# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_name 'You Song' _publ_contact_author_email songxiao607@126.com _publ_author_name 'Xiaojiao Song' # Attachment '- MnFe2.cif' data_MnFe2 _database_code_depnum_ccdc_archive 'CCDC 872240' #TrackingRef '- MnFe2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C38 H32 Fe2 Mn N14 O4' _chemical_formula_weight 915.42 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 '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 Monoclinic _symmetry_space_group_name_H-M C2/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 11.587(2) _cell_length_b 28.862(6) _cell_length_c 6.7100(12) _cell_angle_alpha 90.00 _cell_angle_beta 114.655(4) _cell_angle_gamma 90.00 _cell_volume 2039.4(7) _cell_formula_units_Z 2 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 3204 _cell_measurement_theta_min 2.82 _cell_measurement_theta_max 28.21 _exptl_crystal_description block _exptl_crystal_colour nigger-brown _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.491 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 934 _exptl_absorpt_coefficient_mu 1.065 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7547 _exptl_absorpt_correction_T_max 0.7994 _exptl_absorpt_process_details 'SADABS; Bruker, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart Aepex CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5508 _diffrn_reflns_av_R_equivalents 0.0825 _diffrn_reflns_av_sigmaI/netI 0.0636 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -35 _diffrn_reflns_limit_k_max 35 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.06 _diffrn_reflns_theta_max 26.00 _reflns_number_total 2043 _reflns_number_gt 1821 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0528P)^2^+0.9926P] 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 2043 _refine_ls_number_parameters 160 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0413 _refine_ls_R_factor_gt 0.0377 _refine_ls_wR_factor_ref 0.1060 _refine_ls_wR_factor_gt 0.1039 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.084 _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 C1 C 1.1636(3) 0.86890(8) 0.7524(5) 0.0417(6) Uani 1 1 d . . . C2 C 1.0473(2) 0.91693(8) 0.3569(4) 0.0327(5) Uani 1 1 d . . . C3 C 1.0338(2) 0.77415(8) 0.4292(4) 0.0384(5) Uani 1 1 d . . . C4 C 1.0693(3) 0.73453(9) 0.3532(5) 0.0496(7) Uani 1 1 d . . . H3 H 1.0491 0.7054 0.3886 0.060 Uiso 1 1 calc R . . C5 C 1.1352(3) 0.73889(10) 0.2240(5) 0.0553(7) Uani 1 1 d . . . H4 H 1.1595 0.7127 0.1700 0.066 Uiso 1 1 calc R . . C6 C 1.1642(3) 0.78216(10) 0.1766(5) 0.0521(7) Uani 1 1 d . . . H5 H 1.2105 0.7858 0.0930 0.063 Uiso 1 1 calc R . . C7 C 1.1248(3) 0.82007(9) 0.2527(4) 0.0442(6) Uani 1 1 d . . . H6 H 1.1437 0.8494 0.2173 0.053 Uiso 1 1 calc R . . C8 C 0.7048(4) 