Supplementary Material (ESI) for Journal of Materials Chemistry This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_name_full J.Mater.Chem. _journal_coden_Cambridge 1145 _publ_contact_author_name 'Song Gao' _publ_contact_author_address ; State Key Lab. of Rare Earth Materialds Chemistry Peking University & Applications College of Chemistry & Molecular En Beijing 100871 CHINA ; _publ_contact_author_email GAOSONG@PKU.EDU.CN _publ_section_title ; Structures and magnetism of cyano-bridged grid-like two-dimensional 4f-3d arrays ; loop_ _publ_author_name 'Song Gao' 'Gong-Ping Duan' 'Osamu Sato' 'Yuanzhu Zhang' ## Crystallographic Data of Complex SmFe data_SmFe _database_code_depnum_ccdc_archive 'CCDC 298760' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 2D-grid-FeSm _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H18 Fe N8 O7 Sm' _chemical_formula_weight 640.58 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' Sm Sm -0.1638 3.4418 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' _cell_length_a 13.6684(4) _cell_length_b 7.4084(2) _cell_length_c 23.4344(8) _cell_angle_alpha 90.00 _cell_angle_beta 101.6915(12) _cell_angle_gamma 90.00 _cell_volume 2323.76(12) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 59801 _cell_measurement_theta_min 3.395 _cell_measurement_theta_max 27.485 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.831 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1256 _exptl_absorpt_coefficient_mu 3.179 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.738 _exptl_absorpt_correction_T_max 0.891 _exptl_absorpt_process_details '(Blessing, 1995, 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'NONIUS KappaCCD' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 0.76 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 25832 _diffrn_reflns_av_R_equivalents 0.1111 _diffrn_reflns_av_sigmaI/netI 0.1287 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 3.45 _diffrn_reflns_theta_max 27.45 _reflns_number_total 5269 _reflns_number_gt 3137 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'KappaCCD (Nonius B. V., 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor, 1997)' _computing_data_reduction 'HKL Denzo (Otwinowski & Minor, 1997) & maXus (Mackay et al., 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL V5.1 (Sheldrick, 1998)' _computing_publication_material 'SHELXL-97 (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^)+(0.0697P)^2^+40.2354P] 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 5269 _refine_ls_number_parameters 289 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1310 _refine_ls_R_factor_gt 0.0739 _refine_ls_wR_factor_ref 0.1987 _refine_ls_wR_factor_gt 