# Electronic Supplementary Material (ESI) for Chemical Science # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full 'Chemical Science' _journal_coden_cambridge 1475 #TrackingRef 'TRLIG.CIF' #==================================================================== # 1. SUBMISSION DETAILS _publ_contact_author 'Prof. Malcolm A. Halcrow' _publ_contact_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 data are for one of four structures included in a manuscript that we will shortly submit to Angewandte Chemie ; #======================================================================= # 2. TITLE AND AUTHOR LIST _publ_section_title ; An Iron(II) Complex Exhibiting Four Different Anhydrous Phases, Two of Which Interconvert by Spin-Crossover with Wide Hysteresis ; loop_ _publ_author_name _publ_author_address 'Thomas D. Roberts' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Floriana Tuna' ; School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK ; 'Tamsin Malkin' ; 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 ; data_tr10a _database_code_depnum_ccdc_archive 'CCDC 836761' #TrackingRef 'TR10A.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-bis(5-methylpyrazol-3-yl)pyridine]iron(II) ditetrafluoroborate dihydrate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H26 Fe N10, 2[B F4], 2[H2 O]' _chemical_formula_sum 'C26 H30 B2 F8 Fe N10 O2' _chemical_formula_weight 744.07 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'I 41/a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y+3/4, x+1/4, z+1/4' '-x, -y+1/2, z' 'y+1/4, -x+1/4, z+1/4' 'x+1/2, y+1/2, z+1/2' '-y+5/4, x+3/4, z+3/4' '-x+1/2, -y+1, z+1/2' 'y+3/4, -x+3/4, z+3/4' '-x, -y, -z' 'y-3/4, -x-1/4, -z-1/4' 'x, y-1/2, -z' '-y-1/4, x-1/4, -z-1/4' '-x+1/2, -y+1/2, -z+1/2' 'y-1/4, -x+1/4, -z+1/4' 'x+1/2, y, -z+1/2' '-y+1/4, x+1/4, -z+1/4' _cell_length_a 13.7494(19) _cell_length_b 13.7494(19) _cell_length_c 35.336(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 6680.2(14) _cell_formula_units_Z 8 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 35446 _cell_measurement_theta_min 1.59 _cell_measurement_theta_max 28.86 _exptl_crystal_description 'rectangular prism' _exptl_crystal_colour brown _exptl_crystal_size_max 0.41 _exptl_crystal_size_mid 0.32 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.480 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3040 _exptl_absorpt_coefficient_mu 0.538 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.586 _exptl_absorpt_correction_T_max 0.752 _exptl_absorpt_process_details ; Sheldrick, G. M. (2002). SADABS v. 2.03. University of G/ottingen, Germany. ; _exptl_special_details ; Rotating anode power 3 kW. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker X8 Apex diffractometer' _diffrn_measurement_method 'Rotation images' _diffrn_detector_area_resol_mean '120 microns' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 35446 _diffrn_reflns_av_R_equivalents 0.0855 _diffrn_reflns_av_sigmaI/netI 0.0497 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -48 _diffrn_reflns_limit_l_max 47 _diffrn_reflns_theta_min 1.59 _diffrn_reflns_theta_max 28.86 _reflns_number_total 4363 _reflns_number_gt 2833 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX 2 software, Bruker Nonius 2004' _computing_cell_refinement 'APEX 2 software, Bruker Nonius 2004' _computing_data_reduction 'SAINT, Bruker Nonius 2004' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSEED (Barbour, 2001)' _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 two unique quarter-cations, whose Fe atoms lie on the -4 sites 0, 1/4, 1/8 (Fe1) and 1/2, 3/4, 1/8 (Fe12); and, one BF~4~^-^ ion and one water molecule lying on general crystallogaphic positions. No disorder was detected during refinement, and no restraints were applied. All non-H atoms were refined anisotropically, and C- and N-bound H atoms were placed in calculated positions and refined using a riding model. The water H atoms were located in the difference map, and allowed to refine subject to the restraint O---H = 0.90(2)\%A. ; _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^)+(0.0462P)^2^+7.7563P] 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 4363 _refine_ls_number_parameters 233 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0771 _refine_ls_R_factor_gt 0.0428 _refine_ls_wR_factor_ref 0.1211 _refine_ls_wR_factor_gt 0.1034 _refine_ls_goodness_of_fit_ref 