0.98426(19) -0.1694(8) 0.0502(17) Uani 0.50 1 d P . . H8 H 0.7165 0.9753 -0.2974 0.060 Uiso 0.50 1 d PR . . C9 C 0.5841(4) 0.9836(2) -0.1793(9) 0.0533(18) Uani 0.50 1 d P . . H9 H 0.5277 0.9783 -0.3301 0.064 Uiso 0.50 1 d PR . . C10 C 0.5650(3) 1.0000 0.0040(6) 0.0445(9) Uani 1 2 d S . . C11 C 0.6712(4) 1.0000 0.1896(7) 0.0567(11) Uani 1 2 d S . . H11 H 0.6653 1.0000 0.3237 0.068 Uiso 1 2 calc SR . . C12 C 0.7890(3) 1.0000 0.1858(6) 0.0522(10) Uani 1 2 d S . . H12 H 0.8599 1.0000 0.3194 0.063 Uiso 1 2 calc SR . . Fe1 Fe 1.0000 0.868420(14) 0.5000 0.03048(18) Uani 1 2 d S . . Mn1 Mn 1.0000 1.0000 0.0000 0.02496(19) Uani 1 4 d S . . N1 N 1.2582(3) 0.86773(9) 0.9006(5) 0.0674(8) Uani 1 1 d . . . N2 N 1.0657(2) 0.94600(7) 0.2598(3) 0.0394(5) Uani 1 1 d . . . N3 N 1.05986(19) 0.81647(6) 0.3762(3) 0.0357(4) Uani 1 1 d . . . N4 N 0.8074(3) 1.0000 0.0085(5) 0.0409(7) Uani 1 2 d S . . O1 O 0.0568(10) 0.6371(2) 0.6288(12) 0.142(3) Uani 0.50 1 d P . 1 H1B H 0.1191 0.6185 0.6837 0.213 Uiso 0.50 1 d PRD . 1 H1A H 0.0258 0.6164 0.6821 0.213 Uiso 0.50 1 d PRD . 1 O1A O -0.0240(9) 0.6165(4) 0.770(2) 0.207(5) Uani 0.50 1 d P A 2 H1C H -0.0877 0.6175 0.8014 0.310 Uiso 0.50 1 d PR A 2 H1D H 0.0550 0.6180 0.8515 0.310 Uiso 0.50 1 d PR A 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 C1 0.0498(15) 0.0336(13) 0.0419(15) 0.0017(10) 0.0192(13) 0.0026(10) C2 0.0371(12) 0.0293(11) 0.0360(12) 0.0014(10) 0.0194(10) 0.0048(9) C3 0.0488(14) 0.0300(12) 0.0331(12) -0.0007(9) 0.0137(10) 0.0027(10) C4 0.0658(17) 0.0306(13) 0.0463(15) -0.0017(11) 0.0173(13) 0.0083(12) C5 0.0693(19) 0.0473(16) 0.0486(17) -0.0087(13) 0.0241(14) 0.0198(14) C6 0.0620(17) 0.0542(17) 0.0477(15) 0.0010(13) 0.0305(14) 0.0166(13) C7 0.0557(15) 0.0418(14) 0.0427(14) 0.0024(11) 0.0282(13) 0.0083(11) C8 0.035(2) 0.084(5) 0.039(2) -0.005(2) 0.023(2) 0.005(2) C9 0.030(2) 0.095(5) 0.036(2) -0.006(2) 0.0153(19) 0.002(2) C10 0.0289(17) 0.069(2) 0.043(2) 0.000 0.0223(15) 0.000 C11 0.0384(19) 0.101(3) 0.042(2) 0.000 0.0279(17) 0.000 C12 0.0316(18) 0.087(3) 0.042(2) 0.000 0.0191(16) 0.000 Fe1 0.0407(3) 0.0245(3) 0.0316(3) 0.000 0.0204(2) 0.000 Mn1 0.0252(3) 0.0239(3) 0.0325(4) 0.000 0.0186(3) 0.000 N1 0.0595(17) 0.0627(17) 0.0623(18) -0.0031(13) 0.0079(15) 0.0075(12) N2 0.0460(12) 0.0347(10) 0.0449(12) 0.0075(9) 0.0261(10) 0.0042(9) N3 0.0465(11) 0.0295(10) 0.0334(10) 0.0004(8) 0.0189(9) 0.0048(8) N4 0.0290(14) 0.0599(18) 0.0411(16) 0.000 0.0219(12) 0.000 O1 0.190(9) 0.092(5) 0.110(6) 0.032(4) 0.029(6) 0.031(5) O1A 0.082(5) 0.239(11) 0.245(12) 0.070(11) 0.016(7) -0.002(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 C1 N1 1.133(4) . ? C1 Fe1 1.945(3) . ? C2 N2 1.135(3) . ? C2 Fe1 1.903(2) . ? C3 N3 1.341(3) . ? C3 C4 1.383(3) . ? C3 C3 1.462(5) 2_756 ? C4 C5 1.379(4) . ? C4 