0.1842 _refine_ls_goodness_of_fit_ref 1.088 _refine_ls_restrained_S_all 1.088 _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 Sm1 Sm 0.28413(4) 0.54393(9) 0.84963(3) 0.0183(2) Uani 1 1 d . . . Fe1 Fe 0.0000 1.0328(4) 0.7500 0.0229(5) Uani 1 2 d S . . Fe2 Fe 0.5000 0.0510(4) 0.7500 0.0226(5) Uani 1 2 d S . . O1 O 0.1566(6) 0.5598(15) 0.9050(4) 0.038(2) Uani 1 1 d . . . O2 O -0.5495(6) 0.5394(17) 0.9060(4) 0.046(3) Uani 1 1 d . . . O3 O 0.3055(7) 0.2836(14) 0.9136(4) 0.038(2) Uani 1 1 d . . . O4 O 0.3074(9) 0.8174(18) 0.9091(7) 0.093(6) Uani 1 1 d . . . O5 O 0.1690(7) 0.0497(15) 0.9451(5) 0.049(3) Uani 1 1 d . . . O6 O 0.1788(9) -0.0934(17) 1.0501(5) 0.062(3) Uani 1 1 d . . . O7 O 0.4700(9) 0.0531(19) 0.9427(6) 0.074(4) Uani 1 1 d . . . N1 N 0.1541(8) 0.7287(18) 0.7879(6) 0.044(3) Uani 1 1 d . . . N2 N 0.0382(10) 1.042(2) 0.6250(6) 0.056(4) Uani 1 1 d . . . N3 N 0.1609(8) 1.3231(14) 0.7923(5) 0.027(3) Uani 1 1 d . . . N4 N 0.3719(10) 0.065(2) 0.6259(6) 0.058(4) Uani 1 1 d . . . N6 N 0.3709(8) -0.2419(16) 0.7927(5) 0.035(3) Uani 1 1 d . . . N7 N 0.0593(7) 0.5742(14) 0.9021(4) 0.026(2) Uani 1 1 d . . . N8 N -0.4533(7) 0.5507(19) 0.9039(5) 0.038(3) Uani 1 1 d . . . C1 C 0.0979(11) 0.8454(18) 0.7741(7) 0.036(4) Uani 1 1 d . . . C2 C 0.0259(10) 1.036(2) 0.6712(6) 0.034(3) Uani 1 1 d . . . C3 C 0.1011(9) 1.2130(18) 0.7742(6) 0.025(3) Uani 1 1 d . . . C4 C 0.4177(11) 0.057(2) 0.6717(6) 0.035(3) Uani 1 1 d . . . C6 C 0.4172(11) -0.1306(19) 0.7754(6) 0.032(3) Uani 1 1 d . . . C7 C 0.0260(9) 0.648(2) 0.9470(6) 0.033(3) Uani 1 1 d . . . H7 H 0.0714 0.6984 0.9780 0.040 Uiso 1 1 calc R . . C8 C -0.0727(9) 0.651(2) 0.9477(6) 0.034(3) Uani 1 1 d . . . H8 H -0.0936 0.7007 0.9797 0.041 Uiso 1 1 calc R . . C9 C -0.1438(9) 0.5827(17) 0.9020(6) 0.026(3) Uani 1 1 d . . . C10 C -0.1068(10) 0.521(2) 0.8539(6) 0.036(3) Uani 1 1 d . . . H10 H -0.1510 0.4771 0.8214 0.043 Uiso 1 1 calc R . . C11 C -0.0097(8) 0.5258(17) 0.8539(5) 0.021(3) Uiso 1 1 d . . . H11 H 0.0120 0.4949 0.8200 0.025 Uiso 1 1 calc R . . C12 C -0.2514(9) 0.5734(18) 0.9026(5) 0.028(3) Uani 1 1 d . . . C13 C -0.2851(10) 0.562(3) 0.9545(6) 0.053(5) Uani 1 1 d . . . H13 H -0.2394 0.5614 0.9898 0.064 Uiso 1 1 calc R . . C14 C -0.3845(10) 0.552(3) 0.9542(6) 0.061(5) Uani 1 1 d . . . H14 H -0.4057 0.5449 0.9894 0.073 Uiso 1 1 calc R . . C15 C -0.4189(7) 0.5593(14) 0.8522(4) 0.010(2) Uiso 1 1 d . . . H15 H -0.4645 0.5543 0.8168 0.012 Uiso 1 1 calc R . . C16 C -0.3238(10) 0.5743(18) 0.8522(5) 0.030(3) Uani 1 1 d . . . H16 H -0.3040 0.5861 0.8167 0.036 Uiso 1 1 calc R . . N5 N 0.3710(9) 0.3471(17) 0.7897(5) 0.039(3) Uani 1 1 d . . . C5 C 0.4172(9) 0.2363(18) 0.7743(6) 