# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_email peter.scott@warwick.ac.uk _publ_contact_author_name 'Peter Scott' loop_ _publ_author_name 'Lihong Li' 'Guy J. Clarkson' 'David J. Evans' 'Martin R. Lees' 'Scott S. Turner' 'Peter Scott' data_ll10 _database_code_depnum_ccdc_archive 'CCDC 839545' #TrackingRef '7590_web_deposit_cif_file_0_LihongLi_1318324179.ll10.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24.50 H22.50 Fe N4 O3.75' _chemical_formula_weight 488.82 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' 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 I-42d loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x, -y+1/2, -z+1/4' '-y+1/2, -x, z+3/4' '-x, y+1/2, -z+1/4' 'y+1/2, x, z+3/4' 'x+1/2, y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, -z+1/2' 'x+1/2, -y+1, -z+3/4' '-y+1, -x+1/2, z+5/4' '-x+1/2, y+1, -z+3/4' 'y+1, x+1/2, z+5/4' _cell_length_a 19.3307(2) _cell_length_b 19.3307(2) _cell_length_c 27.7612(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 10373.7(3) _cell_formula_units_Z 16 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 5869 _cell_measurement_theta_min 3.22 _cell_measurement_theta_max 29.04 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.252 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4056 _exptl_absorpt_coefficient_mu 0.615 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.88 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details 'ABSPACK(CrysAlis, Oxford Diffraction)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cobra. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of four sets of exposures with different \f angles for the crystal; each 10 s exposure covered 0.3\% in \w. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached. Both merohedral and racemic twinning were investigated. No twin matrix could be found that gave any indication of merohedral twinning. The inversion matrix gave a BASF value of 0.545(33). Several small electron density peaks around the complex were modelled as partially occupied water (25% O5 and O6, 50% O4) and one site dual occupancy by a water (25% O3A) and a methanol (50% O3-C25). These were refined isotropically. No hydrogens were located on these molecules but were included in the formula so as to calculate the correct density. There are solvent accessible voids in the structure (Platon) Total Potential Solvent Area Vol 754.3 Ang^3 (per Unit Cell Vol 10373.7 Ang^3 [ 7.3%]) Structure occupies (A^3) 6282.01 (60.56%) Radius of the largest spherical void is 2.20 Ang ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini R' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean 10.2833 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 23628 _diffrn_reflns_av_R_equivalents 0.0795 _diffrn_reflns_av_sigmaI/netI 0.1067 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -37 _diffrn_reflns_limit_l_max 34 _diffrn_reflns_theta_min 3.22 _diffrn_reflns_theta_max 29.11 _reflns_number_total 3577 _reflns_number_gt 2125 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0830P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881, 1782 Friedel pairs' _refine_ls_abs_structure_Flack 0.545(33) _chemical_absolute_configuration ad _refine_ls_number_reflns 3577 _refine_ls_number_parameters 307 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1068 _refine_ls_R_factor_gt 0.0553 _refine_ls_wR_factor_ref 0.1407 _refine_ls_wR_factor_gt 0.1291 _refine_ls_goodness_of_fit_ref 0.922 _refine_ls_restrained_S_all 0.922 _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 Fe2 Fe 0.5000 0.5000 0.77955(4) 0.0347(3) Uani 1 2 d S . . Fe1 Fe 0.2500 0.20476(5) 0.8750 0.0310(3) Uani 1 2 d S . . O1 O 0.16874(19) 0.19944(18) 0.92142(14) 0.0367(9) Uani 1 1 d . . . C1 C 0.1843(3) 0.2188(3) 0.9656(2) 0.0354(13) Uani 1 1 d . . . C2 C 0.1502(3) 0.1922(3) 1.0064(2) 0.0459(16) Uani 1 1 d . . . H2A H 0.1148 0.1585 1.0025 0.055 Uiso 1 1 calc R . . C3 C 0.1677(4) 0.2146(4) 1.0522(2) 0.0539(18) Uani 1 1 d . . . H3A H 0.1442 0.1958 1.0792 0.065 Uiso 1 1 calc R . . C4 C 0.2187(3) 0.2638(3) 1.0593(2) 0.0464(16) Uani 1 1 d . . . H4A H 0.2296 0.2797 1.0908 0.056 Uiso 1 1 calc R . . C5 C 0.2526(3) 0.2889(3) 1.02020(18) 0.0368(12) Uani 1 1 d . . . H5A H 0.2887 0.3215 1.0249 0.044 Uiso 1 1 calc R . . C6 C 0.2367(3) 0.2688(2) 0.9740(2) 0.0311(12) Uani 1 1 d . . . N1 N 0.2739(2) 0.2901(2) 0.93251(15) 0.0298(10) Uani 1 1 d . . . C7 C 0.2975(3) 0.3525(3) 0.93338(19) 0.0334(12) Uani 1 1 d . . . H7A H 0.2820 0.3818 0.9586 0.040 Uiso 1 1 calc R . . C8 C 0.3462(3) 0.3815(3) 0.8986(2) 0.0365(14) Uani 1 1 d . . . C9 C 0.3593(4) 0.4531(3) 0.9005(2) 0.0526(17) Uani 1 1 d . . . H9A H 0.3365 0.4818 0.9234 0.063 Uiso 1 1 calc R . . C10 C 0.4063(4) 0.4806(3) 0.8680(2) 0.0560(19) Uani 1 1 d . . . H10A H 0.4136 0.5292 0.8684 0.067 Uiso 1 1 calc R . . N2 N 0.4418(3) 0.4435(2) 0.83634(17) 0.0413(12) Uani 1 1 d . . . C11 C 0.4287(3) 0.3753(3) 0.8349(2) 0.0362(13) Uani 1 1 d . . . H11A H 0.4521 0.3482 0.8115 0.043 Uiso 1 1 calc R . . C12 C 0.3836(3) 0.3428(3) 0.86530(19) 0.0337(13) Uani 1 1 d . . . H12A H 0.3778 0.2940 0.8637 0.040 Uiso 1 1 calc R . . O2 O 0.5787(2) 0.43155(18) 0.78068(15) 0.0408(9) Uani 1 1 d . . . C13 C 0.6368(3) 0.4534(3) 0.7619(2) 0.0402(14) Uani 1 1 d . . . C14 C 0.6994(4) 0.4170(3) 0.7670(2) 0.0526(17) Uani 1 1 d . . . H14A