H3 0.9300 . ? C5 C6 1.365(4) . ? C5 H4 0.9300 . ? C6 C7 1.364(3) . ? C6 H5 0.9300 . ? C7 N3 1.335(3) . ? C7 H6 0.9300 . ? C8 C8 0.908(11) 6_575 ? C8 N4 1.364(6) . ? C8 C9 1.371(7) . ? C8 C9 1.656(7) 6_575 ? C8 H8 0.9600 . ? C9 C9 0.949(12) 6_575 ? C9 C10 1.419(6) . ? C9 C8 1.656(7) 6_575 ? C9 H9 0.9601 . ? C10 C11 1.337(6) . ? C10 C9 1.419(6) 6_575 ? C10 C10 1.485(6) 5_675 ? C11 C12 1.376(5) . ? C11 H11 0.9300 . ? C12 N4 1.294(4) . ? C12 H12 0.9300 . ? Fe1 C2 1.903(2) 2_756 ? Fe1 C1 1.945(3) 2_756 ? Fe1 N3 1.9747(19) 2_756 ? Fe1 N3 1.9747(19) . ? Mn1 N2 2.223(2) 2_755 ? Mn1 N2 2.223(2) 6_575 ? Mn1 N2 2.223(2) . ? Mn1 N2 2.223(2) 5_775 ? Mn1 N4 2.256(3) . ? Mn1 N4 2.256(3) 5_775 ? N4 C8 1.364(6) 6_575 ? O1 O1 1.680(16) 2_556 ? O1 H1B 0.8500 . ? O1 H1A 0.8500 . ? O1A H1A 0.9800 . ? O1A H1C 0.8499 . ? O1A H1D 0.8500 . ? 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 N1 C1 Fe1 177.8(2) . . ? N2 C2 Fe1 174.5(2) . . ? N3 C3 C4 121.4(2) . . ? N3 C3 C3 114.40(12) . 2_756 ? C4 C3 C3 124.22(15) . 2_756 ? C5 C4 C3 119.0(3) . . ? C5 C4 H3 120.5 . . ? C3 C4 H3 120.5 . . ? C6 C5 C4 119.0(2) . . ? C6 C5 H4 120.5 . . ? C4 C5 H4 120.5 . . ? C7 C6 C5 119.6(2) . . ? C7 C6 H5 120.2 . . ? C5 C6 H5 120.2 . . ? N3 C7 C6 122.2(2) . . ? N3 C7 H6 118.9 . . ? C6 C7 H6 118.9 . . ? C8 C8 N4 70.6(2) 6_575 . ? C8 C8 C9 90.8(3) 6_575 . ? N4 C8 C9 123.1(4) . . ? C8 C8 C9 55.9(3) 6_575 6_575 ? N4 C8 C9 105.2(4) . 6_575 ? C9 C8 C9 35.0(4) . 6_575 ? C8 C8 H8 105.6 6_575 . ? N4 C8 H8 118.4 . . ? C9 C8 H8 118.4 . . ? C9 C8 H8 123.2 6_575 . ? C9 C9 C8 89.2(3) 6_575 . ? C9 C9 C10 70.5(2) 6_575 . ? C8 C9 C10 118.5(4) . . ? C9 C9 C8 55.9(3) 6_575 6_575 ? C8 C9 C8 33.3(4) . 6_575 ? C10 C9 C8 102.2(4) . 6_575 ? C9 C9 H9 99.0 6_575 . ? C8 C9 H9 106.7 . . ? C10 C9 H9 132.9 . . ? C8 C9 H9 108.9 6_575 . ? C11 C10 C9 113.1(3) . . ? C11 C10 C9 113.1(3) . 6_575 ? C9 C10 C9 39.1(5) . 6_575 ? C11 C10 C10 124.0(4) . 5_675 ? C9 C10 C10 119.5(4) . 5_675 ? C9 C10 C10 119.5(4) 6_575 5_675 ? C10 C11 C12 121.2(3) . . ? C10 C11 H11 119.4 . . ? C12 C11 H11 119.4 . . ? N4 C12 C11 124.2(4) . . ? N4 C12 H12 117.9 . . ? C11 C12 H12 117.9 . . ? C2 Fe1 C2 85.29(13) . 2_756 ? C2 Fe1 C1 93.04(10) . . ? C2 Fe1 C1 86.36(10) 2_756 . ? C2 Fe1 C1 86.36(10) . 2_756 ? C2 Fe1 C1 93.04(10) 2_756 2_756 ? C1 Fe1 C1 179.19(14) . 2_756 ? C2 Fe1 N3 175.14(9) . 2_756 ? C2 Fe1 N3 96.92(9) 2_756 2_756 ? C1 Fe1 N3 91.42(10) . 2_756 ? C1 Fe1 N3 89.20(10) 2_756 2_756 ? C2 Fe1 N3 96.92(9) . . ? C2 Fe1 N3 175.14(9) 2_756 . ? C1 Fe1 N3 89.20(10) . . ? C1 Fe1 N3 91.42(10) 2_756 . ? N3 Fe1 N3 81.21(11) 2_756 . ? N2 Mn1 N2 180.00(7) 2_755 6_575 ? N2 Mn1 N2 90.96(11) 2_755 . ? N2 Mn1 N2 89.04(11) 6_575 . ? N2 Mn1 N2 89.04(11) 2_755 5_775 ? N2 Mn1 N2 90.96(11) 6_575 5_775 ? N2 Mn1 N2 180.00(7) . 