0.024(3) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Sm1 0.0121(3) 0.0188(3) 0.0248(3) -0.0009(3) 0.0054(2) -0.0007(3) Fe1 0.0162(11) 0.0180(12) 0.0314(14) 0.000 -0.0024(10) 0.000 Fe2 0.0227(12) 0.0187(12) 0.0301(13) 0.000 0.0140(10) 0.000 O1 0.012(4) 0.068(7) 0.035(5) -0.005(5) 0.011(4) -0.001(5) O2 0.014(4) 0.093(8) 0.031(5) 0.005(6) 0.006(4) -0.009(5) O3 0.029(5) 0.045(6) 0.042(6) 0.015(5) 0.009(4) 0.006(5) O4 0.053(8) 0.080(10) 0.163(14) -0.088(10) 0.064(9) -0.042(7) O5 0.039(6) 0.049(7) 0.060(7) 0.004(6) 0.011(5) -0.006(6) O6 0.055(7) 0.085(10) 0.046(7) -0.003(7) 0.011(5) 0.000(7) O7 0.051(7) 0.092(10) 0.083(9) 0.025(8) 0.022(7) 0.024(7) N1 0.016(6) 0.034(8) 0.076(10) 0.010(7) -0.005(6) 0.004(6) N2 0.058(9) 0.069(10) 0.043(8) -0.014(8) 0.015(7) 0.011(8) N3 0.025(6) 0.015(6) 0.042(7) -0.005(5) 0.007(5) -0.002(5) N4 0.053(9) 0.080(12) 0.037(8) 0.006(8) 0.001(7) -0.001(8) N6 0.028(6) 0.027(7) 0.056(8) 0.014(6) 0.022(6) 0.006(5) N7 0.019(5) 0.031(7) 0.029(6) 0.000(5) 0.010(4) 0.005(5) N8 0.014(5) 0.063(8) 0.037(7) 0.000(7) 0.006(5) -0.004(6) C1 0.039(8) 0.015(7) 0.051(10) 0.002(7) 0.003(7) 0.001(7) C2 0.029(7) 0.028(7) 0.038(8) -0.005(7) -0.008(6) 0.003(7) C3 0.011(6) 0.030(8) 0.033(8) -0.004(6) 0.004(5) 0.001(6) C4 0.040(8) 0.028(8) 0.038(9) -0.004(7) 0.012(7) -0.005(7) C6 0.041(8) 0.023(7) 0.035(8) 0.000(6) 0.017(7) 0.003(7) C7 0.024(7) 0.047(9) 0.030(7) -0.006(7) 0.010(6) -0.012(6) C8 0.023(7) 0.050(10) 0.031(8) -0.008(7) 0.006(6) -0.004(7) C9 0.018(6) 0.025(8) 0.032(7) -0.001(5) 0.001(5) 0.001(5) C10 0.040(8) 0.043(9) 0.022(7) -0.008(6) 0.000(6) -0.003(7) C12 0.023(6) 0.035(9) 0.026(7) -0.004(6) 0.006(5) 0.002(6) C13 0.016(7) 0.113(16) 0.031(8) -0.010(9) 0.005(6) -0.001(9) C14 0.022(7) 0.136(18) 0.025(8) -0.008(10) 0.007(6) -0.010(10) C16 0.040(8) 0.035(9) 0.019(6) 0.009(6) 0.011(6) 0.017(6) N5 0.031(7) 0.038(8) 0.053(8) 0.000(6) 0.019(6) 0.003(6) C5 0.018(6) 0.022(7) 0.037(8) -0.003(6) 0.020(6) -0.006(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 Sm1 O1 2.377(8) . ? Sm1 O2 2.388(8) 1_655 ? Sm1 O3 2.423(9) . ? Sm1 O4 2.443(11) . ? Sm1 N1 2.467(12) . ? Sm1 N5 2.487(12) . ? Sm1 N6 2.520(11) 1_565 ? Sm1 N3 2.530(11) 1_545 ? Fe1 C3 1.922(13) . ? Fe1 C3 1.922(13) 2_556 ? Fe1 C1 1.932(15) 2_556 ? Fe1 C1 1.932(14) . ? Fe1 C2 1.950(16) . ? Fe1 C2 1.950(16) 2_556 ? Fe2 C6 1.928(14) 2_656 ? Fe2 C6 1.928(15) . ? Fe2 C5 1.937(13) 2_656 ? Fe2 C5 1.937(13) . ? Fe2 C4 1.948(15) . ? Fe2 C4 1.948(15) 2_656 ? O1 N7 1.322(12) . ? O2 N8 1.329(12) . ? O2 Sm1 2.388(8) 1_455 ? N1 C1 1.158(17) . ? N2 C2 1.129(18) . ? N3 C3 1.172(15) . ? N3 Sm1 2.530(11) 1_565 ? N4 C4 1.130(18) . ? N6 C6 1.161(17) . ? N6 Sm1 2.520(11) 1_545 ? N7 C7 1.346(16) . ? N7 C11 1.366(15) . ? N8 C14 1.350(17) . ? N8 C15 1.388(14) . ? C7 C8 1.353(17) . ? C8 C9 1.389(17) . ? C9 C10 1.401(18) . ? C9 C12 1.475(17) . ? C10 C11 1.328(17) . ? C12 C16 1.378(18) . ? C12 C13 1.389(18) . ? C13 C14 1.360(18) . ? C15 C16 1.304(16) . ? N5 C5 1.138(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 O1 Sm1 O2 114.8(3) . 