) 0.9022(5) 0.0477(15) Uani 1 1 d . . . N8 N 0.0264(6) 0.1481(6) 0.8555(3) 0.0438(12) Uani 1 1 d . . . N9 N 0.0446(6) 0.1659(6) 0.7730(3) 0.0411(11) Uani 1 1 d . . . C10 C -0.0730(7) 0.1185(7) 0.7398(5) 0.0462(15) Uani 1 1 d . . . H10 H -0.0922 0.1162 0.6832 0.055 Uiso 1 1 calc R . . C11 C -0.1644(7) 0.0725(7) 0.7993(5) 0.0521(17) Uani 1 1 d . . . C12 C -0.0976(8) 0.0907(8) 0.8709(5) 0.0521(17) Uani 1 1 d . . . H12 H -0.1320 0.0671 0.9228 0.062 Uiso 1 1 calc R . . Cl13 Cl -0.3256(2) 0.0040(2) 0.78610(16) 0.0703(6) Uani 1 1 d . . . N14 N 0.4557(6) 0.3256(6) 0.8441(4) 0.0473(13) Uani 1 1 d . . . N15 N 0.4191(6) 0.3103(6) 0.7643(4) 0.0428(12) Uani 1 1 d . . . C16 C 0.5287(7) 0.3544(7) 0.7240(5) 0.0491(16) Uani 1 1 d . . . H16 H 0.5348 0.3569 0.6667 0.059 Uiso 1 1 calc R . . C17 C 0.6331(8) 0.3965(7) 0.7769(6) 0.059(2) Uani 1 1 d . . . C18 C 0.5873(7) 0.3761(8) 0.8547(5) 0.0544(18) Uani 1 1 d . . . H18 H 0.6358 0.3932 0.9042 0.065 Uiso 1 1 calc R . . Cl19 Cl 0.7922(2) 0.4649(2) 0.75083(18) 0.0753(7) Uani 1 1 d . . . N20 N 0.2288(5) 0.2306(6) 0.6335(3) 0.0408(10) Uani 1 1 d . . . C21 C 0.1843(8) 0.3424(7) 0.5898(4) 0.0443(14) Uani 1 1 d . . . C22 C 0.1830(9) 0.3406(8) 0.5055(5) 0.0533(17) Uani 1 1 d . . . H22 H 0.1474 0.4162 0.4749 0.064 Uiso 1 1 calc R . . C23 C 0.2360(10) 0.2234(10) 0.4682(4) 0.063(2) Uani 1 1 d . . . H23 H 0.2398 0.2210 0.4107 0.075 Uiso 1 1 calc R . . C24 C 0.2841(10) 0.1089(8) 0.5121(5) 0.0563(18) Uani 1 1 d . . . H24 H 0.3195 0.0284 0.4865 0.068 Uiso 1 1 calc R . . C25 C 0.2763(7) 0.1210(7) 0.5960(4) 0.0453(14) Uani 1 1 d . . . N26 N 0.1399(6) 0.4465(6) 0.6421(4) 0.0458(12) Uani 1 1 d . . . N27 N 0.1589(6) 0.4263(5) 0.7235(4) 0.0407(11) Uani 1 1 d . . . C28 C 0.1167(6) 0.5444(7) 0.7581(5) 0.0446(15) Uani 1 1 d . . . H28 H 0.1142 0.5616 0.8147 0.054 Uiso 1 1 calc R . . C29 C 0.0765(7) 0.6391(7) 0.6971(5) 0.0505(17) Uani 1 1 d . . . C30 C 0.0897(8) 0.5756(7) 0.6236(5) 0.0488(16) Uani 1 1 d . . . H30 H 0.0687 0.6127 0.5716 0.059 Uiso 1 1 calc R . . Cl31 Cl 0.0093(2) 0.80175(19) 0.71228(15) 0.0650(6) Uani 1 1 d . . . N32 N 0.3188(6) 0.0173(6) 0.6516(4) 0.0444(12) Uani 1 1 d . . . N33 N 0.3037(6) 0.0500(6) 0.7322(4) 0.0428(12) Uani 1 1 d . . . C34 C 0.3487(7) -0.0572(7) 0.7726(5) 0.0485(16) Uani 1 1 d . . . H34 H 0.3502 -0.0650 0.8299 0.058 Uiso 1 1 calc R . . C35 C 0.3946(8) -0.1590(7) 0.7189(5) 0.0519(17) Uani 1 1 d . . . C36 C 0.3735(8) -0.1109(7) 