5_775 ? N2 Mn1 N4 90.06(7) 2_755 . ? N2 Mn1 N4 89.94(7) 6_575 . ? N2 Mn1 N4 89.94(7) . . ? N2 Mn1 N4 90.06(7) 5_775 . ? N2 Mn1 N4 89.94(7) 2_755 5_775 ? N2 Mn1 N4 90.06(7) 6_575 5_775 ? N2 Mn1 N4 90.06(7) . 5_775 ? N2 Mn1 N4 89.94(7) 5_775 5_775 ? N4 Mn1 N4 180.00(15) . 5_775 ? C2 N2 Mn1 152.05(19) . . ? C7 N3 C3 118.8(2) . . ? C7 N3 Fe1 126.14(17) . . ? C3 N3 Fe1 114.99(15) . . ? C12 N4 C8 112.8(3) . . ? C12 N4 C8 112.8(3) . 6_575 ? C8 N4 C8 38.9(5) . 6_575 ? C12 N4 Mn1 124.6(2) . . ? C8 N4 Mn1 119.2(2) . . ? C8 N4 Mn1 119.2(2) 6_575 . ? O1 O1 H1B 127.2 2_556 . ? O1 O1 H1A 98.3 2_556 . ? H1B O1 H1A 78.7 . . ? H1A O1A H1C 160.1 . . ? H1A O1A H1D 69.1 . . ? H1C O1A H1D 130.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N3 C3 C4 C5 1.3(4) . . . . ? C3 C3 C4 C5 -178.6(3) 2_756 . . . ? C3 C4 C5 C6 0.5(4) . . . . ? C4 C5 C6 C7 -1.7(4) . . . . ? C5 C6 C7 N3 1.1(4) . . . . ? C8 C8 C9 C9 0.0 6_575 . . 6_575 ? N4 C8 C9 C9 67.2(5) . . . 6_575 ? C8 C8 C9 C10 -67.1(4) 6_575 . . . ? N4 C8 C9 C10 0.0(8) . . . . ? C9 C8 C9 C10 -67.1(4) 6_575 . . . ? N4 C8 C9 C8 67.2(5) . . . 6_575 ? C9 C8 C9 C8 0.0 6_575 . . 6_575 ? C9 C9 C10 C11 -98.68(17) 6_575 . . . ? C8 C9 C10 C11 -20.8(6) . . . . ? C8 C9 C10 C11 -52.0(4) 6_575 . . . ? C8 C9 C10 C9 77.8(5) . . . 6_575 ? C8 C9 C10 C9 46.7(4) 6_575 . . 6_575 ? C9 C9 C10 C10 101.6(3) 6_575 . . 5_675 ? C8 C9 C10 C10 179.4(4) . . . 5_675 ? C8 C9 C10 C10 148.3(3) 6_575 . . 5_675 ? C9 C10 C11 C12 21.3(3) . . . . ? C9 C10 C11 C12 -21.3(3) 6_575 . . . ? C10 C10 C11 C12 180.0 5_675 . . . ? C10 C11 C12 N4 0.0 . . . . ? N2 C2 Fe1 C2 -84(2) . . . 2_756 ? N2 C2 Fe1 C1 -170(2) . . . . ? N2 C2 Fe1 C1 10(2) . . . 2_756 ? N2 C2 Fe1 N3 33(3) . . . 2_756 ? N2 C2 Fe1 N3 100(2) . . . . ? N1 C1 Fe1 C2 -154(7) . . . . ? N1 C1 Fe1 C2 121(7) . . . 2_756 ? N1 C1 Fe1 C1 164(7) . . . 2_756 ? N1 C1 Fe1 N3 24(7) . . . 2_756 ? N1 C1 Fe1 N3 -57(7) . . . . ? Fe1 C2 N2 Mn1 9(2) . . . . ? N2 Mn1 N2 C2 -69.0(4) 2_755 . . . ? N2 Mn1 N2 C2 111.0(4) 6_575 . . . ? N2 Mn1 N2 C2 112(53) 5_775 . . . ? N4 Mn1 N2 C2 21.1(4) . . . . ? N4 Mn1 N2 C2 -158.9(4) 5_775 . . . ? C6 C7 N3 C3 0.7(4) . . . . ? C6 C7 N3 Fe1 179.0(2) . . . . ? C4 C3 N3 C7 -1.9(4) . . . . ? C3 C3 N3 C7 178.0(3) 2_756 . . . ? C4 C3 N3 Fe1 179.6(2) . . . . ? C3 C3 N3 Fe1 -0.4(3) 2_756 . . . ? C2 Fe1 N3 C7 6.4(2) . . . . ? C2 Fe1 N3 C7 -110.4(9) 2_756 . . . ? C1 Fe1 N3 C7 -86.6(2) . . . . ? C1 Fe1 N3 C7 92.9(2) 2_756 . . . ? N3 Fe1 N3 C7 -178.1(3) 2_756 . . . ? C2 Fe1 N3 C3 -175.32(18) . . . . ? C2 Fe1 N3 C3 67.8(10) 2_756 . . . ? C1 Fe1 N3 C3 91.71(19) . . . . ? C1 Fe1 N3 C3 -88.82(19) 2_756 . . . ? N3 Fe1 N3 C3 0.15(13) 2_756 . . . ? C11 C12 N4 C8 -21.2(3) . . . . ? C11 C12 N4 C8 21.2(3) . . . 