1.009 _refine_ls_restrained_S_all 1.009 _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 0.2500 0.1250 0.02241(14) Uani 1 4 d S . . N2 N 0.0000 0.2500 0.06381(7) 0.0253(5) Uani 1 2 d S . . C3 C 0.03520(14) 0.32763(15) 0.04458(6) 0.0275(4) Uani 1 1 d . . . C4 C 0.03679(16) 0.33014(17) 0.00501(6) 0.0359(5) Uani 1 1 d . . . H4 H 0.0622 0.3848 -0.0082 0.043 Uiso 1 1 calc R . . C5 C 0.0000 0.2500 -0.01454(9) 0.0406(8) Uani 1 2 d S . . H5 H 0.0000 0.2500 -0.0414 0.049 Uiso 1 2 calc SR . . C6 C 0.06989(14) 0.40554(15) 0.06972(6) 0.0284(4) Uani 1 1 d . . . N7 N 0.06393(12) 0.38948(12) 0.10740(5) 0.0274(4) Uani 1 1 d . . . N8 N 0.09964(13) 0.47183(13) 0.12332(5) 0.0307(4) Uani 1 1 d . . . H8 H 0.1041 0.4810 0.1479 0.037 Uiso 1 1 calc R . . C9 C 0.12771(15) 0.53838(16) 0.09722(7) 0.0356(5) Uani 1 1 d . . . C10 C 0.10933(16) 0.49833(16) 0.06215(7) 0.0353(5) Uani 1 1 d . . . H10 H 0.1207 0.5270 0.0381 0.042 Uiso 1 1 calc R . . C11 C 0.17031(18) 0.63531(17) 0.10828(8) 0.0470(6) Uani 1 1 d . . . H11A H 0.1685 0.6794 0.0865 0.070 Uiso 1 1 calc R . . H11B H 0.2378 0.6263 0.1165 0.070 Uiso 1 1 calc R . . H11C H 0.1323 0.6632 0.1291 0.070 Uiso 1 1 calc R . . Fe12 Fe 0.5000 0.7500 0.1250 0.02284(14) Uani 1 4 d S . . N13 N 0.5000 0.7500 0.07004(7) 0.0252(5) Uani 1 2 d S . . C14 C 0.47014(14) 0.66959(15) 0.05087(6) 0.0299(4) Uani 1 1 d . . . C15 C 0.47059(17) 0.66688(18) 0.01139(6) 0.0381(5) Uani 1 1 d . . . H15 H 0.4514 0.6099 -0.0019 0.046 Uiso 1 1 calc R . . C16 C 0.5000 0.7500 -0.00808(10) 0.0432(8) Uani 1 2 d S . . H16 H 0.5000 0.7500 -0.0350 0.052 Uiso 1 2 calc SR . . C17 C 0.43837(14) 0.59372(15) 0.07724(6) 0.0283(4) Uani 1 1 d . . . N18 N 0.44769(12) 0.61760(12) 0.11421(5) 0.0263(4) Uani 1 1 d . . . N19 N 0.41252(12) 0.54049(12) 0.13401(5) 0.0283(4) Uani 1 1 d . . . H19 H 0.4097 0.5376 0.1589 0.034 Uiso 1 1 calc R . . C20 C 0.38210(15) 0.46825(15) 0.11036(7) 0.0328(5) Uani 1 1 d . . . C21 C 0.39722(16) 0.50013(15) 0.07368(7) 0.0345(5) Uani 1 1 d . . . H21 H 0.3829 0.4662 0.0509 0.041 Uiso 1 1 calc R . . C22 C 0.34167(18) 0.37422(17) 0.12549(8) 0.0444(6) Uani 1 1 d . . . H22A H 0.3946 0.3272 0.1287 0.067 Uiso 1 1 calc R . . H22B H 0.2937 0.3482 0.1076 0.067 Uiso 1 1 calc R . . H22C H 0.3104 0.3860 0.1500 0.067 Uiso 1 1 calc R . . B23 B 0.1607(2) 0.4971(2) 0.22316(8) 0.0402(6) Uani 1 1 d . . . F24 F 0.23907(12) 0.55419(15) 0.23473(6) 0.0773(6) Uani 1 1 d . . . F25 F 0.10447(12) 0.47825(14) 0.25494(5) 0.0706(5) Uani 1 1 d . . . F26 F 0.19559(13) 0.41229(12) 0.20725(5) 0.0707(5) Uani 1 1 d . . . F27 F 0.10560(15) 0.54934(14) 0.19733(5) 0.0785(6) Uani 1 1 d . . . O28 O 0.42694(14) 0.51701(16) 0.21054(5) 0.0522(5) Uani 1 1 d D . . H28A H 0.3749(19) 0.527(3) 0.2242(9) 0.088(12) Uiso 1 1 d D . . H28B H 0.4765(18) 0.506(2) 0.2252(8) 0.077(11) Uiso 1 1 d 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 Fe1 0.02185(19) 0.02185(19) 0.0235(3) 0.000 0.000 0.000 N2 0.0241(12) 0.0255(12) 0.0264(12) 0.000 0.000 0.0000(10) C3 0.0226(10) 0.0304(10) 0.0296(11) 0.0027(8) 0.0015(8) 0.0015(8) C4 0.0376(12) 0.0413(12) 0.0287(11) 0.0072(10) 0.0044(9) 0.0019(10) C5 0.0446(19) 0.054(2) 0.0230(15) 0.000 0.000 0.0035(16) C6 0.0247(10) 0.0266(10) 0.0339(11) 0.0057(8) 0.0010(8) 0.0001(8) N7 0.0260(9) 0.0234(9) 0.0329(10) 0.0008(7) -0.0008(7) -0.0020(7) N8 0.0296(9) 0.0256(9) 0.0368(10) -0.0026(7) -0.0035(8) -0.0026(7) C9 0.0251(10) 0.0274(11) 0.0543(15) 0.0042(10) -0.0010(10) -0.0008(9) C10 0.0316(11) 0.0301(11) 0.0443(13) 0.0101(10) 0.0024(10) -0.0037(9) C11 0.0399(13) 0.0278(12) 0.0732(18) 0.0019(12) -0.0074(13) -0.0061(10) Fe12 0.02019(18) 0.02019(18) 0.0281(3) 0.000 0.000 0.000 N13 0.0229(12) 0.0251(12) 0.0277(12) 0.000 0.000 0.0001(10) C14 0.0268(10) 0.0299(11) 0.0330(11) -0.0033(9) -0.0012(9) -0.0018(9) C15 0.0388(13) 0.0405(13) 0.0351(12) -0.0068(10) -0.0022(10) -0.0057(10) C16 0.049(2) 0.051(2) 0.0299(16) 0.000 0.000 -0.0057(17) C17 0.0246(10) 0.0258(10) 0.0346(11) -0.0043(8) -0.0022(8) 0.0005(8) N18 0.0215(8) 0.0220(8) 0.0353(9) 0.0010(7) 0.0004(7) -0.0008(6) N19 0.0233(8) 0.0240(8) 0.0377(10) 0.0042(7) 0.0011(7) 0.0001(7) C20 0.0241(10) 0.0252(10) 0.0491(13) -0.0017(10) -0.0030(9) -0.0015(8) C21 0.0310(11) 0.0271(11) 0.0453(14) -0.0055(9) -0.0031(10) -0.0025(9) C22 0.0382(13) 0.0282(12) 0.0668(17) 0.0038(11) -0.0002(12) -0.0064(10) B23 0.0351(14) 0.0443(16) 0.0410(15) -0.0049(12) 0.0008(12) -0.0004(12) F24 0.0429(9) 0.0882(14) 0.1009(14) -0.0485(12) 