H 0.6998 0.3753 0.7852 0.063 Uiso 1 1 calc R . . C15 C 0.7598(3) 0.4399(3) 0.7467(3) 0.0543(17) Uani 1 1 d . . . H15A H 0.8018 0.4157 0.7526 0.065 Uiso 1 1 calc R . . C16 C 0.7600(3) 0.4996(3) 0.7168(2) 0.0490(15) Uani 1 1 d . . . H16A H 0.8009 0.5138 0.7005 0.059 Uiso 1 1 calc R . . C17 C 0.6999(3) 0.5360(3) 0.7121(2) 0.0397(13) Uani 1 1 d . . . H17A H 0.6997 0.5765 0.6928 0.048 Uiso 1 1 calc R . . C18 C 0.6388(3) 0.5156(2) 0.7346(2) 0.0340(13) Uani 1 1 d . . . N3 N 0.5739(2) 0.5494(2) 0.72862(16) 0.0310(10) Uani 1 1 d . . . C19 C 0.5704(3) 0.6116(3) 0.71102(19) 0.0329(12) Uani 1 1 d . . . H19A H 0.6115 0.6380 0.7076 0.040 Uiso 1 1 calc R . . C20 C 0.5044(3) 0.6413(3) 0.69653(18) 0.0334(12) Uani 1 1 d . . . C21 C 0.4918(3) 0.7123(3) 0.7015(2) 0.0377(13) Uani 1 1 d . . . H21A H 0.5256 0.7419 0.7154 0.045 Uiso 1 1 calc R . . C22 C 0.4292(3) 0.7385(3) 0.6858(2) 0.0425(15) Uani 1 1 d . . . H22A H 0.4213 0.7867 0.6895 0.051 Uiso 1 1 calc R . . N4 N 0.3797(2) 0.7010(3) 0.66616(17) 0.0366(11) Uani 1 1 d . . . C23 C 0.3920(3) 0.6328(3) 0.6621(2) 0.0376(14) Uani 1 1 d . . . H23A H 0.3569 0.6045 0.6484 0.045 Uiso 1 1 calc R . . C24 C 0.4525(3) 0.6017(3) 0.6765(2) 0.0365(13) Uani 1 1 d . . . H24A H 0.4585 0.5532 0.6727 0.044 Uiso 1 1 calc R . . O3 O 0.9183(4) 0.2960(4) 0.9329(3) 0.083(2) Uiso 0.50 1 d P A . C25 C 0.9084(9) 0.3261(9) 0.8941(7) 0.077(5) Uiso 0.50 1 d P . . O3A O 0.9183(4) 0.2960(4) 0.9329(3) 0.083(2) Uiso 0.25 1 d P A 2 O4 O 0.1884(4) -0.0169(4) 1.0693(3) 0.053(2) Uani 0.50 1 d P . . O5 O -0.0018(8) 0.0998(6) 1.0183(4) 0.028(3) Uiso 0.25 1 d P . . O6 O 0.0853(9) 0.0661(9) 1.1068(6) 0.049(4) Uiso 0.25 1 d P . . 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 Fe2 0.0376(6) 0.0264(6) 0.0401(6) 0.000 0.000 -0.0078(5) Fe1 0.0315(6) 0.0244(5) 0.0371(6) 0.000 0.0020(5) 0.000 O1 0.033(2) 0.0267(19) 0.050(3) 0.0037(18) -0.0008(18) -0.0009(17) C1 0.035(3) 0.031(3) 0.040(3) 0.010(3) 0.006(3) 0.014(2) C2 0.036(3) 0.039(3) 0.063(4) 0.011(3) 0.021(3) 0.012(3) C3 0.062(4) 0.054(4) 0.046(4) 0.017(3) 0.027(4) 0.018(4) C4 0.056(4) 0.049(4) 0.035(3) 0.006(3) 0.011(3) 0.018(3) C5 0.033(3) 0.044(3) 0.034(3) 0.007(3) 0.003(3) 0.015(3) C6 0.030(3) 0.026(3) 0.037(3) 0.005(2) 0.005(2) 0.006(2) N1 0.027(2) 0.032(2) 0.031(2) 0.004(2) 0.0019(18) 0.0072(19) C7 0.039(3) 0.031(3) 0.030(3) 0.000(2) 0.001(3) 0.001(3) C8 0.046(3) 0.039(3) 0.025(3) -0.001(2) 0.002(3) -0.005(3) C9 0.077(5) 0.037(3) 0.044(4) -0.007(3) 0.016(3) -0.010(3) C10 0.092(5) 0.030(3) 0.046(4) -0.009(3) 0.009(4) -0.022(3) N2 0.053(3) 0.032(3) 0.039(3) -0.002(2) 0.006(2) -0.017(2) C11 0.035(3) 0.035(3) 0.038(3) 0.001(3) 0.000(3) -0.012(3) C12 0.036(3) 0.030(3) 