6_575 ? C11 C12 N4 Mn1 180.0 . . . . ? C8 C8 N4 C12 98.52(16) 6_575 . . . ? C9 C8 N4 C12 20.7(6) . . . . ? C9 C8 N4 C12 53.9(4) 6_575 . . . ? C9 C8 N4 C8 -77.8(5) . . . 6_575 ? C9 C8 N4 C8 -44.6(3) 6_575 . . 6_575 ? C8 C8 N4 Mn1 -101.40(18) 6_575 . . . ? C9 C8 N4 Mn1 -179.2(4) . . . . ? C9 C8 N4 Mn1 -146.0(2) 6_575 . . . ? N2 Mn1 N4 C12 135.48(5) 2_755 . . . ? N2 Mn1 N4 C12 -44.52(5) 6_575 . . . ? N2 Mn1 N4 C12 44.52(5) . . . . ? N2 Mn1 N4 C12 -135.48(5) 5_775 . . . ? N4 Mn1 N4 C12 180.0 5_775 . . . ? N2 Mn1 N4 C8 -22.1(3) 2_755 . . . ? N2 Mn1 N4 C8 157.9(3) 6_575 . . . ? N2 Mn1 N4 C8 -113.0(3) . . . . ? N2 Mn1 N4 C8 67.0(3) 5_775 . . . ? N4 Mn1 N4 C8 22.4(3) 5_775 . . . ? N2 Mn1 N4 C8 -67.0(3) 2_755 . . 6_575 ? N2 Mn1 N4 C8 113.0(3) 6_575 . . 6_575 ? N2 Mn1 N4 C8 -157.9(3) . . . 6_575 ? N2 Mn1 N4 C8 22.1(3) 5_775 . . 6_575 ? N4 Mn1 N4 C8 -22.4(3) 5_775 . . 6_575 ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.453 _refine_diff_density_min -0.369 _refine_diff_density_rms 0.073 data_CuFe2 _database_code_depnum_ccdc_archive 'CCDC 872241' #TrackingRef '- CuFe2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C38 H32 Cu Fe2 N14 O4' _chemical_formula_sum 'C38 H32 Cu Fe2 N14 O4' _chemical_formula_weight 924.02 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' Cu Cu 0.3201 1.2651 '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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 11.1851(9) _cell_length_b 29.1351(8) _cell_length_c 6.8304(5) _cell_angle_alpha 90.00 _cell_angle_beta 113.5410(10) _cell_angle_gamma 90.00 _cell_volume 2040.6(2) _cell_formula_units_Z 2 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 4909 _cell_measurement_theta_min 2.80 _cell_measurement_theta_max 27.54 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.504 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 942 _exptl_absorpt_coefficient_mu 1.276 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7164 _exptl_absorpt_correction_T_max 0.7666 _exptl_absorpt_process_details 'SADABS; Bruker, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6227 _diffrn_reflns_av_R_equivalents 0.0459 _diffrn_reflns_av_sigmaI/netI 0.0576 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -35 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 1.40 _diffrn_reflns_theta_max 26.00 _reflns_number_total 2051 _reflns_number_gt 1619 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0690P)^2^+2.2915P] 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 2051 _refine_ls_number_parameters 162 _refine_ls_number_restraints 9 _refine_ls_R_factor_all 0.0736 _refine_ls_R_factor_gt 0.0550 _refine_ls_wR_factor_ref 0.1318 _refine_ls_wR_factor_gt 0.1260 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.076 _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 C1 C 0.8718(4) 0.17831(15) 0.7505(7) 0.0334(9) Uani 