0.6415(5) 0.0512(16) Uani 1 1 d . . . H36 H 0.3927 -0.1571 0.5920 0.061 Uiso 1 1 calc R . . Cl37 Cl 0.4665(2) -0.3173(2) 0.74438(17) 0.0717(6) Uani 1 1 d . . . B38A B 0.299(2) 0.6705(19) 0.4506(11) 0.044(6) Uiso 0.33 1 d PD A 1 F39A F 0.347(2) 0.613(2) 0.5218(12) 0.083(11) Uiso 0.33 1 d PD A 1 F40A F 0.356(2) 0.603(2) 0.3843(12) 0.082(7) Uiso 0.33 1 d PD A 1 F41A F 0.3350(17) 0.8101(13) 0.4447(10) 0.058(5) Uiso 0.33 1 d PD A 1 F42A F 0.1545(15) 0.6643(17) 0.4466(9) 0.053(4) Uiso 0.33 1 d PD A 1 B38B B 0.332(2) 0.676(2) 0.4633(14) 0.10(3) Uiso 0.33 1 d PD B 2 F39B F 0.3573(19) 0.6132(14) 0.5379(10) 0.035(3) Uiso 0.33 1 d PD B 2 F40B F 0.368(3) 0.582(2) 0.4026(13) 0.079(8) Uiso 0.33 1 d PD B 2 F41B F 0.415(2) 0.7931(19) 0.4590(14) 0.084(9) Uiso 0.33 1 d PD B 2 F42B F 0.1904(18) 0.707(2) 0.4580(12) 0.092(7) Uiso 0.33 1 d PD B 2 B38C B 0.3409(19) 0.6648(19) 0.4613(11) 0.036(8) Uiso 0.33 1 d PD C 3 F39C F 0.377(3) 0.612(3) 0.5365(12) 0.131(18) Uiso 0.33 1 d PD C 3 F40C F 0.4137(17) 0.5903(17) 0.4034(10) 0.062(4) Uiso 0.33 1 d PD C 3 F41C F 0.381(2) 0.8021(14) 0.4559(10) 0.045(4) Uiso 0.33 1 d PD C 3 F42C F 0.1987(15) 0.6529(16) 0.4457(9) 0.051(4) Uiso 0.33 1 d PD C 3 B43C B 0.193(2) -0.176(2) 0.9625(12) 0.048(13) Uiso 0.33 1 d PD D 3 B43A B 0.188(2) -0.210(2) 0.9522(12) 0.055(8) Uiso 0.33 1 d PD E 1 F44A F 0.1705(18) -0.3534(16) 0.9466(11) 0.066(5) Uiso 0.33 1 d PD E 1 F45A F 0.3269(13) -0.1787(18) 0.9439(9) 0.059(4) Uiso 0.33 1 d PD E 1 F46A F 0.147(3) -0.169(3) 1.0296(12) 0.084(11) Uiso 0.33 1 d PD E 1 F47A F 0.1071(19) -0.146(2) 0.8938(12) 0.057(5) Uiso 0.33 1 d PD E 1 B43B B 0.207(2) -0.184(2) 0.9614(13) 0.057(16) Uiso 0.33 1 d PD F 2 F44B F 0.256(3) -0.320(2) 0.9723(17) 0.139(11) Uiso 0.33 1 d PD F 2 F45B F 0.315(2) -0.090(2) 0.9625(14) 0.087(9) Uiso 0.33 1 d PD F 2 F46B F 0.114(2) -0.156(2) 1.0249(12) 0.072(7) Uiso 0.33 1 d PD F 2 F47B F 0.133(2) -0.181(3) 0.8884(12) 0.101(9) Uiso 0.33 1 d PD F 2 F44C F 0.201(2) -0.3206(14) 0.9518(11) 0.058(4) Uiso 0.33 1 d PD D 3 F45C F 0.3277(12) -0.1251(19) 0.9568(8) 0.036(3) Uiso 0.33 1 d PD D 3 F46C F 0.141(2) -0.145(2) 1.0390(9) 0.049(5) Uiso 0.33 1 d PD D 3 F47C F 0.1086(16) -0.1126(18) 0.9045(10) 0.059(5) Uiso 0.33 1 d PD D 3 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 0.0363(4) 0.0350(4) 0.0421(4) -0.0005(4) 0.0020(3) 0.0008(4) N2 0.033(2) 0.046(3) 0.048(3) 0.003(3) 0.0014(19) 0.002(2) C3 0.042(3) 