1_655 ? O1 Sm1 O3 73.2(3) . . ? O2 Sm1 O3 70.4(3) 1_655 . ? O1 Sm1 O4 70.9(4) . . ? O2 Sm1 O4 72.3(4) 1_655 . ? O3 Sm1 O4 108.8(5) . . ? O1 Sm1 N1 76.8(4) . . ? O2 Sm1 N1 145.6(4) 1_655 . ? O3 Sm1 N1 141.9(4) . . ? O4 Sm1 N1 82.5(5) . . ? O1 Sm1 N5 145.5(4) . . ? O2 Sm1 N5 78.1(4) 1_655 . ? O3 Sm1 N5 82.6(4) . . ? O4 Sm1 N5 141.9(4) . . ? N1 Sm1 N5 111.3(4) . . ? O1 Sm1 N6 137.2(4) . 1_565 ? O2 Sm1 N6 78.7(4) 1_655 1_565 ? O3 Sm1 N6 144.9(3) . 1_565 ? O4 Sm1 N6 76.0(5) . 1_565 ? N1 Sm1 N6 72.6(4) . 1_565 ? N5 Sm1 N6 75.0(4) . 1_565 ? O1 Sm1 N3 80.7(3) . 1_545 ? O2 Sm1 N3 137.9(4) 1_655 1_545 ? O3 Sm1 N3 78.3(4) . 1_545 ? O4 Sm1 N3 146.6(4) . 1_545 ? N1 Sm1 N3 74.0(4) . 1_545 ? N5 Sm1 N3 70.4(4) . 1_545 ? N6 Sm1 N3 117.4(4) 1_565 1_545 ? C3 Fe1 C3 92.1(8) . 2_556 ? C3 Fe1 C1 178.0(6) . 2_556 ? C3 Fe1 C1 89.9(5) 2_556 2_556 ? C3 Fe1 C1 89.9(5) . . ? C3 Fe1 C1 178.0(6) 2_556 . ? C1 Fe1 C1 88.1(8) 2_556 . ? C3 Fe1 C2 90.7(6) . . ? C3 Fe1 C2 88.3(6) 2_556 . ? C1 Fe1 C2 88.9(6) 2_556 . ? C1 Fe1 C2 92.2(6) . . ? C3 Fe1 C2 88.3(6) . 2_556 ? C3 Fe1 C2 90.7(6) 2_556 2_556 ? C1 Fe1 C2 92.2(6) 2_556 2_556 ? C1 Fe1 C2 88.9(6) . 2_556 ? C2 Fe1 C2 178.6(9) . 2_556 ? C6 Fe2 C6 91.5(8) 2_656 . ? C6 Fe2 C5 89.4(5) 2_656 2_656 ? C6 Fe2 C5 178.9(6) . 2_656 ? C6 Fe2 C5 178.9(6) 2_656 . ? C6 Fe2 C5 89.4(5) . . ? C5 Fe2 C5 89.7(7) 2_656 . ? C6 Fe2 C4 89.3(6) 2_656 . ? C6 Fe2 C4 92.4(6) . . ? C5 Fe2 C4 88.2(6) 2_656 . ? C5 Fe2 C4 90.1(6) . . ? C6 Fe2 C4 92.4(6) 2_656 2_656 ? C6 Fe2 C4 89.3(6) . 2_656 ? C5 Fe2 C4 90.1(6) 2_656 2_656 ? C5 Fe2 C4 88.2(6) . 2_656 ? C4 Fe2 C4 177.6(9) . 2_656 ? N7 O1 Sm1 144.9(7) . . ? N8 O2 Sm1 144.8(8) . 1_455 ? C1 N1 Sm1 159.4(13) . . ? C3 N3 Sm1 169.5(10) . 1_565 ? C6 N6 Sm1 168.7(12) . 1_545 ? O1 N7 C7 119.3(10) . . ? O1 N7 C11 122.6(10) . . ? C7 N7 C11 117.9(10) . . ? O2 N8 C14 119.1(11) . . ? O2 N8 C15 123.2(10) . . ? C14 N8 C15 117.6(10) . . ? N1 C1 Fe1 177.6(13) . . ? N2 C2 Fe1 177.5(14) . . ? N3 C3 Fe1 175.6(12) . . ? N4 C4 Fe2 177.6(15) . . ? N6 C6 Fe2 176.9(13) . . ? N7 C7 C8 120.8(12) . . ? C7 C8 C9 121.9(13) . . ? C8 C9 C10 115.4(12) . . ? C8 C9 C12 123.5(12) . . ? C10 C9 C12 121.0(11) . . ? C11 C10 C9 121.1(12) . . ? C10 C11 N7 121.9(11) . . ? C16 C12 C13 116.2(12) . . ? C16 C12 C9 122.4(11) . . ? C13 C12 C9 121.3(12) . . ? C14 C13 C12 120.5(13) . . ? N8 C14 C13 121.6(13) . . ? C16 C15 N8 121.1(10) . . ? C15 C16 