1 1 d . . . H1 H 0.8528 0.1493 0.7869 0.040 Uiso 1 1 calc R . . C2 C 0.8318(4) 0.21560(15) 0.8252(7) 0.0332(9) Uani 1 1 d . . . H2 H 0.7828 0.2123 0.9069 0.040 Uiso 1 1 calc R . . C3 C 0.8651(4) 0.25915(15) 0.7777(7) 0.0343(10) Uani 1 1 d . . . H3 H 0.8419 0.2852 0.8331 0.041 Uiso 1 1 calc R . . C4 C 0.9308(4) 0.26323(14) 0.6520(7) 0.0321(9) Uani 1 1 d . . . H4 H 0.9530 0.2921 0.6193 0.038 Uiso 1 1 calc R . . C5 C 0.9659(4) 0.22378(14) 0.5699(7) 0.0321(9) Uani 1 1 d . . . C6 C 1.1681(4) 0.12969(14) 0.7502(7) 0.0359(9) Uani 1 1 d U . . C7 C 0.9526(4) 0.08227(14) 0.6467(7) 0.0313(8) Uani 1 1 d U . . C8 C 0.7979(6) 0.0000 1.1950(9) 0.0294(12) Uani 1 2 d S . . H8 H 0.8700 0.0000 1.3247 0.035 Uiso 1 2 calc SR . . C9 C 0.6811(4) 0.0000 1.1958(10) 0.0309(13) Uani 1 2 d S . . H9 H 0.6722 0.0000 1.3255 0.037 Uiso 1 2 calc SRD . . C10 C 0.5680(6) 0.0000 1.0028(9) 0.0301(12) Uani 1 2 d S . . C11 C 0.5924(4) 0.0000 0.8133(10) 0.0310(12) Uani 1 2 d S . . H11 H 0.5217 0.0000 0.6819 0.037 Uiso 1 2 calc SR . . C12 C 0.7114(6) 0.0000 0.8162(10) 0.0313(13) Uani 1 2 d S . . H12 H 0.7227 0.0000 0.6885 0.038 Uiso 1 2 calc SR . . Cu1 Cu 1.0000 0.0000 1.0000 0.0228(3) Uani 1 4 d SU . . Fe1 Fe 1.0000 0.12983(3) 0.5000 0.0226(2) Uani 1 2 d SU . . N1 N 0.9385(3) 0.18185(12) 0.6250(5) 0.0311(8) Uani 1 1 d . . . N2 N 1.2644(4) 0.13139(13) 0.8962(6) 0.0362(9) Uani 1 1 d . . . N3 N 0.9356(3) 0.05319(12) 0.7428(6) 0.0309(7) Uani 1 1 d U . . N4 N 0.8179(5) 0.0000 1.0067(8) 0.0288(10) Uani 1 2 d S . . O1WA O 0.4692(9) 0.1284(3) 0.8018(18) 0.039(3) Uani 0.303(9) 1 d P . . H1A H 0.4536 0.1007 0.7603 0.047 Uiso 0.303(9) 1 d PR . . H1B H 0.4774 0.1304 0.9306 0.047 Uiso 0.303(9) 1 d PR . . O1WB O 0.5000 0.1247(2) 0.5000 0.0338(17) Uani 0.760(13) 2 d SP . . H1C H 0.4535 0.1111 0.3845 0.041 Uiso 0.380(6) 1 d PR . . H1D H 0.5678 0.1136 0.5982 0.041 Uiso 0.380(6) 1 d PR . . O1WC O 0.6478(9) 0.0901(3) 0.4543(16) 0.037(3) Uani 0.317(8) 1 d P . . H1E H 0.6152 0.0716 0.3499 0.044 Uiso 0.317(8) 1 d PR . . H1F H 0.6969 0.1092 0.4281 0.044 Uiso 0.317(8) 1 d PR . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.038(2) 0.028(2) 0.030(2) 0.0016(16) 0.0086(18) 0.0017(17) C2 0.033(2) 0.039(2) 0.034(2) -0.0004(18) 0.0202(18) 0.0023(18) C3 0.030(2) 0.034(2) 0.040(2) -0.0131(18) 0.0160(19) -0.0020(18) C4 0.032(2) 0.025(2) 0.034(2) -0.0009(17) 0.0082(18) 0.0007(16) C5 0.041(2) 0.029(2) 0.032(2) -0.0014(17) 0.0196(19) -0.0003(19) C6 0.0339(18) 0.030(2) 0.036(2) -0.0077(18) 0.0054(15) 0.0009(15) C7 0.038(2) 0.0271(19) 0.031(2) -0.0010(13) 0.0161(17) -0.0012(15) C8 0.032(3) 0.032(3) 0.021(3) 0.000 0.007(2) 0.000 C9 0.035(3) 0.026(3) 0.030(3) 0.000 0.011(3) 0.000 C10 0.030(3) 0.031(3) 0.025(3) 0.000 0.007(2) 0.000 C11 0.030(3) 0.027(3) 0.031(3) 0.000 0.007(2) 0.000 