0.035(3) -0.001(3) 0.000(3) 0.001(2) O2 0.047(2) 0.0232(19) 0.052(2) 0.0055(18) -0.006(2) -0.0036(18) C13 0.039(3) 0.034(3) 0.048(4) -0.001(3) -0.009(3) 0.002(3) C14 0.061(4) 0.028(3) 0.069(4) 0.000(3) -0.002(4) 0.006(3) C15 0.042(4) 0.049(4) 0.072(5) -0.009(4) -0.003(3) 0.018(3) C16 0.046(3) 0.038(3) 0.063(4) -0.009(3) 0.003(3) 0.009(3) C17 0.035(3) 0.032(3) 0.052(4) -0.002(3) 0.004(3) 0.000(3) C18 0.039(3) 0.021(3) 0.042(3) -0.005(2) -0.006(3) 0.000(2) N3 0.032(2) 0.028(2) 0.033(2) 0.000(2) -0.0038(19) -0.001(2) C19 0.031(3) 0.031(3) 0.037(3) 0.002(2) 0.004(2) -0.006(2) C20 0.026(3) 0.035(3) 0.040(3) 0.003(2) 0.002(3) 0.000(3) C21 0.026(3) 0.030(3) 0.057(3) -0.006(3) -0.004(3) -0.001(3) C22 0.034(3) 0.028(3) 0.065(4) 0.000(3) -0.009(3) 0.010(2) N4 0.024(2) 0.035(3) 0.050(3) -0.001(2) -0.005(2) -0.002(2) C23 0.036(3) 0.030(3) 0.047(3) 0.003(3) -0.003(3) -0.006(3) C24 0.040(3) 0.025(3) 0.045(3) 0.005(3) -0.005(3) 0.000(3) O4 0.053(5) 0.026(4) 0.081(6) 0.001(4) -0.003(5) 0.002(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 Fe2 O2 2.016(4) . ? Fe2 O2 2.016(4) 3_665 ? Fe2 N2 2.224(5) 3_665 ? Fe2 N2 2.224(5) . ? Fe2 N3 2.225(4) 3_665 ? Fe2 N3 2.225(4) . ? Fe1 O1 2.034(4) 15_546 ? Fe1 O1 2.034(4) . ? Fe1 N4 2.206(5) 14_554 ? Fe1 N4 2.206(5) 10_456 ? Fe1 N1 2.342(5) . ? Fe1 N1 2.342(5) 15_546 ? O1 C1 1.317(7) . ? C1 C2 1.408(8) . ? C1 C6 1.420(8) . ? C2 C3 1.384(10) . ? C2 H2A 0.9500 . ? C3 C4 1.384(10) . ? C3 H3A 0.9500 . ? C4 C5 1.358(8) . ? C4 H4A 0.9500 . ? C5 C6 1.374(8) . ? C5 H5A 0.9500 . ? C6 N1 1.421(7) . ? N1 C7 1.289(7) . ? C7 C8 1.460(8) . ? C7 H7A 0.9500 . ? C8 C12 1.392(8) . ? C8 C9 1.409(9) . ? C9 C10 1.388(9) . ? C9 H9A 0.9500 . ? C10 N2 1.324(8) . ? C10 H10A 0.9500 . ? N2 C11 1.343(7) . ? C11 C12 1.367(8) . ? C11 H11A 0.9500 . ? C12 H12A 0.9500 . ? O2 C13 1.308(7) . ? C13 C14 1.407(9) . ? C13 C18 1.422(8) . ? C14 C15 1.371(10) . ? C14 H14A 0.9500 . ? C15 C16 1.423(9) . ? C15 H15A 0.9500 . ? C16 C17 1.364(8) . ? C16 H16A 0.9500 . ? C17 C18 1.394(8) . ? C17 H17A 0.9500 . ? C18 N3 1.425(7) . ? N3 C19 1.300(7) . ? C19 C20 1.456(8) . ? C19 H19A 0.9500 . ? C20 C24 1.380(8) . ? C20 C21 1.402(7) . ? C21 C22 1.381(8) . ? C21 H21A 0.9500 . ? C22 N4 1.319(7) . ? C22 H22A 0.9500 . ? N4 C23 1.346(7) . ? N4 Fe1 2.206(5) 12_556 ? C23 C24 1.374(8) . ? C23 H23A 0.9500 . ? C24 H24A 0.9500 . ? O3 C25 1.241(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 O2 Fe2 O2 178.2(2) . 3_665 ? O2 Fe2 N2 85.95(18) . 3_665 ? O2 Fe2 N2 92.79(18) 3_665 3_665 ? O2 Fe2 N2 92.79(18) . . ? O2 Fe2 N2 85.95(18) 3_665 . ? N2 Fe2 N2 89.7(2) 3_665 . ? O2 Fe2 N3 102.27(16) . 3_665 ? O2 Fe2 N3 78.89(16) 3_665 3_665 ? N2 Fe2 N3 170.47(18) 3_665 3_665 ? N2 Fe2 N3 85.13(16) . 