C12 123.0(11) . . ? C5 N5 Sm1 164.0(12) . . ? N5 C5 Fe2 177.9(13) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 27.45 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 6.149 _refine_diff_density_min -2.320 _refine_diff_density_rms 0.267 ## Crystallographic Data of Complex TbFe data_TbFe _database_code_depnum_ccdc_archive 'CCDC 298761' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common TbFe-2D _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H18 Fe N8 O7 Tb' _chemical_formula_weight 649.15 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' Tb Tb -0.1723 4.1537 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.3467(2) _cell_length_b 11.7325(3) _cell_length_c 13.5919(4) _cell_angle_alpha 101.5635(16) _cell_angle_beta 90.6115(17) _cell_angle_gamma 92.7337(12) _cell_volume 1146.23(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 22561 _cell_measurement_theta_min 3.395 _cell_measurement_theta_max 27.485 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.881 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 634 _exptl_absorpt_coefficient_mu 3.746 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.788 _exptl_absorpt_correction_T_max 0.902 _exptl_absorpt_process_details '(Blessing, 1995, 1997)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'NONIUS KappaCCD' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 0.76 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9340 _diffrn_reflns_av_R_equivalents 0.0681 _diffrn_reflns_av_sigmaI/netI 0.1416 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.43 _diffrn_reflns_theta_max 27.45 _reflns_number_total 5205 _reflns_number_gt 3448 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'KappaCCD (Nonius B. V., 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor, 1997)' _computing_data_reduction 'HKL Denzo (Otwinowski & Minor, 1997) & maXus (Mackay et al., 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL V5.1 (Sheldrick, 1998)' _computing_publication_material 'SHELXL-97 (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^)+(0.1649P)^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 5205 _refine_ls_number_parameters 301 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1326 _refine_ls_R_factor_gt 0.0935 _refine_ls_wR_factor_ref 0.2499 _refine_ls_wR_factor_gt 0.2335 _refine_ls_goodness_of_fit_ref 1.004 _refine_ls_restrained_S_all 1.004 _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 Tb1 Tb 0.51742(8) 0.69836(6) 0.78410(4) 0.0173(2) Uani 1 1 d . . . Fe1 Fe 1.0000 0.5000 1.0000 0.0214(6) Uani 1 2 d S . . Fe2 Fe 1.0000 0.5000 0.5000 0.0202(6) Uani 1 2 d S . . O1 O 0.5354(17) 0.8109(9) 0.6595(7) 0.038(3) Uani 1 1 d . . . O2 O 0.5311(19) 