C12 0.031(3) 0.035(3) 0.030(3) 0.000 0.014(2) 0.000 Cu1 0.0211(5) 0.0194(5) 0.0265(5) 0.000 0.0082(4) 0.000 Fe1 0.0228(4) 0.0245(4) 0.0231(4) 0.000 0.0119(3) 0.000 N1 0.0318(18) 0.0307(19) 0.0312(19) -0.0004(14) 0.0129(15) 0.0027(14) N2 0.038(2) 0.038(2) 0.033(2) -0.0008(15) 0.0137(17) 0.0057(15) N3 0.0337(18) 0.0330(18) 0.0323(19) 0.0033(12) 0.0200(15) 0.0011(14) N4 0.035(3) 0.029(3) 0.026(3) 0.000 0.016(2) 0.000 O1WA 0.027(5) 0.039(6) 0.045(7) 0.000(5) 0.009(5) -0.002(4) O1WB 0.029(3) 0.043(4) 0.037(3) 0.000 0.021(2) 0.000 O1WC 0.035(5) 0.040(6) 0.034(5) 0.005(4) 0.013(4) -0.001(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 C1 N1 1.346(6) . ? C1 C2 1.351(6) . ? C1 H1 0.9300 . ? C2 C3 1.397(6) . ? C2 H2 0.9300 . ? C3 C4 1.339(6) . ? C3 H3 0.9300 . ? C4 C5 1.402(6) . ? C4 H4 0.9300 . ? C5 N1 1.349(5) . ? C5 C5 1.439(8) 2_756 ? C6 N2 1.140(6) . ? C6 Fe1 1.972(4) . ? C7 N3 1.133(5) . ? C7 Fe1 1.905(4) . ? C8 C9 1.309(7) . ? C8 N4 1.391(7) . ? C8 H8 0.9300 . ? C9 C10 1.416(8) . ? C9 H9 0.9300 . ? C10 C11 1.426(8) . ? C10 C10 1.507(12) 5_657 ? C11 C12 1.323(7) . ? C11 H11 0.9300 . ? C12 N4 1.369(8) . ? C12 H12 0.9300 . ? Cu1 N4 2.055(5) . ? Cu1 N4 2.055(5) 5_757 ? Cu1 N3 2.235(3) 6 ? Cu1 N3 2.235(3) 2_757 ? Cu1 N3 2.235(3) . ? Cu1 N3 2.235(3) 5_757 ? Fe1 C7 1.905(4) 2_756 ? Fe1 C6 1.972(4) 2_756 ? Fe1 N1 1.992(4) . ? Fe1 N1 1.992(4) 2_756 ? O1WA H1A 0.8500 . ? O1WA H1B 0.8500 . ? O1WB H1C 0.8500 . ? O1WB H1D 0.8501 . ? O1WC H1E 0.8500 . ? O1WC H1F 0.8500 . ? 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 N1 C1 C2 122.1(4) . . ? N1 C1 H1 119.0 . . ? C2 C1 H1 119.0 . . ? C1 C2 C3 118.9(4) . . ? C1 C2 H2 120.6 . . ? C3 C2 H2 120.6 . . ? C4 C3 C2 119.7(4) . . ? C4 C3 H3 120.2 . . ? C2 C3 H3 120.2 . . ? C3 C4 C5 119.8(4) . . ? C3 C4 H4 120.1 . . ? C5 C4 H4 120.1 . . ? N1 C5 C4 119.9(4) . . ? N1 C5 C5 115.1(2) . 2_756 ? C4 C5 C5 124.9(2) . 2_756 ? N2 C6 Fe1 177.3(4) . . ? N3 C7 Fe1 174.0(4) . . ? C9 C8 N4 122.3(5) . . ? C9 C8 H8 118.9 . . ? N4 C8 H8 118.9 . . ? C8 C9 C10 121.2(5) . . ? C8 C9 H9 119.4 . . ? C10 C9 H9 119.4 . . ? C9 C10 C11 114.9(4) . . ? C9 C10 C10 122.7(6) . 5_657 ? C11 C10 C10 122.3(6) . 5_657 ? C12 C11 C10 122.9(6) . . ? C12 C11 H11 118.6 . . ? C10 C11 H11 118.6 . . ? C11 C12 N4 120.2(6) . . ? C11 C12 H12 119.9 . . ? N4 C12 H12 119.9 . . ? N4 Cu1 N4 180.000(1) . 5_757 ? N4 Cu1 N3 90.38(13) . 6 ? N4 Cu1 N3 89.62(13) 5_757 6 ? N4 Cu1 N3 89.62(13) . 2_757 ? N4 Cu1 N3 90.38(13) 5_757 2_757 ? N3 Cu1 N3 180.00(13) 6 2_757 ? N4 Cu1 N3 90.38(13) . . ? N4 Cu1 N3 89.62(13) 5_757 . ? N3 Cu1 N3 87.78(18) 6 . ? N3 Cu1 N3 92.22(18) 2_757 . ? N4 Cu1 N3 89.62(13) . 5_757 ? N4 Cu1 N3 90.38(13) 5_757 5_757 ? N3 Cu1 N3 92.22(18) 6 5_757 ? N3 Cu1 N3 87.78(18) 2_757 5_757 ? N3 Cu1 N3 180.00(13) . 