0.0142(9) -0.0081(9) F25 0.0576(10) 0.0823(12) 0.0720(12) 0.0261(9) 0.0267(9) 0.0237(9) F26 0.0678(11) 0.0497(9) 0.0946(14) -0.0196(9) 0.0230(10) -0.0031(8) F27 0.1090(15) 0.0810(13) 0.0456(10) -0.0065(9) -0.0191(10) 0.0255(11) O28 0.0347(10) 0.0789(14) 0.0432(11) 0.0135(10) 0.0000(9) 0.0018(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe1 N2 2.162(2) . ? Fe1 N7 2.1994(16) . ? N2 C3 1.355(2) . ? C3 C4 1.399(3) . ? C3 C6 1.471(3) . ? C4 C5 1.395(3) . ? C6 N7 1.352(3) . ? C6 C10 1.412(3) . ? N7 N8 1.356(2) . ? N8 C9 1.355(3) . ? C9 C10 1.380(3) . ? C9 C11 1.507(3) . ? Fe12 N13 1.942(2) . ? Fe12 N18 1.9941(16) . ? N13 C14 1.360(2) . ? C14 C15 1.395(3) . ? C14 C17 1.465(3) . ? C15 C16 1.394(3) . ? C17 N18 1.353(3) . ? C17 C21 1.411(3) . ? N18 N19 1.359(2) . ? N19 C20 1.364(3) . ? C20 C21 1.384(3) . ? C20 C22 1.505(3) . ? B23 F26 1.380(3) . ? B23 F27 1.386(3) . ? B23 F25 1.388(3) . ? B23 F24 1.395(3) . ? O28 H28A 0.874(18) . ? O28 H28B 0.869(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 N2 Fe1 N2 180.00 . 14 ? N2 Fe1 N7 73.58(5) . . ? N7 Fe1 N7 147.15(9) 3 . ? N2 Fe1 N7 106.42(5) . 14 ? N7 Fe1 N7 94.59(2) . 14 ? C3 N2 C3 119.8(2) 3 . ? C3 N2 Fe1 120.10(12) 3 . ? C3 N2 Fe1 120.10(12) . . ? N2 C3 C4 121.8(2) . . ? N2 C3 C6 112.75(18) . . ? C4 C3 C6 125.5(2) . . ? C5 C4 C3 118.0(2) . . ? C4 C5 C4 120.7(3) . 3 ? N7 C6 C10 110.95(19) . . ? N7 C6 C3 117.14(18) . . ? C10 C6 C3 131.9(2) . . ? C6 N7 N8 104.48(16) . . ? C6 N7 Fe1 116.43(13) . . ? N8 N7 Fe1 139.06(14) . . ? C9 N8 N7 112.62(18) . . ? N8 C9 C10 106.84(19) . . ? N8 C9 C11 122.1(2) . . ? C10 C9 C11 131.1(2) . . ? C9 C10 C6 105.1(2) . . ? N13 Fe12 N13 180.00 . 14_565 ? N13 Fe12 N18 78.98(5) . . ? N18 Fe12 N18 157.95(10) . 3_665 ? N13 Fe12 N18 101.02(5) . 14_565 ? N18 Fe12 N18 92.095(19) . 14_565 ? C14 N13 C14 120.3(3) . 3_665 ? C14 N13 Fe12 119.86(13) . . ? C14 N13 Fe12 119.86(13) 3_665 . ? N13 C14 C15 121.2(2) . . ? N13 C14 C17 110.61(18) . . ? C15 C14 C17 128.2(2) . . ? C16 C15 C14 118.2(2) . . ? N18 C17 C21 110.20(19) . . ? N18 C17 C14 114.39(17) . . ? C21 C17 C14 135.4(2) . . ? C17 N18 N19 105.89(16) . . ? C17 N18 Fe12 116.13(13) . . ? N19 N18 Fe12 137.91(14) . . ? N18 N19 C20 111.22(18) . . ? N19 C20 C21 107.28(19) . . ? N19 C20 C22 121.4(2) . . ? C21 C20 C22 131.3(2) . . ? C20 C21 C17 105.4(2) . . ? F26 B23 F27 111.1(2) . . ? F26 B23 F25 111.5(2) . . ? F27 B23 F25 109.0(2) . . ? F26 B23 F24 109.0(2) . . ? F27 B23 F24 108.9(2) . . ? F25 B23 F24 107.3(2) . . ? H28A O28 H28B 110(3) . . ? 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 N8 H8 F27 0.88 1.98 2.825(3) 159.8 . N19 H19 O28 0.88 1.86 2.731(3) 168.4 . O28 H28A F24 0.874(18) 1.94(2) 2.769(3) 158(3) . O28 H28B F25 0.869(18) 1.93(2) 2.780(2) 165(3) 15 _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 28.86 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.482 _refine_diff_density_min -0.463 _refine_diff_density_rms 0.054 # Attachment 'TR10LT.CIF' data_tr10lt _database_code_depnum_ccdc_archive 'CCDC 836762' #TrackingRef 'TR10LT.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-bis(5-methylpyrazol-3-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H26 Fe N10, 2[B F4]' _chemical_formula_sum 'C26 H26 B2 F8 Fe N10' _chemical_formula_weight 708.04 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' Fe Fe 0.3463 0.8444 '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(2)/n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x+1/2, z+1/2' '-x+1/2, -y+1/2, z' 'y+1/2, -x, z+1/2' '-x, -y, -z' 'y, -x-1/2, -z-1/2' 'x-1/2, y-1/2, -z' '-y-1/2, x, -z-1/2' _cell_length_a 9.7481(2) _cell_length_b 9.7481(2) _cell_length_c 17.6848(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1680.51(7) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 29002 _cell_measurement_theta_min 2.03 _cell_measurement_theta_max 28.72 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.399 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 0.527 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.713 _exptl_absorpt_correction_T_max 1.086 _exptl_absorpt_process_details ; Sheldrick, G. M. (2002). SADABS v. 2.03. University of G/ottingen, Germany. ; _exptl_special_details ; Rotating anode power 3 kW. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker X8 Apex diffractometer' _diffrn_measurement_method 'Rotation images' _diffrn_detector_area_resol_mean '120 microns' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 29002 _diffrn_reflns_av_R_equivalents 0.0536 _diffrn_reflns_av_sigmaI/netI 0.0204 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.30 _diffrn_reflns_theta_max 28.72 _reflns_number_total 2179 _reflns_number_gt 1721 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX 2 software, Bruker Nonius 2004' _computing_cell_refinement 'APEX 2 software, Bruker Nonius 2004' _computing_data_reduction 'SAINT, Bruker Nonius 2004' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSEED (Barbour, 2001)' _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, 1/4, 1/4] and N2 and C5 lying on the C2 axis [1/4, 1/4, z]; and, half a BF~4~^-^ anion that is disordered about the C~2~ axis [1/4, 3/4, z]. Two equally occupied partial environments for this disordered half-anion B12-F16 were refined, labelled 'A' and 'B', which shared a common half-occupied B atom B12. These were subject to the refined restraints B---F = 1.42(2)\%A and F...F = 2.32(2)\%A. All non-H atoms except the disordered F atoms were refined anisotropically, and all H atoms were placed in calculated positions and refined using a riding model. The highest residual Fourier peak of +1.1 e.\%A^-3^ lies within the disordered anion. ; _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^)+(0.1682P)^2^+2.3649P] 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 2179 _refine_ls_number_parameters 128 _refine_ls_number_restraints 20 _refine_ls_R_factor_all 0.1048 _refine_ls_R_factor_gt 0.0909 _refine_ls_wR_factor_ref 0.2881 _refine_ls_wR_factor_gt 0.2721 _refine_ls_goodness_of_fit_ref 1.072 _refine_ls_restrained_S_all 1.099 _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 0.2500 0.2500 0.2500 0.0362(4) Uani 1 4 d S . . N2 N 0.2500 0.2500 0.1378(4) 0.0576(14) Uani 1 2 d S . . C3 C 0.2966(7) 0.3619(6) 0.0999(3) 0.0775(16) Uani 1 1 d . . . C4 C 0.2988(13) 0.3589(10) 0.0203(4) 0.132(4) Uani 1 1 d . . . H4 H 0.3352 0.4347 -0.0068 0.159 Uiso 1 1 calc R . . C5 C 0.2500 0.2500 -0.0176(7) 0.165(9) Uani 1 2 d S . . H5 H 0.2500 0.2500 -0.0713 0.198 Uiso 1 2 calc SR . . C6 C 0.3391(5) 0.4689(5) 0.1518(3) 0.0637(12) Uani 1 1 d . . . N7 N 0.3280(3) 0.4380(3) 0.2251(3) 0.0514(9) Uani 1 1 d . . . N8 N 0.3717(4) 0.5496(5) 0.2623(3) 0.0700(14) Uani 1 1 d . . . H8 H 0.3753 0.5577 0.3118 0.084 Uiso 1 1 calc R . . C9 C 0.4102(5) 0.6499(5) 0.2113(6) 0.085(2) Uani 1 1 d . . . C10 C 0.3878(6) 0.6011(6) 0.1411(5) 0.087(2) Uani 1 1 d . . . H10 H 0.4022 0.6472 0.0945 0.104 Uiso 1 1 calc R . . C11 C 0.4647(7) 0.7869(7) 0.2408(7) 0.140(5) Uani 1 1 d . . . H11A H 0.5617 0.7772 0.2543 0.209 Uiso 1 1 calc R . . H11B H 0.4122 0.8144 0.2856 0.209 Uiso 1 1 calc R . . H11C H 0.4550 0.8570 0.2014 0.209 Uiso 1 1 calc R . . B12 B 0.3363(13) 0.6488(13) 0.4454(7) 0.25(3) Uani 0.50 1 d PD . . F13A F 0.4083(15) 0.5284(14) 0.4212(8) 0.066(4) Uiso 0.25 1 d PD A 1 F14A F 0.1883(12) 0.6408(15) 0.4448(9) 0.076(4) Uiso 0.25 1 d PD . 1 F15A F 0.3709(14) 0.6589(16) 0.5227(6) 0.073(3) Uiso 0.25 1 d PD A 1 F16A F 0.378(2) 0.7677(17) 0.4068(12) 0.121(7) Uiso 0.25 1 d PD . 1 F13B F 0.4310(18) 0.556(2) 0.4122(11) 0.096(7) Uiso 0.25 1 d PD A 2 F14B F 0.2030(15) 0.627(2) 0.4183(12) 0.117(8) Uiso 0.25 1 d PD . 2 F15B F 0.344(2) 0.606(2) 0.5235(9) 0.130(8) Uiso 0.25 1 d PD A 2 F16B F 0.369(3) 0.7879(19) 0.4411(18) 0.199(15) Uiso 0.25 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 0.0332(4) 0.0332(4) 0.0422(6) 0.000 0.000 0.000 N2 0.075(4) 0.041(2) 0.056(3) 0.000 0.000 0.000(2) C3 0.100(4) 0.065(3) 0.068(3) 0.018(2) 0.007(3) -0.008(3) C4 0.213(12) 0.112(6) 0.072(5) 0.027(4) 0.016(6) -0.025(7) C5 0.28(3) 0.154(14) 0.058(6) 0.000 0.000 -0.044(14) C6 0.061(3) 0.045(2) 0.085(3) 0.012(2) 0.007(2) 0.0010(18) N7 0.0408(16) 0.0371(16) 0.076(2) -0.0113(16) -0.0008(16) 0.0018(13) N8 0.0372(17) 0.046(2) 0.126(4) -0.031(2) -0.004(2) 0.0031(14) C9 0.039(2) 0.042(2) 0.174(7) -0.001(3) -0.001(3) 0.0024(17) C10 0.077(4) 0.047(3) 0.135(6) 0.025(3) 0.001(4) -0.006(2) C11 0.056(3) 0.045(3) 0.318(16) -0.033(5) 0.002(5) -0.005(3) B12 0.33(5) 0.17(2) 0.24(3) 0.14(3) -0.23(4) -0.18(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe1 N2 1.984(6) . ? Fe1 N7 2.033(4) . ? N2 C3 1.358(6) . ? C3 C4 1.408(10) . ? C3 C6 1.449(8) . ? C4 C5 1.343(12) . ? C6 N7 1.335(7) . ? C6 C10 1.386(7) . ? N7 N8 1.341(5) . ? N8 C9 1.382(9) . ? C9 C10 1.347(12) . ? C9 C11 1.529(8) . ? B12 F16A 1.405(15) . ? B12 F15A 1.412(15) . ? B12 F13A 1.432(16) . ? B12 F14A 1.445(15) . ? B12 F16B 1.397(17) . ? B12 F14B 1.401(16) . ? B12 F13B 1.419(16) . ? B12 F15B 1.444(16) . ? 