3_665 ? O2 Fe2 N3 78.89(16) . . ? O2 Fe2 N3 102.27(16) 3_665 . ? N2 Fe2 N3 85.13(16) 3_665 . ? N2 Fe2 N3 170.47(18) . . ? N3 Fe2 N3 101.1(2) 3_665 . ? O1 Fe1 O1 174.2(2) 15_546 . ? O1 Fe1 N4 87.68(17) 15_546 14_554 ? O1 Fe1 N4 88.04(16) . 14_554 ? O1 Fe1 N4 88.04(16) 15_546 10_456 ? O1 Fe1 N4 87.68(17) . 10_456 ? N4 Fe1 N4 84.5(2) 14_554 10_456 ? O1 Fe1 N1 108.37(15) 15_546 . ? O1 Fe1 N1 75.88(15) . . ? N4 Fe1 N1 94.81(15) 14_554 . ? N4 Fe1 N1 163.56(16) 10_456 . ? O1 Fe1 N1 75.88(15) 15_546 15_546 ? O1 Fe1 N1 108.37(15) . 15_546 ? N4 Fe1 N1 163.56(16) 14_554 15_546 ? N4 Fe1 N1 94.81(15) 10_456 15_546 ? N1 Fe1 N1 90.4(2) . 15_546 ? C1 O1 Fe1 113.5(3) . . ? O1 C1 C2 122.6(6) . . ? O1 C1 C6 120.7(5) . . ? C2 C1 C6 116.7(6) . . ? C3 C2 C1 120.6(6) . . ? C3 C2 H2A 119.7 . . ? C1 C2 H2A 119.7 . . ? C4 C3 C2 121.4(6) . . ? C4 C3 H3A 119.3 . . ? C2 C3 H3A 119.3 . . ? C5 C4 C3 118.3(6) . . ? C5 C4 H4A 120.8 . . ? C3 C4 H4A 120.8 . . ? C4 C5 C6 122.5(6) . . ? C4 C5 H5A 118.8 . . ? C6 C5 H5A 118.8 . . ? C5 C6 C1 120.4(5) . . ? C5 C6 N1 124.2(5) . . ? C1 C6 N1 115.1(5) . . ? C7 N1 C6 115.8(5) . . ? C7 N1 Fe1 137.9(4) . . ? C6 N1 Fe1 104.4(3) . . ? N1 C7 C8 125.1(5) . . ? N1 C7 H7A 117.4 . . ? C8 C7 H7A 117.4 . . ? C12 C8 C9 117.4(5) . . ? C12 C8 C7 124.6(5) . . ? C9 C8 C7 117.9(5) . . ? C10 C9 C8 118.0(6) . . ? C10 C9 H9A 121.0 . . ? C8 C9 H9A 121.0 . . ? N2 C10 C9 124.3(5) . . ? N2 C10 H10A 117.8 . . ? C9 C10 H10A 117.8 . . ? C10 N2 C11 116.9(5) . . ? C10 N2 Fe2 117.8(4) . . ? C11 N2 Fe2 123.8(4) . . ? N2 C11 C12 123.6(6) . . ? N2 C11 H11A 118.2 . . ? C12 C11 H11A 118.2 . . ? C11 C12 C8 119.6(5) . . ? C11 C12 H12A 120.2 . . ? C8 C12 H12A 120.2 . . ? C13 O2 Fe2 115.4(3) . . ? O2 C13 C14 122.4(5) . . ? O2 C13 C18 120.6(5) . . ? C14 C13 C18 116.9(5) . . ? C15 C14 C13 122.0(6) . . ? C15 C14 H14A 119.0 . . ? C13 C14 H14A 119.0 . . ? C14 C15 C16 120.3(6) . . ? C14 C15 H15A 119.8 . . ? C16 C15 H15A 119.8 . . ? C17 C16 C15 118.1(6) . . ? C17 C16 H16A 120.9 . . ? C15 C16 H16A 120.9 . . ? C16 C17 C18 122.3(6) . . ? C16 C17 H17A 118.9 . . ? C18 C17 H17A 118.9 . . ? C17 C18 C13 120.1(5) . . ? C17 C18 N3 124.4(5) . . ? C13 C18 N3 115.2(5) . . ? C19 N3 C18 120.9(4) . . ? C19 N3 Fe2 127.1(4) . . ? C18 N3 Fe2 107.1(3) . . ? N3 C19 C20 120.9(5) . . ? N3 C19 H19A 119.6 . . ? C20 C19 H19A 119.6 . . ? C24 C20 C21 117.2(5) . . ? C24 C20 C19 122.1(5) . . ? C21 C20 C19 120.8(5) . . ? C22 C21 C20 118.7(5) . . ? C22 C21 H21A 120.7 . . ? C20 C21 H21A 120.7 . . ? N4 C22 C21 124.4(5) . . ? N4 C22 H22A 117.8 . . ? C21 C22 H22A 117.8 . . ? C22 N4 C23 116.4(5) . . ? C22 N4 Fe1 121.1(4) . 12_556 ? C23 N4 Fe1 120.5(4) . 