5_757 ? C7 Fe1 C7 86.7(2) 2_756 . ? C7 Fe1 C6 84.96(19) 2_756 2_756 ? C7 Fe1 C6 94.87(18) . 2_756 ? C7 Fe1 C6 94.87(18) 2_756 . ? C7 Fe1 C6 84.96(19) . . ? C6 Fe1 C6 179.8(2) 2_756 . ? C7 Fe1 N1 174.29(16) 2_756 . ? C7 Fe1 N1 96.40(16) . . ? C6 Fe1 N1 89.99(17) 2_756 . ? C6 Fe1 N1 90.19(16) . . ? C7 Fe1 N1 96.40(16) 2_756 2_756 ? C7 Fe1 N1 174.29(16) . 2_756 ? C6 Fe1 N1 90.19(16) 2_756 2_756 ? C6 Fe1 N1 89.99(17) . 2_756 ? N1 Fe1 N1 80.9(2) . 2_756 ? C1 N1 C5 119.5(4) . . ? C1 N1 Fe1 126.1(3) . . ? C5 N1 Fe1 114.4(3) . . ? C7 N3 Cu1 153.9(3) . . ? C12 N4 C8 118.6(5) . . ? C12 N4 Cu1 118.2(4) . . ? C8 N4 Cu1 123.2(4) . . ? H1A O1WA H1B 109.5 . . ? H1C O1WB H1D 125.3 . . ? H1E O1WC H1F 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 C1 C2 C3 -2.6(7) . . . . ? C1 C2 C3 C4 2.9(6) . . . . ? C2 C3 C4 C5 -0.3(7) . . . . ? C3 C4 C5 N1 -2.8(7) . . . . ? C3 C4 C5 C5 178.7(5) . . . 2_756 ? N4 C8 C9 C10 0.000(3) . . . . ? C8 C9 C10 C11 0.000(3) . . . . ? C8 C9 C10 C10 180.000(3) . . . 5_657 ? C9 C10 C11 C12 0.000(3) . . . . ? C10 C10 C11 C12 180.000(2) 5_657 . . . ? C10 C11 C12 N4 0.000(2) . . . . ? N3 C7 Fe1 C7 70(4) . . . 2_756 ? N3 C7 Fe1 C6 154(4) . . . 2_756 ? N3 C7 Fe1 C6 -25(4) . . . . ? N3 C7 Fe1 N1 -115(4) . . . . ? N3 C7 Fe1 N1 -53(5) . . . 2_756 ? N2 C6 Fe1 C7 155(9) . . . 2_756 ? N2 C6 Fe1 C7 -119(9) . . . . ? N2 C6 Fe1 C6 -162(21) . . . 2_756 ? N2 C6 Fe1 N1 -22(9) . . . . ? N2 C6 Fe1 N1 59(9) . . . 2_756 ? C2 C1 N1 C5 -0.4(6) . . . . ? C2 C1 N1 Fe1 -178.7(3) . . . . ? C4 C5 N1 C1 3.2(6) . . . . ? C5 C5 N1 C1 -178.2(5) 2_756 . . . ? C4 C5 N1 Fe1 -178.3(3) . . . . ? C5 C5 N1 Fe1 0.3(6) 2_756 . . . ? C7 Fe1 N1 C1 115.8(16) 2_756 . . . ? C7 Fe1 N1 C1 -6.8(4) . . . . ? C6 Fe1 N1 C1 88.1(4) 2_756 . . . ? C6 Fe1 N1 C1 -91.8(4) . . . . ? N1 Fe1 N1 C1 178.3(4) 2_756 . . . ? C7 Fe1 N1 C5 -62.6(17) 2_756 . . . ? C7 Fe1 N1 C5 174.8(3) . . . . ? C6 Fe1 N1 C5 -90.3(3) 2_756 . . . ? C6 Fe1 N1 C5 89.9(3) . . . . ? N1 Fe1 N1 C5 -0.1(2) 2_756 . . . ? Fe1 C7 N3 Cu1 10(4) . . . . ? N4 Cu1 N3 C7 156.4(8) . . . . ? N4 Cu1 N3 C7 -23.6(8) 5_757 . . . ? N3 Cu1 N3 C7 -113.3(7) 6 . . . ? N3 Cu1 N3 C7 66.7(7) 2_757 . . . ? N3 Cu1 N3 C7 -113(100) 5_757 . . . ? C11 C12 N4 C8 0.000(2) . . . . ? C11 C12 N4 Cu1 180.000(2) . . . . ? C9 C8 N4 C12 0.000(3) . . . . ? C9 C8 N4 Cu1 180.000(3) . . . . ? N4 Cu1 N4 C12 180(17) 5_757 . . . ? N3 Cu1 N4 C12 -43.89(9) 6 . . . ? N3 Cu1 N4 C12 136.11(9) 2_757 . . . ? N3 Cu1 N4 C12 43.89(9) . . . . ? N3 Cu1 N4 C12 -136.11(9) 5_757 . . . ? N4 Cu1 N4 C8 0(17) 5_757 . . . ? N3 Cu1 N4 C8 136.11(9) 6 . . . ? N3 Cu1 N4 C8 -43.89(9) 2_757 . . . ? N3 Cu1 N4 C8 -136.11(9) . . . . ? N3 Cu1 N4 C8 43.89(9) 5_757 . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.762 _refine_diff_density_min -1.078 _refine_diff_density_rms 0.093