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 6_566 . ? N2 Fe1 N7 102.53(12) . 6_566 ? N2 Fe1 N7 77.47(12) . . ? N7 Fe1 N7 92.70(5) 6_566 . ? N7 Fe1 N7 154.9(2) 3 . ? C3 N2 C3 120.9(7) . 3 ? C3 N2 Fe1 119.5(4) . . ? N2 C3 C4 118.8(7) . . ? N2 C3 C6 111.2(5) . . ? C4 C3 C6 130.0(6) . . ? C5 C4 C3 120.7(8) . . ? C4 C5 C4 120.0(12) 3 . ? N7 C6 C10 111.7(6) . . ? N7 C6 C3 115.4(4) . . ? C10 C6 C3 132.9(6) . . ? C6 N7 N8 105.6(4) . . ? C6 N7 Fe1 116.4(3) . . ? N8 N7 Fe1 138.1(4) . . ? N7 N8 C9 109.9(6) . . ? C10 C9 N8 107.9(5) . . ? C10 C9 C11 132.8(8) . . ? N8 C9 C11 119.3(8) . . ? C9 C10 C6 105.0(6) . . ? F16A B12 F15A 110.1(12) . . ? F16A B12 F13A 113.0(13) . . ? F15A B12 F13A 103.3(10) . . ? F16A B12 F14A 109.1(12) . . ? F15A B12 F14A 104.4(12) . . ? F13A B12 F14A 116.3(12) . . ? F16B B12 F14B 110.0(14) . . ? F16B B12 F13B 116.5(15) . . ? F14B B12 F13B 111.4(13) . . ? F16B B12 F15B 108.6(14) . . ? F14B B12 F15B 109.2(13) . . ? F13B B12 F15B 100.4(12) . . ? 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 N8 H8 F13A 0.88 1.98 2.840(16) 164.8 . N8 H8 F13B 0.88 1.86 2.71(2) 164.3 . _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 28.72 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.090 _refine_diff_density_min -0.320 _refine_diff_density_rms 0.115 # Attachment 'TR10RT.CIF' data_tr10rt _database_code_depnum_ccdc_archive 'CCDC 836763' #TrackingRef 'TR10RT.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[2,6-bis(5-methylpyrazol-3-yl)pyridine]iron(II) ditetrafluoroborate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H26 Fe N10, 2[B F4]' _chemical_formula_sum 'C26 H26 B2 F8 Fe N10' _chemical_formula_weight 708.04 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' Fe Fe 0.3463 0.8444 '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(2)/n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x+1/2, z+1/2' '-x+1/2, -y+1/2, z' 'y+1/2, -x, z+1/2' '-x, -y, -z' 'y, -x-1/2, -z-1/2' 'x-1/2, y-1/2, -z' '-y-1/2, x, -z-1/2' _cell_length_a 9.8046(5) _cell_length_b 9.8046(5) _cell_length_c 17.8869(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1719.47(18) _cell_formula_units_Z 2 _cell_measurement_temperature 300(2) _cell_measurement_reflns_used 29025 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 28.41 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.368 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 0.515 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.648 _exptl_absorpt_correction_T_max 0.801 _exptl_absorpt_process_details ; Sheldrick, G. M. (2002). SADABS v. 2.03. University of G/ottingen, Germany. ; _exptl_special_details ; Rotating anode power 3 kW. ; _diffrn_ambient_temperature 300(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker X8 Apex diffractometer' _diffrn_measurement_method 'Rotation images' _diffrn_detector_area_resol_mean '120 microns' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 29025 _diffrn_reflns_av_R_equivalents 0.0697 _diffrn_reflns_av_sigmaI/netI 0.0300 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.28 _diffrn_reflns_theta_max 28.41 _reflns_number_total 2165 _reflns_number_gt 1612 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX 2 software, Bruker Nonius 2004' _computing_cell_refinement 'APEX 2 software, Bruker Nonius 2004' _computing_data_reduction 'SAINT, Bruker Nonius 2004' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSEED (Barbour, 2001)' _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, 1/4, 1/4] and N2 and C5 lying on the C2 axis [1/4, 1/4, z]; and, half a BF~4~^-^ anion that is disordered about the C~2~ axis [1/4, 3/4, z]. Three partial environments for this disordered half-anion B12-F16 were refined, labelled 'A' (occupancy 0.25), 'B' (0.20) and 'C' (0.05), which shared a common half-occupied B atom B12. These were subject to the fixed restraints B---F = 1.38(2)\%A and F...F = 2.25(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^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2165 _refine_ls_number_parameters 137 _refine_ls_number_restraints 30 _refine_ls_R_factor_all 0.0952 _refine_ls_R_factor_gt 0.0797 _refine_ls_wR_factor_ref 0.2717 _refine_ls_wR_factor_gt 0.2612 _refine_ls_goodness_of_fit_ref 2.031 _refine_ls_restrained_S_all 2.110 _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 0.2500 