0.047(3) 0.051(4) -0.001(3) 0.004(3) -0.007(3) C4 0.064(4) 0.067(5) 0.045(4) 0.001(3) 0.010(3) -0.010(4) C5 0.075(5) 0.079(5) 0.043(3) 0.001(5) -0.008(3) -0.002(5) C6 0.054(4) 0.062(4) 0.055(4) -0.006(3) -0.005(3) -0.009(3) C7 0.046(3) 0.043(3) 0.055(4) 0.004(3) -0.001(3) -0.007(3) N8 0.039(3) 0.049(3) 0.043(3) -0.003(2) 0.002(2) -0.007(2) N9 0.040(3) 0.034(3) 0.049(3) 0.003(2) -0.001(2) -0.002(2) C10 0.046(4) 0.038(3) 0.055(4) -0.001(3) -0.004(3) 0.002(3) C11 0.038(3) 0.040(3) 0.078(5) 0.001(3) 0.005(3) -0.002(3) C12 0.050(4) 0.047(4) 0.059(4) -0.001(3) 0.011(3) -0.008(3) Cl13 0.0469(10) 0.0679(13) 0.0959(16) -0.0005(11) -0.0040(10) -0.0160(9) N14 0.040(3) 0.050(3) 0.052(3) -0.001(3) -0.001(2) -0.008(2) N15 0.045(3) 0.032(2) 0.052(3) 0.003(2) 0.007(2) 0.003(2) C16 0.040(3) 0.033(3) 0.074(5) 0.000(3) 0.013(3) 0.002(3) C17 0.044(4) 0.029(3) 0.104(7) 0.004(4) 0.013(4) 0.001(3) C18 0.041(3) 0.047(4) 0.075(5) 0.003(3) -0.003(3) -0.007(3) Cl19 0.0389(9) 0.0604(12) 0.127(2) 0.0068(12) 0.0178(10) -0.0093(8) N20 0.046(3) 0.030(2) 0.046(3) 0.003(3) 0.000(2) -0.001(2) C21 0.055(4) 0.032(3) 0.047(3) 0.001(3) 0.005(3) 0.004(3) C22 0.070(5) 0.045(4) 0.044(4) 0.007(3) 0.002(3) 0.002(3) C23 0.087(5) 0.060(5) 0.041(3) 0.001(4) -0.001(3) 0.007(4) C24 0.079(5) 0.044(4) 0.046(4) -0.003(3) -0.004(4) 0.012(3) C25 0.037(3) 0.045(3) 0.054(4) 0.001(3) 0.006(3) 0.007(3) N26 0.056(3) 0.033(3) 0.049(3) 0.000(2) 0.002(2) 0.005(2) N27 0.041(3) 0.027(2) 0.054(3) -0.005(2) 0.006(2) 0.0028(19) C28 0.030(3) 0.043(3) 0.061(4) -0.006(3) 0.004(3) 0.000(2) C29 0.041(3) 0.039(3) 0.072(5) -0.006(3) 0.009(3) 0.006(3) C30 0.054(4) 0.031(3) 0.061(4) 0.000(3) -0.001(3) 0.012(3) Cl31 0.0663(12) 0.0391(9) 0.0896(15) -0.0120(9) -0.0040(10) 0.0127(8) N32 0.053(3) 0.030(2) 0.051(3) 0.000(2) 0.005(2) 0.004(2) N33 0.039(3) 0.041(3) 0.049(3) 0.007(2) 0.003(2) 0.006(2) C34 0.037(3) 0.034(3) 0.074(5) 0.010(3) 0.005(3) -0.002(3) C35 0.052(4) 0.030(3) 0.074(5) 0.004(3) 0.001(3) 0.001(3) C36 0.060(4) 0.033(3) 0.060(4) -0.013(3) 0.006(3) 0.006(3) Cl37 0.0690(12) 0.0362(8) 0.1096(18) 0.0105(10) -0.0068(12) 0.0133(8) _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 N20 1.890(5) . ? Fe1 N2 1.898(5) . ? Fe1 N15 1.955(6) . ? Fe1 N33 1.963(6) . ? Fe1 N9 1.974(5) . ? Fe1 N27 1.985(5) . ? N2 C3 1.330(9) . ? N2 C7 1.368(9) . ? C3 C4 1.386(11) . ? C3 N8 1.401(9) . ? C4 C5 1.381(12) . ? C5 C6 1.365(12) . ? C6 C7 1.385(11) . ? C7 