12_556 ? N4 C23 C24 123.7(5) . . ? N4 C23 H23A 118.2 . . ? C24 C23 H23A 118.2 . . ? C23 C24 C20 119.6(5) . . ? C23 C24 H24A 120.2 . . ? C20 C24 H24A 120.2 . . ? _diffrn_measured_fraction_theta_max 0.952 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.598 _refine_diff_density_min -0.263 _refine_diff_density_rms 0.078 # Attachment '7591_web_deposit_cif_file_1_LihongLi_1318324179.ll39.cif' data_ll39 _database_code_depnum_ccdc_archive 'CCDC 839546' #TrackingRef '7591_web_deposit_cif_file_1_LihongLi_1318324179.ll39.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C24 H18 Fe N4 O2' _chemical_formula_sum 'C24 H18 Fe N4 O2' _chemical_formula_weight 450.27 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pbca _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 9.9499(6) _cell_length_b 11.0634(5) _cell_length_c 19.3835(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2133.73(19) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3961 _cell_measurement_theta_min 3.99 _cell_measurement_theta_max 70.56 _exptl_crystal_description plate _exptl_crystal_colour brown _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.402 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 928 _exptl_absorpt_coefficient_mu 5.899 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.36 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details 'ABSPACK(CrysAlis, Oxford Diffraction)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cobra. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of nineteen sets of exposures with different \f angles for the crystal; low angle were recorded at 20s and high angle at 80s exposure covered 1.0\% in \w. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached. All crystals examined were twinned. Using the twin option in CrysAlis, two twins were located Twin ratio 69:31 with R(int) 8% for the major and 16% for the minor twin. The HKLF5 refinenment was not as good as refienment with data for the major twin so refinement was completed using the major twin data. Twin relationship (relative to component 1) was Rot= 177.3934 deg around the following vectors: Reciprocal space (hkl): 0.0012 0.9983 -0.0579 Direct space (uvw) : 0.0024 0.9998 -0.0181 ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Gemini R' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean 10.2833 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 11020 _diffrn_reflns_av_R_equivalents 0.1488 _diffrn_reflns_av_sigmaI/netI 0.0692 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 4.56 _diffrn_reflns_theta_max 70.57 _reflns_number_total 2026 _reflns_number_gt 1625 