0.8130(10) -0.0512(7) 0.047(3) Uani 1 1 d . . . O3 O 0.2723(15) 0.8247(10) 0.8055(8) 0.038(3) Uani 1 1 d . . . O4 O 0.8002(19) 0.8105(15) 0.8057(10) 0.076(5) Uani 1 1 d . . . O5 O 0.0361(17) 0.8855(11) 0.6687(9) 0.049(3) Uani 1 1 d . . . O6 O 0.037(2) 0.8836(15) 0.9696(11) 0.070(4) Uani 1 1 d . . . O7 O -0.086(2) 1.0986(11) 0.6788(9) 0.063(4) Uani 1 1 d . . . N1 N 0.971(2) 0.2515(14) 0.8716(12) 0.055(4) Uani 1 1 d . . . N2 N 0.7119(18) 0.5800(14) 0.8648(10) 0.041(4) Uani 1 1 d . . . N3 N 1.3032(17) 0.5876(12) 0.8753(9) 0.034(3) Uani 1 1 d . . . N4 N 1.2968(18) 0.5808(12) 0.6644(9) 0.035(3) Uani 1 1 d . . . N5 N 0.7037(17) 0.5830(12) 0.6533(9) 0.033(3) Uani 1 1 d . . . N6 N 1.030(2) 0.7503(13) 0.4612(12) 0.052(4) Uani 1 1 d . . . N7 N 0.5554(18) 0.8028(10) 0.5610(8) 0.030(3) Uani 1 1 d . . . N8 N 0.5393(19) 0.8066(10) 0.0465(8) 0.030(3) Uani 1 1 d . . . C1 C 0.982(2) 0.3467(15) 0.9177(11) 0.032(3) Uani 1 1 d . . . C2 C 0.822(2) 0.5479(13) 0.9123(11) 0.027(3) Uani 1 1 d . . . C3 C 1.1901(18) 0.5523(12) 0.9200(9) 0.022(3) Uani 1 1 d . . . C4 C 1.1819(18) 0.5484(11) 0.6046(11) 0.023(3) Uani 1 1 d . . . C5 C 0.8109(19) 0.5501(13) 0.5964(10) 0.025(3) Uani 1 1 d . . . C6 C 1.016(2) 0.6570(14) 0.4744(11) 0.034(4) Uani 1 1 d . . . C7 C 0.492(2) 0.7087(13) 0.4933(11) 0.034(4) Uani 1 1 d . . . H7 H 0.4444 0.6439 0.5157 0.041 Uiso 1 1 calc R . . C8 C 0.4963(19) 0.7065(12) 0.3952(11) 0.027(3) Uani 1 1 d . . . H8 H 0.4500 0.6408 0.3503 0.033 Uiso 1 1 calc R . . C9 C 0.638(2) 0.8942(14) 0.5278(11) 0.034(4) Uani 1 1 d . . . H9 H 0.6928 0.9559 0.5740 0.041 Uiso 1 1 calc R . . C10 C 0.642(2) 0.8966(14) 0.4295(11) 0.037(4) Uani 1 1 d . . . H10 H 0.6925 0.9620 0.4091 0.045 Uiso 1 1 calc R . . C11 C 0.571(2) 0.8035(13) 0.3581(11) 0.032(3) Uani 1 1 d . . . C12 C 0.560(2) 0.8042(14) 0.2482(10) 0.031(3) Uani 1 1 d . . . C13 C 0.559(3) 0.9082(17) 0.2139(13) 0.055(5) Uani 1 1 d . . . H13 H 0.5631 0.9786 0.2600 0.066 Uiso 1 1 calc R . . C14 C 0.554(3) 0.9085(16) 0.1136(12) 0.059(6) Uani 1 1 d . . . H14 H 0.5604 0.9786 0.0915 0.071 Uiso 1 1 calc R . . C15 C 0.5389(19) 0.7069(13) 0.0773(10) 0.026(3) Uani 1 1 d . . . H15 H 0.5352 0.6373 0.0302 0.031 Uiso 1 1 calc R . . C16 C 0.544(2) 0.7044(13) 0.1767(11) 0.029(3) Uani 1 1 d . . . H16 H 0.5367 0.6329 0.1964 0.035 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 Tb1 0.0174(4) 0.0220(4) 0.0132(3) 0.0055(2) 0.0007(2) 0.0007(2) Fe1 0.0171(13) 0.0267(15) 0.0238(14) 0.0131(11) 0.0006(11) 0.0010(11) Fe2 0.0175(13) 0.0251(15) 0.0160(13) -0.0005(11) 0.0003(11) 0.0022(11) O1 0.069(8) 0.035(6) 0.012(5) 0.010(4) 0.006(5) 0.002(6) O2 0.085(10) 0.037(7) 0.017(5) 0.005(5) -0.007(6) -0.004(6) O3 0.037(6) 0.051(7) 0.029(6) 