N14 1.410(9) . ? N8 C12 1.343(9) . ? N8 N9 1.386(8) . ? N9 C10 1.333(9) . ? C10 C11 1.399(11) . ? C11 C12 1.350(12) . ? C11 Cl13 1.698(7) . ? N14 C18 1.366(9) . ? N14 N15 1.367(9) . ? N15 C16 1.325(9) . ? C16 C17 1.383(12) . ? C17 C18 1.378(13) . ? C17 Cl19 1.728(8) . ? N20 C25 1.311(9) . ? N20 C21 1.363(9) . ? C21 C22 1.391(10) . ? C21 N26 1.395(9) . ? C22 C23 1.388(12) . ? C23 C24 1.397(12) . ? C24 C25 1.392(11) . ? C25 N32 1.415(9) . ? N26 N27 1.369(8) . ? N26 C30 1.370(8) . ? N27 C28 1.340(8) . ? C28 C29 1.410(11) . ? C29 C30 1.366(11) . ? C29 Cl31 1.718(7) . ? N32 C36 1.356(8) . ? N32 N33 1.376(8) . ? N33 C34 1.301(9) . ? C34 C35 1.398(11) . ? C35 C36 1.372(12) . ? C35 Cl37 1.727(7) . ? B38A F39A 1.374(17) . ? B38A F40A 1.391(16) . ? B38A F42A 1.394(17) . ? B38A F41A 1.395(16) . ? B38B F41B 1.383(18) . ? B38B F39B 1.392(18) . ? B38B F40B 1.397(18) . ? B38B F42B 1.398(18) . ? B38C F41C 1.382(15) . ? B38C F39C 1.383(16) . ? B38C F40C 1.391(16) . ? B38C F42C 1.395(16) . ? B43C F45C 1.388(17) . ? B43C F47C 1.389(17) . ? B43C F46C 1.396(17) . ? B43C F44C 1.411(17) . ? B43A F47A 1.379(17) . ? B43A F45A 1.380(17) . ? B43A F44A 1.397(17) . ? B43A F46A 1.399(17) . ? B43B F45B 1.385(17) . ? B43B F47B 1.393(18) . ? B43B F44B 1.402(18) . ? B43B F46B 1.409(18) . ? 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 N20 Fe1 N2 176.9(3) . . ? N20 Fe1 N15 98.7(2) . . ? N2 Fe1 N15 80.1(2) . . ? N20 Fe1 N33 80.4(2) . . ? N2 Fe1 N33 96.8(3) . . ? N15 Fe1 N33 91.0(2) . . ? N20 Fe1 N9 101.4(2) . . ? N2 Fe1 N9 79.8(2) . . ? N15 Fe1 N9 160.0(2) . . ? N33 Fe1 N9 91.6(2) . . ? N20 Fe1 N27 80.3(2) . . ? N2 Fe1 N27 102.5(3) . . ? N15 Fe1 N27 91.3(2) . . ? N33 Fe1 N27 160.7(2) . . ? N9 Fe1 N27 92.7(2) . . ? C3 N2 C7 118.9(6) . . ? C3 N2 Fe1 120.9(5) . . ? C7 N2 Fe1 120.2(4) . . ? N2 C3 C4 122.5(7) . . ? N2 C3 N8 110.2(6) . . ? C4 C3 N8 127.2(7) . . ? C5 C4 C3 117.2(7) . . ? C6 C5 C4 122.0(7) . . ? C5 C6 C7 117.4(7) . . ? N2 C7 C6 121.9(6) . . ? N2 C7 N14 108.9(6) . . ? C6 C7 N14 129.2(7) . . ? C12 N8 N9 111.1(6) . . ? C12 N8 C3 132.0(6) . . ? N9 N8 C3 116.8(5) . . ? C10 N9 N8 104.2(6) . . ? C10 N9 Fe1 143.6(5) . . ? N8 N9 Fe1 112.1(4) . . ? N9 C10 C11 111.0(7) . . ? C12 C11 C10 106.0(6) . . ? C12 C11 Cl13 126.0(6) . . ? C10 C11 Cl13 128.0(7) . . ? N8 C12 C11 107.6(7) . . ? C18 N14 N15 112.9(6) . . ? C18 N14 C7 129.8(7) . . ? N15 N14 C7 117.2(6) . . ? C16 N15 N14 104.6(6) . . ? C16 