0.2500 0.2500 0.0502(4) Uani 1 4 d S . . N2 N 0.2500 0.2500 0.1321(3) 0.0632(10) Uani 1 2 d S . . C3 C 0.3589(4) 0.2972(4) 0.0935(2) 0.0760(10) Uani 1 1 d . . . C4 C 0.3616(6) 0.2980(6) 0.0161(3) 0.1075(17) Uani 1 1 d . . . H4 H 0.4395 0.3311 -0.0097 0.129 Uiso 1 1 calc R . . C5 C 0.2500 0.2500 -0.0231(5) 0.122(4) Uani 1 2 d S . . H5 H 0.2500 0.2500 -0.0763 0.146 Uiso 1 2 calc SR . . C6 C 0.4713(3) 0.3408(4) 0.1434(2) 0.0705(9) Uani 1 1 d . . . N7 N 0.4472(3) 0.3312(3) 0.2173(2) 0.0649(8) Uani 1 1 d . . . N8 N 0.5633(4) 0.3765(4) 0.24982(17) 0.0757(10) Uani 1 1 d . . . H8 H 0.5760 0.3807 0.2985 0.091 Uiso 1 1 calc RD . . C9 C 0.6573(4) 0.4144(4) 0.1988(3) 0.0905(15) Uani 1 1 d . . . C10 C 0.6022(5) 0.3926(5) 0.1307(3) 0.0918(14) Uani 1 1 d . . . H10 H 0.6439 0.4091 0.0837 0.110 Uiso 1 1 calc R . . C11 C 0.7959(5) 0.4678(6) 0.2226(5) 0.135(2) Uani 1 1 d . . . H11A H 0.8096 0.4496 0.2760 0.203 Uiso 1 1 calc R . . H11B H 0.8004 0.5662 0.2136 0.203 Uiso 1 1 calc R . . H11C H 0.8674 0.4219 0.1937 0.203 Uiso 1 1 calc R . . B12 B 0.6500(11) 0.3387(10) 0.4410(6) 0.116(4) Uiso 0.50 1 d PD . . F13A F 0.6181(19) 0.4403(12) 0.3956(7) 0.122(5) Uiso 0.25 1 d PD A 1 F14A F 0.7832(12) 0.3144(14) 0.4631(8) 0.126(4) Uiso 0.25 1 d PD . 1 F15A F 0.5701(17) 0.354(2) 0.5031(8) 0.156(7) Uiso 0.25 1 d PD A 1 F16A F 0.6164(17) 0.2200(14) 0.3986(9) 0.143(5) Uiso 0.25 1 d PD . 1 F13B F 0.5447(10) 0.4149(10) 0.4131(6) 0.068(2) Uiso 0.20 1 d PD A 2 F14B F 0.638(2) 0.367(2) 0.5183(7) 0.125(8) Uiso 0.20 1 d PD A 2 F15B F 0.7704(16) 0.376(2) 0.4127(13) 0.186(9) Uiso 0.20 1 d PD . 2 F16B F 0.632(2) 0.1963(14) 0.4344(14) 0.166(9) Uiso 0.20 1 d PD . 2 F13C F 0.678(3) 0.450(2) 0.3913(15) 0.054(8) Uiso 0.05 1 d PD A 3 F14C F 0.613(5) 0.398(4) 0.5101(14) 0.066(11) Uiso 0.05 1 d PD A 3 F15C F 0.525(2) 0.287(4) 0.414(3) 0.19(4) Uiso 0.05 1 d PD A 3 F16C F 0.7500 0.2500 0.4301(19) 0.29(6) Uiso 0.10 2 d SPD . 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 0.0489(4) 0.0489(4) 0.0527(6) 0.000 0.000 0.000 N2 0.060(2) 0.070(2) 0.059(2) 0.000 0.000 0.0035(16) C3 0.078(2) 0.082(2) 0.069(2) 0.0050(17) 0.0111(18) 0.0015(18) C4 0.113(4) 0.130(4) 0.080(3) 0.014(3) 0.025(3) -0.004(3) C5 0.144(7) 0.162(8) 0.060(4) 0.000 0.000 -0.020(5) C6 0.0592(18) 0.071(2) 0.081(2) 0.0038(17) 0.0113(16) -0.0004(15) N7 0.0534(15) 0.0586(15) 0.083(2) 0.0009(15) -0.0025(14) -0.0012(11) N8 0.0597(18) 0.0600(18) 0.107(3) -0.0015(13) -0.0178(14) -0.0036(14) C9 0.056(2) 0.066(2) 0.149(5) 0.001(2) 0.007(2) -0.0005(17) C10 0.068(2) 0.091(3) 0.117(4) 0.006(3) 0.025(3) -0.006(2) C11 0.062(3) 0.086(3) 0.257(7) -0.015(5) -0.011(4) -0.014(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 2.109(5) . ? Fe1 N7 2.171(3) . ? N2 C3 1.353(4) . ? C3 C4 1.384(6) . ? C3 C6 1.481(6) . ? C4 C5 1.383(7) . ? C6 N7 1.347(5) . ? C6 C10 1.399(6) . ? N7 N8 1.353(5) . ? N8 C9 1.349(6) . ? C9 C10 1.348(7) . ? C9 C11 1.518(6) . ? B12 F13A 1.323(12) . ? B12 F14A 1.384(13) . ? B12 F15A 1.367(13) . ? B12 F16A 1.428(13) . ? B12 F15B 1.336(14) . ? B12 F13B 1.369(12) . ? B12 F16B 1.413(14) . ? B12 F14B 1.415(14) . ? B12 F16C 1.325(10) . ? B12 F14C 1.412(18) . ? B12 F15C 1.411(17) . ? B12 F13C 1.431(16) . ? 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 6_566 . ? N2 Fe1 N7 74.38(9) . . ? N2 Fe1 N7 105.62(9) . 6_566 ? N7 Fe1 N7 94.16(5) 6_566 3 ? N7 Fe1 N7 148.77(19) 3 . ? C3 N2 C3 118.6(5) 3 . ? C3 N2 Fe1 120.7(3) . . ? N2 C3 C4 121.8(4) . . ? N2 C3 C6 112.2(3) . . ? C4 C3 C6 125.9(4) . . ? C5 C4 C3 119.4(5) . . ? C4 C5 C4 118.9(7) 3 . ? N7 C6 C10 110.2(4) . . ? N7 C6 C3 116.2(3) . . ? C10 C6 C3 133.7(4) . . ? N8 N7 C6 104.6(3) . . ? N8 N7 Fe1 138.9(3) . . ? C6 N7 Fe1 116.5(2) . . ? N7 N8 C9 112.0(3) . . ? C10 C9 N8 107.1(4) . . ? C10 C9 C11 131.9(5) . . ? N8 C9 C11 121.1(6) . . ? C9 C10 C6 106.2(4) . . ? F13A B12 F14A 121.9(11) . . ? F13A B12 F15A 106.4(11) . . ? F14A B12 F15A 109.1(11) . . ? F13A B12 F16A 103.4(11) . . ? F14A B12 F16A 103.2(10) . . ? F15A B12 F16A 112.7(12) . . ? F15B B12 F13B 112.2(12) . . ? F15B B12 F16B 110.6(13) . . ? F13B B12 F16B 114.4(13) . . ? F15B B12 F14B 113.0(14) . . ? F13B B12 F14B 100.8(10) . . ? F16B B12 F14B 105.3(13) . . ? F16C B12 F14C 126(3) . . ? F16C B12 F15C 110.6(16) . . ? F14C B12 F15C 103.3(16) . . ? F16C B12 F13C 105.2(14) . . ? F14C B12 F13C 106.2(15) . . ? F15C B12 F13C 103.2(16) . . ? 