0.013(5) 0.012(5) 0.012(5) O4 0.059(9) 0.126(14) 0.046(8) 0.043(8) -0.018(7) -0.064(9) O5 0.046(7) 0.054(8) 0.047(7) 0.009(6) -0.005(6) 0.012(6) O6 0.063(10) 0.094(12) 0.059(9) 0.026(8) 0.024(8) 0.010(9) O7 0.104(12) 0.039(8) 0.043(7) 0.007(6) -0.004(8) -0.007(8) N1 0.061(11) 0.039(10) 0.060(10) 0.000(8) 0.010(9) 0.000(8) N2 0.026(7) 0.073(11) 0.030(7) 0.025(7) -0.002(6) 0.012(7) N3 0.032(7) 0.046(8) 0.027(6) 0.018(6) 0.006(6) -0.004(6) N4 0.032(7) 0.049(9) 0.025(6) 0.007(6) -0.001(6) -0.005(6) N5 0.027(7) 0.047(8) 0.025(6) 0.008(6) 0.005(5) 0.004(6) N6 0.068(11) 0.030(9) 0.057(10) 0.011(7) -0.006(8) 0.000(8) N7 0.045(8) 0.024(7) 0.022(6) 0.008(5) 0.007(6) 0.002(6) N8 0.051(8) 0.020(6) 0.018(6) 0.003(5) -0.005(6) -0.003(6) C1 0.031(8) 0.038(10) 0.029(8) 0.011(7) 0.003(7) 0.001(7) C2 0.027(8) 0.033(8) 0.024(7) 0.009(6) 0.006(6) 0.006(6) C3 0.020(7) 0.033(8) 0.015(6) 0.007(6) 0.003(5) -0.003(6) C4 0.019(7) 0.014(7) 0.035(8) 0.003(6) 0.007(6) -0.004(5) C5 0.021(7) 0.031(8) 0.024(7) 0.009(6) -0.003(6) 0.003(6) C6 0.045(10) 0.029(9) 0.026(8) 0.001(6) 0.004(7) 0.004(7) C7 0.048(10) 0.018(8) 0.036(8) 0.009(6) -0.003(7) -0.009(7) C8 0.023(7) 0.021(7) 0.037(8) 0.005(6) 0.019(6) -0.003(6) C9 0.038(9) 0.038(9) 0.026(8) 0.005(7) -0.011(7) -0.007(7) C10 0.051(10) 0.027(8) 0.032(8) 0.001(7) -0.006(8) -0.004(7) C11 0.039(9) 0.028(8) 0.031(8) 0.008(6) 0.009(7) -0.001(7) C12 0.039(9) 0.038(9) 0.019(7) 0.009(6) 0.003(6) 0.000(7) C13 0.088(16) 0.045(11) 0.031(9) 0.007(8) -0.003(10) -0.012(11) C14 0.117(19) 0.036(10) 0.027(9) 0.018(8) 0.000(10) -0.012(11) C15 0.030(8) 0.025(8) 0.020(7) -0.003(6) -0.011(6) 0.000(6) C16 0.035(8) 0.018(7) 0.034(8) 0.002(6) 0.019(7) 0.001(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 Tb1 O1 2.348(10) . ? Tb1 O2 2.368(10) 1_556 ? Tb1 O3 2.370(11) . ? Tb1 O4 2.388(12) . ? Tb1 N2 2.437(13) . ? Tb1 N4 2.451(13) 1_455 ? Tb1 N5 2.475(13) . ? Tb1 N3 2.489(12) 1_455 ? Fe1 C1 1.917(17) 2_767 ? Fe1 C1 1.917(17) . ? Fe1 C3 1.931(13) . ? Fe1 C3 1.931(13) 2_767 ? Fe1 C2 1.938(15) 2_767 ? Fe1 C2 1.938(15) . ? Fe2 C4 1.922(14) . ? Fe2 C4 1.922(14) 2_766 ? Fe2 C6 1.941(17) 2_766 ? Fe2 C6 1.941(17) . ? Fe2 C5 1.950(15) 2_766 ? Fe2 C5 1.950(15) . ? O1 N7 1.333(14) . ? O2 N8 1.346(15) . ? O2 Tb1 2.368(10) 1_554 ? N1 C1 1.16(2) . ? N2 C2 1.152(19) . ? N3 C3 1.145(17) . ? N3 Tb1 2.489(12) 1_655 ? N4 C4 1.161(18) . ? N4 Tb1 2.451(13) 1_655 ? N5 C5 1.136(18) . ? N6 C6 1.14(2) . ? N7 C7 1.348(18) . ? N7 C9 1.364(19) . ? N8 C15 1.318(18) . ? N8 C14 1.35(2) . ? C7 C8 1.33(2) . ? C8 C11 1.42(2) . ? C9 C10 1.34(2) . ? C10 C11 1.38(2) . ? C11 C12 1.50(2) . ? C12 C16 1.36(2) . ? C12 C13 1.39(2) . ? C13 C14 1.36(2) . ? C15 C16 1.36(2) . ? 