N15 Fe1 141.9(6) . . ? N14 N15 Fe1 113.5(4) . . ? N15 C16 C17 110.8(7) . . ? C18 C17 C16 107.9(7) . . ? C18 C17 Cl19 125.6(7) . . ? C16 C17 Cl19 126.5(7) . . ? N14 C18 C17 103.8(7) . . ? C25 N20 C21 119.8(6) . . ? C25 N20 Fe1 120.2(5) . . ? C21 N20 Fe1 119.9(5) . . ? N20 C21 C22 121.2(6) . . ? N20 C21 N26 109.8(6) . . ? C22 C21 N26 128.9(6) . . ? C23 C22 C21 117.1(7) . . ? C22 C23 C24 122.4(7) . . ? C25 C24 C23 115.3(7) . . ? N20 C25 C24 124.1(7) . . ? N20 C25 N32 111.3(6) . . ? C24 C25 N32 124.6(6) . . ? N27 N26 C30 113.0(6) . . ? N27 N26 C21 117.8(5) . . ? C30 N26 C21 128.9(6) . . ? C28 N27 N26 105.0(6) . . ? C28 N27 Fe1 143.1(5) . . ? N26 N27 Fe1 111.8(4) . . ? N27 C28 C29 109.2(6) . . ? C30 C29 C28 108.4(6) . . ? C30 C29 Cl31 125.3(6) . . ? C28 C29 Cl31 126.1(6) . . ? C29 C30 N26 104.3(6) . . ? C36 N32 N33 112.0(6) . . ? C36 N32 C25 132.4(6) . . ? N33 N32 C25 115.6(5) . . ? C34 N33 N32 105.9(6) . . ? C34 N33 Fe1 141.6(6) . . ? N32 N33 Fe1 112.5(4) . . ? N33 C34 C35 109.9(7) . . ? C36 C35 C34 108.0(6) . . ? C36 C35 Cl37 125.4(6) . . ? C34 C35 Cl37 126.6(6) . . ? N32 C36 C35 104.2(6) . . ? F39A B38A F40A 110.6(15) . . ? F39A B38A F42A 110.5(14) . . ? F40A B38A F42A 110.4(15) . . ? F39A B38A F41A 111.4(15) . . ? F40A B38A F41A 107.1(14) . . ? F42A B38A F41A 106.7(13) . . ? F41B B38B F39B 107.9(16) . . ? F41B B38B F40B 110.4(16) . . ? F39B B38B F40B 108.1(16) . . ? F41B B38B F42B 112.4(16) . . ? F39B B38B F42B 107.9(16) . . ? F40B B38B F42B 110.0(16) . . ? F41C B38C F39C 110.0(15) . . ? F41C B38C F40C 108.0(13) . . ? F39C B38C F40C 107.6(15) . . ? F41C B38C F42C 109.8(14) . . ? F39C B38C F42C 111.9(15) . . ? F40C B38C F42C 109.4(14) . . ? F45C B43C F47C 109.8(14) . . ? F45C B43C F46C 109.5(15) . . ? F47C B43C F46C 108.5(15) . . ? F45C B43C F44C 106.8(15) . . ? F47C B43C F44C 112.3(15) . . ? F46C B43C F44C 110.0(14) . . ? F47A B43A F45A 111.8(15) . . ? F47A B43A F44A 109.4(15) . . ? F45A B43A F44A 109.1(15) . . ? F47A B43A F46A 110.3(16) . . ? F45A B43A F46A 108.2(15) . . ? F44A B43A F46A 108.0(15) . . ? F45B B43B F47B 111.9(16) . . ? F45B B43B F44B 110.9(17) . . ? F47B B43B F44B 107.5(16) . . ? F45B B43B F46B 110.2(16) . . ? F47B B43B F46B 108.6(16) . . ? F44B B43B F46B 107.6(15) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.54 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.719 _refine_diff_density_min -0.612 _refine_diff_density_rms 0.134