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0610P)^2^+8.6033P] 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 2026 _refine_ls_number_parameters 142 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1027 _refine_ls_R_factor_gt 0.0830 _refine_ls_wR_factor_ref 0.1936 _refine_ls_wR_factor_gt 0.1831 _refine_ls_goodness_of_fit_ref 1.177 _refine_ls_restrained_S_all 1.177 _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 0.5000 0.5000 0.0171(3) Uani 1 2 d S . . O1 O 0.1367(3) 0.5762(3) 0.43840(17) 0.0204(8) Uani 1 1 d . . . C1 C 0.1533(5) 0.5764(4) 0.3725(3) 0.0182(10) Uani 1 1 d . . . C2 C 0.2467(5) 0.6568(5) 0.3419(3) 0.0256(11) Uani 1 1 d . . . H2A H 0.2971 0.7092 0.3709 0.031 Uiso 1 1 calc R . . C3 C 0.2670(6) 0.6616(5) 0.2719(3) 0.0307(13) Uani 1 1 d . . . H3A H 0.3323 0.7155 0.2537 0.037 Uiso 1 1 calc R . . C4 C 0.1935(6) 0.5889(5) 0.2273(3) 0.0314(13) Uani 1 1 d . . . H4A H 0.2065 0.5939 0.1788 0.038 Uiso 1 1 calc R . . C5 C 0.1023(6) 0.5100(4) 0.2546(3) 0.0271(11) Uani 1 1 d . . . H5A H 0.0517 0.4601 0.2243 0.033 Uiso 1 1 calc R . . C6 C 0.0807(5) 0.5002(5) 0.3260(3) 0.0229(11) Uani 1 1 d . . . N1 N -0.0455(4) 0.3857(4) 0.4118(2) 0.0185(9) Uani 1 1 d . . . C7 C -0.0140(5) 0.4096(4) 0.3486(3) 0.0205(10) Uani 1 1 d . . . H7A H -0.0572 0.3633 0.3138 0.025 Uiso 1 1 calc R . . C8 C -0.1430(5) 0.2945(4) 0.4240(2) 0.0199(10) Uani 1 1 d . . . C9 C -0.1107(5) 0.1926(4) 0.4615(3) 0.0225(11) Uani 1 1 d . . . H9A H -0.0205 0.1779 0.4752 0.027 Uiso 1 1 calc R . . C10 C -0.2124(5) 0.1117(4) 0.4788(3) 0.0221(11) Uani 1 1 d . . . H10A H -0.1898 0.0429 0.5057 0.027 Uiso 1 1 calc R . . N2 N -0.3408(4) 0.1262(4) 0.4595(2) 0.0193(9) Uani 1 1 d . . . C11 C -0.3699(5) 0.2231(4) 0.4207(2) 0.0208(10) Uani 1 1 d . . . H11A H -0.4598 0.2330 0.4052 0.025 Uiso 1 1 calc R . . C12 C -0.2763(5) 0.3090(4) 0.4021(2) 0.0208(10) Uani 1 1 d . . . H12A H -0.3017 0.3766 0.3748 0.025 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Fe1 0.0163(5) 0.0179(5) 0.0169(5) 0.0009(4) 0.0008(4) 0.0000(4) O1 0.0173(16) 0.0218(17) 0.0220(17) 0.0031(14) 0.0029(14) -0.0014(14) C1 0.015(2) 0.015(2) 0.025(2) 0.0021(19) 0.001(2) 0.0050(19) C2 0.024(3) 0.024(3) 0.029(3) -0.001(2) -0.003(2) -0.005(2) C3 0.029(3) 0.030(3) 0.033(3) 0.002(2) 0.009(2) -0.008(2) C4 0.041(3) 0.030(3) 0.023(3) 0.000(2) 0.009(2) -0.006(3) C5 0.035(3) 0.021(2) 0.025(2) 0.001(2) 0.004(2) -0.005(2) C6 0.024(2) 0.021(2) 0.024(2) -0.003(2) 0.004(2) -0.004(2) N1 0.0180(19) 0.019(2) 0.0180(18) 0.0012(17) 0.0022(16) 0.0030(17) C7 0.021(2) 0.018(2) 0.023(2) -0.003(2) -0.002(2) 0.002(2) C8 0.021(2) 0.018(2) 0.021(2) -0.0006(19) 0.000(2) -0.003(2) C9 0.020(2) 0.025(3) 0.023(2) 0.001(2) -0.002(2) -0.001(2) C10 