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 Tb1 O2 112.8(4) . 1_556 ? O1 Tb1 O3 71.9(4) . . ? O2 Tb1 O3 70.5(4) 1_556 . ? O1 Tb1 O4 71.5(4) . . ? O2 Tb1 O4 71.7(5) 1_556 . ? O3 Tb1 O4 109.7(6) . . ? O1 Tb1 N2 139.0(4) . . ? O2 Tb1 N2 80.6(5) 1_556 . ? O3 Tb1 N2 145.5(4) . . ? O4 Tb1 N2 77.4(5) . . ? O1 Tb1 N4 82.3(4) . 1_455 ? O2 Tb1 N4 140.1(5) 1_556 1_455 ? O3 Tb1 N4 80.7(4) . 1_455 ? O4 Tb1 N4 146.3(4) . 1_455 ? N2 Tb1 N4 112.7(5) . 1_455 ? O1 Tb1 N5 76.4(4) . . ? O2 Tb1 N5 143.1(4) 1_556 . ? O3 Tb1 N5 142.1(4) . . ? O4 Tb1 N5 78.6(5) . . ? N2 Tb1 N5 71.8(4) . . ? N4 Tb1 N5 74.8(4) 1_455 . ? O1 Tb1 N3 143.8(4) . 1_455 ? O2 Tb1 N3 77.6(4) 1_556 1_455 ? O3 Tb1 N3 80.2(4) . 1_455 ? O4 Tb1 N3 141.7(4) . 1_455 ? N2 Tb1 N3 75.4(4) . 1_455 ? N4 Tb1 N3 70.5(4) 1_455 1_455 ? N5 Tb1 N3 116.9(5) . 1_455 ? C1 Fe1 C1 180.000(4) 2_767 . ? C1 Fe1 C3 87.1(6) 2_767 . ? C1 Fe1 C3 92.9(6) . . ? C1 Fe1 C3 92.9(6) 2_767 2_767 ? C1 Fe1 C3 87.1(6) . 2_767 ? C3 Fe1 C3 180.000(3) . 2_767 ? C1 Fe1 C2 89.0(6) 2_767 2_767 ? C1 Fe1 C2 91.0(6) . 2_767 ? C3 Fe1 C2 91.3(6) . 2_767 ? C3 Fe1 C2 88.7(6) 2_767 2_767 ? C1 Fe1 C2 91.0(6) 2_767 . ? C1 Fe1 C2 89.0(6) . . ? C3 Fe1 C2 88.7(6) . . ? C3 Fe1 C2 91.3(6) 2_767 . ? C2 Fe1 C2 180.000(5) 2_767 . ? C4 Fe2 C4 180.000(2) . 2_766 ? C4 Fe2 C6 91.7(6) . 2_766 ? C4 Fe2 C6 88.3(6) 2_766 2_766 ? C4 Fe2 C6 88.3(6) . . ? C4 Fe2 C6 91.7(6) 2_766 . ? C6 Fe2 C6 180.00(18) 2_766 . ? C4 Fe2 C5 90.4(6) . 2_766 ? C4 Fe2 C5 89.6(6) 2_766 2_766 ? C6 Fe2 C5 88.0(6) 2_766 2_766 ? C6 Fe2 C5 92.0(6) . 2_766 ? C4 Fe2 C5 89.6(6) . . ? C4 Fe2 C5 90.4(6) 2_766 . ? C6 Fe2 C5 92.0(6) 2_766 . ? C6 Fe2 C5 88.0(6) . . ? C5 Fe2 C5 180.000(3) 2_766 . ? N7 O1 Tb1 142.3(9) . . ? N8 O2 Tb1 143.1(9) . 1_554 ? C2 N2 Tb1 164.8(14) . . ? C3 N3 Tb1 169.2(13) . 1_655 ? C4 N4 Tb1 165.3(12) . 1_655 ? C5 N5 Tb1 166.2(12) . . ? O1 N7 C7 122.1(12) . . ? O1 N7 C9 118.8(12) . . ? C7 N7 C9 119.0(12) . . ? C15 N8 O2 122.9(12) . . ? C15 N8 C14 120.3(12) . . ? O2 N8 C14 116.7(12) . . ? N1 C1 Fe1 177.0(15) . . ? N2 C2 Fe1 176.2(13) . . ? N3 C3 Fe1 177.2(13) . . ? N4 C4 Fe2 176.3(13) . . ? N5 C5 Fe2 177.6(14) . . ? N6 C6 Fe2 177.9(16) . . ? C8 C7 N7 121.6(14) . . ? C7 C8 C11 120.8(14) . . ? C10 C9 N7 121.1(14) . . ? C9 C10 C11 121.1(16) . . ? C10 C11 C8 116.1(14) . . ? C10 C11 C12 123.6(14) . . ? C8 C11 C12 120.2(14) . . ? C16 C12 C13 116.3(14) . . ? C16 C12 C11 122.5(14) . . ? C13 C12 C11 121.1(15) . . ? C14 C13 C12 121.0(17) . . ? N8 C14 C13 119.7(16) . . ? N8 C15 C16 120.9(13) . . ? C15 C16 C12 121.6(14) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.45 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 13.019 _refine_diff_density_min -1.650 _refine_diff_density_rms 0.430