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 N8 H8 F13A 0.88 1.88 2.735(14) 163.8 . N8 H8 F13B 0.88 2.10 2.950(10) 162.2 . N8 H8 F13C 0.88 2.06 2.86(3) 152.1 . _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 28.41 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.846 _refine_diff_density_min -0.309 _refine_diff_density_rms 0.098 #================================================================= data_trlig _database_code_depnum_ccdc_archive 'CCDC 836792' #TrackingRef 'TRLIG.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,6-bis(5-methylpyrazol-3-yl)pyridine methanol solvate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H13 N5, C H4 O' _chemical_formula_sum 'C14 H17 N5 O' _chemical_formula_weight 271.33 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' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' 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' _cell_length_a 10.0640(4) _cell_length_b 11.6546(5) _cell_length_c 12.3944(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1453.76(11) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 25693 _cell_measurement_theta_min 2.40 _cell_measurement_theta_max 28.20 _exptl_crystal_description 'rectangular prism' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.240 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 576 _exptl_absorpt_coefficient_mu 0.083 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.525 _exptl_absorpt_correction_T_max 0.655 _exptl_absorpt_process_details ; Sheldrick, G. M. (2002). SADABS v. 2.03. University of G/ottingen, Germany. ; _exptl_special_details ; Rotating anode power 3 kW. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker X8 Apex diffractometer' _diffrn_measurement_method 'Rotation images' _diffrn_detector_area_resol_mean '120 microns' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 25693 _diffrn_reflns_av_R_equivalents 0.0757 _diffrn_reflns_av_sigmaI/netI 0.0308 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.40 _diffrn_reflns_theta_max 28.20 _reflns_number_total 2046 _reflns_number_gt 1776 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX 2 software, Bruker Nonius 2004' _computing_cell_refinement 'APEX 2 software, Bruker Nonius 2004' _computing_data_reduction 'SAINT, Bruker Nonius 2004' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSEED (Barbour, 2001)' _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. No disorder was detected during refinement and no restraints were applied. All non-H atoms were refined anisotropically. Since not all H atoms could be located in the Fourier map, all C-bound H atoms were placed in calculated positions and refined using a riding model. The N- and O-bound H atoms were all located, and were allowed to refine freely with a common U~iso~ displacement parameter. Since there are no heavy atoms in the crystal the absolute structure of the crystal could not be determined. Therefore, the Friedel opposites in the data were merged for the final cycles of least-squares refinement. ; _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^)+(0.1123P)^2^+0.7018P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 7(3) _refine_ls_number_reflns 2046 _refine_ls_number_parameters 194 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0759 _refine_ls_R_factor_gt 0.0646 _refine_ls_wR_factor_ref 0.1836 _refine_ls_wR_factor_gt 0.1704 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.099 _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 N1 N 0.1277(3) 0.4429(2) 0.2964(2) 0.0253(6) Uani 1 1 d . . . C2 C 0.0421(3) 0.5319(3) 0.3090(2) 0.0254(6) Uani 1 1 d . . . H14 H 0.269(4) 0.269(3) 0.344(4) 0.032(6) Uiso 1 1 d . . . C3 C 0.0370(3) 0.6226(3) 0.2359(3) 0.0305(7) Uani 1 1 d . . . H3 H -0.0235 0.6841 0.2466 0.037 Uiso 1 1 calc R . . C4 C 0.1212(3) 0.6223(3) 0.1472(3) 0.0329(7) Uani 1 1 d . . . H4 H 0.1180 0.6831 0.0962 0.039 Uiso 1 1 calc R . . C5 C 0.2105(3) 0.5320(3) 0.1337(3) 0.0310(7) Uani 1 1 d . . . H5 H 0.2698 0.5302 0.0740 0.037 Uiso 1 1 calc R . . C6 C 0.2102(3) 0.4443(3) 0.2104(2) 0.0266(7) Uani 1 1 d . . . C7 C -0.0425(3) 0.5268(3) 0.4064(2) 0.0253(6) Uani 1 1 d . . . N8 N -0.0214(3) 0.4475(2) 0.4829(2) 0.0273(6) Uani 1 1 d . . . N9 N -0.1109(3) 0.4716(2) 0.5613(2) 0.0287(6) Uani 1 1 d . . . H9 H -0.111(4) 0.425(3) 0.619(3) 0.032(6) Uiso 1 1 d . . . C10 C -0.1879(3) 0.5635(3) 0.5369(3) 0.0284(7) Uani 1 1 d . . . C11 C -0.1464(3) 0.6016(3) 0.4368(3) 0.0292(7) Uani 1 1 d . . . H11 H -0.1806 0.6646 0.3969 0.035 Uiso 1 1 calc