0.024(3) 0.018(2) 0.024(2) 0.004(2) -0.002(2) -0.002(2) N2 0.0187(19) 0.021(2) 0.0185(19) -0.0026(17) 0.0010(17) -0.0036(16) C11 0.019(2) 0.022(2) 0.021(2) -0.001(2) 0.001(2) -0.002(2) C12 0.021(2) 0.020(2) 0.021(2) 0.001(2) -0.003(2) -0.001(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 O1 1.996(3) . ? Fe1 O1 1.996(3) 5_566 ? Fe1 N1 2.175(4) . ? Fe1 N1 2.175(4) 5_566 ? Fe1 N2 2.253(4) 8_565 ? Fe1 N2 2.253(4) 4_556 ? O1 C1 1.288(6) . ? C1 C2 1.416(7) . ? C1 C6 1.431(7) . ? C2 C3 1.374(7) . ? C2 H2A 0.9500 . ? C3 C4 1.389(8) . ? C3 H3A 0.9500 . ? C4 C5 1.367(8) . ? C4 H4A 0.9500 . ? C5 C6 1.404(7) . ? C5 H5A 0.9500 . ? C6 C7 1.444(7) . ? N1 C7 1.291(6) . ? N1 C8 1.420(6) . ? C7 H7A 0.9500 . ? C8 C9 1.379(7) . ? C8 C12 1.403(7) . ? C9 C10 1.393(7) . ? C9 H9A 0.9500 . ? C10 N2 1.340(6) . ? C10 H10A 0.9500 . ? N2 C11 1.341(6) . ? N2 Fe1 2.253(4) 4_456 ? C11 C12 1.379(7) . ? C11 H11A 0.9500 . ? C12 H12A 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Fe1 O1 180.0 . 5_566 ? O1 Fe1 N1 85.24(14) . . ? O1 Fe1 N1 94.76(14) 5_566 . ? O1 Fe1 N1 94.76(14) . 5_566 ? O1 Fe1 N1 85.24(14) 5_566 5_566 ? N1 Fe1 N1 180.000(1) . 5_566 ? O1 Fe1 N2 90.50(14) . 8_565 ? O1 Fe1 N2 89.50(14) 5_566 8_565 ? N1 Fe1 N2 86.55(14) . 8_565 ? N1 Fe1 N2 93.45(14) 5_566 8_565 ? O1 Fe1 N2 89.50(14) . 4_556 ? O1 Fe1 N2 90.50(14) 5_566 4_556 ? N1 Fe1 N2 93.45(14) . 4_556 ? N1 Fe1 N2 86.55(14) 5_566 4_556 ? N2 Fe1 N2 180.00(18) 8_565 4_556 ? C1 O1 Fe1 132.9(3) . . ? O1 C1 C2 120.0(4) . . ? O1 C1 C6 124.0(4) . . ? C2 C1 C6 116.0(4) . . ? C3 C2 C1 122.3(5) . . ? C3 C2 H2A 118.9 . . ? C1 C2 H2A 118.9 . . ? C2 C3 C4 121.1(5) . . ? C2 C3 H3A 119.5 . . ? C4 C3 H3A 119.5 . . ? C5 C4 C3 118.5(5) . . ? C5 C4 H4A 120.7 . . ? C3 C4 H4A 120.7 . . ? C4 C5 C6 122.3(5) . . ? C4 C5 H5A 118.9 . . ? C6 C5 H5A 118.9 . . ? C5 C6 C1 119.9(5) . . ? C5 C6 C7 117.0(5) . . ? C1 C6 C7 123.1(4) . . ? C7 N1 C8 118.1(4) . . ? C7 N1 Fe1 125.2(3) . . ? C8 N1 Fe1 115.1(3) . . ? N1 C7 C6 126.1(5) . . ? N1 C7 H7A 117.0 . . ? C6 C7 H7A 117.0 . . ? C9 C8 C12 118.3(4) . . ? C9 C8 N1 120.6(4) . . ? C12 C8 N1 121.0(4) . . ? C8 C9 C10 118.9(5) . . ? C8 C9 H9A 120.6 . . ? C10 C9 H9A 120.6 . . ? N2 C10 C9 123.2(4) . . ? N2 C10 H10A 118.4 . . ? C9 C10 H10A 118.4 . . ? C10 N2 C11 117.3(4) . . ? C10 N2 Fe1 119.9(3) . 4_456 ? C11 N2 Fe1 122.6(3) . 4_456 ? N2 C11 C12 123.5(5) . . ? N2 C11 H11A 118.3 . . ? C12 C11 H11A 118.3 . . ? C11 C12 C8 118.7(4) . . ? C11 C12 H12A 120.6 . . ? C8 C12 H12A 120.6 . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 70.57 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.867 _refine_diff_density_min -0.704 _refine_diff_density_rms 0.102