R . . C12 C -0.2943(4) 0.6056(4) 0.6135(3) 0.0403(9) Uani 1 1 d . . . H12A H -0.3566 0.5431 0.6289 0.060 Uiso 1 1 calc R . . H12B H -0.3423 0.6697 0.5803 0.060 Uiso 1 1 calc R . . H12C H -0.2530 0.6314 0.6809 0.060 Uiso 1 1 calc R . . C13 C 0.3011(3) 0.3455(3) 0.2044(2) 0.0264(7) Uani 1 1 d . . . N14 N 0.3007(3) 0.2636(3) 0.2809(2) 0.0283(6) Uani 1 1 d . . . N15 N 0.3900(3) 0.1791(2) 0.2611(2) 0.0297(6) Uani 1 1 d . . . C16 C 0.4494(3) 0.2093(3) 0.1683(3) 0.0281(7) Uani 1 1 d . . . C17 C 0.3974(3) 0.3128(3) 0.1290(3) 0.0274(7) Uani 1 1 d . . . H17 H 0.4221 0.3522 0.0650 0.033 Uiso 1 1 calc R . . C18 C 0.5560(4) 0.1341(3) 0.1201(3) 0.0385(8) Uani 1 1 d . . . H18A H 0.6384 0.1429 0.1615 0.058 Uiso 1 1 calc R . . H18B H 0.5716 0.1567 0.0450 0.058 Uiso 1 1 calc R . . H18C H 0.5273 0.0538 0.1225 0.058 Uiso 1 1 calc R . . C19 C 0.1262(4) 0.1836(3) 0.5647(3) 0.0392(8) Uani 1 1 d . . . H19A H 0.1941 0.1236 0.5701 0.059 Uiso 1 1 calc R . . H19B H 0.0387 0.1480 0.5557 0.059 Uiso 1 1 calc R . . H19C H 0.1267 0.2301 0.6306 0.059 Uiso 1 1 calc R . . O20 O 0.1539(3) 0.2545(2) 0.4745(2) 0.0353(6) Uani 1 1 d . . . H20 H 0.120(4) 0.314(4) 0.473(3) 0.032(6) Uiso 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 N1 0.0209(13) 0.0297(13) 0.0252(12) 0.0018(11) -0.0011(10) -0.0008(11) C2 0.0188(14) 0.0322(16) 0.0254(14) 0.0001(12) -0.0039(11) -0.0017(12) C3 0.0218(15) 0.0357(17) 0.0338(16) 0.0031(14) -0.0027(13) 0.0025(14) C4 0.0293(16) 0.0354(17) 0.0339(17) 0.0112(15) -0.0016(14) -0.0009(14) C5 0.0248(15) 0.0384(18) 0.0298(15) 0.0046(14) 0.0026(13) -0.0030(13) C6 0.0212(14) 0.0325(16) 0.0262(13) 0.0006(13) -0.0024(11) -0.0032(13) C7 0.0209(14) 0.0284(15) 0.0265(14) -0.0013(12) -0.0044(12) -0.0017(12) N8 0.0254(13) 0.0310(13) 0.0253(11) 0.0011(11) 0.0008(10) -0.0021(12) N9 0.0267(13) 0.0329(14) 0.0265(13) 0.0044(11) -0.0009(11) -0.0017(12) C10 0.0238(15) 0.0311(15) 0.0303(15) 0.0000(13) -0.0003(12) -0.0017(13) C11 0.0240(14) 0.0343(16) 0.0294(15) 0.0037(13) -0.0043(13) 0.0009(13) C12 0.0316(18) 0.052(2) 0.0368(19) 0.0018(17) 0.0094(15) 0.0050(17) C13 0.0214(14) 0.0329(16) 0.0249(14) 0.0006(12) -0.0008(12) -0.0045(13) N14 0.0270(14) 0.0337(14) 0.0240(13) 0.0028(11) -0.0013(11) -0.0006(12) N15 0.0286(14) 0.0330(14) 0.0275(13) 0.0012(11) -0.0021(12) 0.0009(12) C16 0.0222(15) 0.0336(16) 0.0284(14) -0.0002(13) -0.0028(12) -0.0024(13) C17 0.0262(15) 0.0298(15) 0.0263(14) 0.0015(12) 0.0013(13) -0.0040(13) C18 0.0351(18) 0.0374(18) 0.0431(19) 0.0007(16) 0.0026(16) 0.0050(15) C19 0.041(2) 0.0372(18) 0.0392(19) 0.0044(15) -0.0006(17) 0.0048(16) O20 0.0433(15) 0.0321(12) 0.0306(12) 0.0047(11) 0.0041(11) 0.0062(11) _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 C6 1.351(4) . ? N1 C2 1.358(4) . ? C2 C3 1.394(4) . ? C2 C7 1.478(4) . ? C3 C4 1.387(5) . ? C4 C5 1.394(5) . ? C5 C6 1.397(4) . ? C6 C13 1.473(5) . ? C7 N8 1.341(4) . ? C7 C11 1.413(5) . ? N8 N9 1.354(4) . ? N9 C10 1.356(4) . ? N9 H9 0.90(4) . ? C10 C11 1.382(5) . ? C10 C12 1.514(5) . ? C13 N14 1.345(4) . ? C13 C17 1.399(5) . ? N14 N15 1.356(4) . ? N14 H14 0.85(4) . ? N15 C16 1.342(4) . ? C16 C17 1.402(5) . ? C16 C18 1.509(5) . ? C19 O20 1.418(5) . ? O20 H20 0.77(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 N1 C2 118.1(3) . . ? N1 C2 C3 121.9(3) . . ? N1 C2 C7 115.4(3) . . ? C3 C2 C7 122.7(3) . . ? C4 C3 C2 119.4(3) . . ? C3 C4 C5 119.4(3) . . ? C4 C5 C6 118.0(3) . . ? N1 C6 C5 123.2(3) . . ? N1 C6 C13 114.4(3) . . ? C5 C6 C13 122.4(3) . . ? N8 C7 C11 110.7(3) . . ? N8 C7 C2 121.0(3) . . ? C11 C7 C2 128.2(3) . . ? C7 N8 N9 105.0(3) . . ? N8 N9 C10 112.6(3) . . ? N8 N9 H9 117(3) . . ? C10 N9 H9 131(3) . . ? N9 C10 C11 106.3(3) . . ? N9 C10 C12 121.4(3) . . ? C11 C10 C12 132.2(3) . . ? C10 C11 C7 105.4(3) . . ? N14 C13 C17 106.2(3) . . ? N14 C13 C6 121.2(3) . . ? C17 C13 C6 132.6(3) . . ? C13 N14 N15 112.7(3) . . ? C13 N14 H14 127(3) . . ? N15 N14 H14 118(3) . . ? C16 N15 N14 105.1(3) . . ? N15 C16 C17 110.9(3) . . ? N15 C16 C18 120.2(3) . . ? C17 C16 C18 128.9(3) . . ? C13 C17 C16 105.1(3) . . ? C19 O20 H20 117(3) . . ? 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 N9 H9 N15 0.90(4) 1.92(4) 2.817(4) 178(4) 3_456 N14 H14 O20 0.85(4) 1.99(4) 2.820(4) 164(4) . O20 H20 N8 0.77(4) 2.12(5) 2.860(4) 163(4) . _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 28.20 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.486 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.085