# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/1756 # 1-D Mixed Stack of Coordinated and Uncoordinated radicals in # Mn(II)(NITpPy)4[N(CN)2]2 (NITpPy = nitronyl nitroxide radical) data_calcul _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H64 Mn N18 O8' _chemical_formula_weight 1124.15 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' 'Mn' 'Mn' 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, z+1/2' '-x, -y, -z' '-x-1/2, y-1/2, -z-1/2' _cell_length_a 17.768(7) _cell_length_b 7.368(4) _cell_length_c 21.404(8) _cell_angle_alpha 90.00 _cell_angle_beta 92.780(18) _cell_angle_gamma 90.00 _cell_volume 2799(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 1.904 _cell_measurement_theta_max 12.000 _exptl_crystal_description needle _exptl_crystal_colour blue _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.334 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1182 _exptl_absorpt_coefficient_mu 0.305 _exptl_absorpt_correction_type '\y scan' _exptl_absorpt_correction_T_min 0.962087 _exptl_absorpt_correction_T_max 0.997850 _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 'Enraf Nonius CAD4' _diffrn_measurement_method \q-2\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 250 _diffrn_standards_interval_time 60 _diffrn_standards_decay_% ? _diffrn_reflns_number 6983 _diffrn_reflns_av_R_equivalents 0.0795 _diffrn_reflns_av_sigmaI/netI 0.2514 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.46 _diffrn_reflns_theta_max 27.96 _reflns_number_total 6735 _reflns_number_gt 2227 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf Nonius CAD4' _computing_cell_refinement 'Enraf Nonius CAD4' _computing_data_reduction MolEN _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP III' _computing_publication_material ? _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 w=1/[\s^2^(Fo^2^)+(0.0468P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6735 _refine_ls_number_parameters 358 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.2800 _refine_ls_R_factor_gt 0.0662 _refine_ls_wR_factor_ref 0.1517 _refine_ls_wR_factor_gt 0.1082 _refine_ls_goodness_of_fit_ref 0.927 _refine_ls_restrained_S_all 0.927 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Mn1 Mn 0.0000 0.5000 0.0000 0.0365(3) Uani 1 d S . . N1 N -0.03486(19) 0.5351(5) 0.10027(14) 0.0410(10) Uani 1 d . . . N2 N -0.17125(19) 0.5228(6) 0.30664(14) 0.0452(10) Uani 1 d . . . N3 N -0.0603(2) 0.6179(5) 0.33771(16) 0.0452(10) Uani 1 d . . . N4 N -0.0898(2) 1.0842(6) 0.1706(2) 0.0666(13) Uani 1 d . . . N5 N 0.11108(19) 1.0106(6) 0.35277(16) 0.0524(10) Uani 1 d . . . N6 N 0.15733(19) 0.8513(5) 0.27800(16) 0.0430(10) Uani 1 d . . . N7 N 0.14945(19) 0.0030(7) 0.03473(18) 0.0600(11) Uani 1 d . . . N8 N 0.0858(2) 0.2938(6) 0.02934(18) 0.0490(11) Uani 1 d . . . N9 N 0.0864(2) 0.7126(6) 0.01417(19) 0.0542(12) Uani 1 d . . . O1 O -0.22491(16) 0.4544(5) 0.27268(13) 0.0732(12) Uani 1 d . . . O2 O 0.0082(2) 0.6681(5) 0.33963(14) 0.0754(11) Uani 1 d . . . O3 O 0.0688(2) 1.1165(6) 0.38320(17) 0.0927(14) Uani 1 d . . . O4 O 0.16644(18) 0.7789(5) 0.22526(15) 0.0687(11) Uani 1 d . . . C1 C -0.1065(2) 0.5621(6) 0.11390(19) 0.0483(13) Uani 1 d . . . H1 H -0.1423 0.5718 0.0809 0.058 Uiso 1 calc R . . C2 C -0.1306(2) 0.5763(6) 0.17355(18) 0.0474(13) Uani 1 d . . . H2 H -0.1812 0.5960 0.1803 0.057 Uiso 1 calc R . . C3 C -0.0786(2) 0.5611(5) 0.22376(17) 0.0346(11) Uani 1 d . . . C4 C -0.0036(2) 0.5358(6) 0.21037(17) 0.0428(13) Uani 1 d . . . H4 H 0.0335 0.5266 0.2424 0.051 Uiso 1 calc R . . C5 C 0.0145(2) 0.5247(6) 0.14879(18) 0.0419(11) Uani 1 d . . . H5 H 0.0650 0.5088 0.1405 0.050 Uiso 1 calc R . . C6 C -0.1022(2) 0.5698(6) 0.28791(18) 0.0392(11) Uani 1 d . . . C7 C -0.1798(2) 0.5742(7) 0.37411(19) 0.0492(13) Uani 1 d . . . C8 C -0.0981(2) 0.5869(7) 0.39775(19) 0.0481(13) Uani 1 d . . . C9 C -0.2210(3) 0.7583(8) 0.3722(2) 0.085(2) Uani 1 d . . . H9A H -0.1931 0.8436 0.3485 0.128 Uiso 1 calc R . . H9B H -0.2252 0.8028 0.4140 0.128 Uiso 1 calc R . . H9C H -0.2705 0.7431 0.3527 0.128 Uiso 1 calc R . . C10 C -0.2286(3) 0.4349(8) 0.4050(2) 0.081(2) Uani 1 d . . . H10A H -0.2802 0.4519 0.3910 0.122 Uiso 1 calc R . . H10B H -0.2239 0.4495 0.4496 0.122 Uiso 1 calc R . . H10C H -0.2126 0.3151 0.3940 0.122 Uiso 1 calc R . . C11 C -0.0779(3) 0.7354(8) 0.4439(2) 0.084(2) Uani 1 d . . . H11A H -0.0242 0.7518 0.4464 0.125 Uiso 1 calc R . . H11B H -0.0947 0.7025 0.4843 0.125 Uiso 1 calc R . . H11C H -0.1018 0.8464 0.4304 0.125 Uiso 1 calc R . . C12 C -0.0668(3) 0.4040(8) 0.4231(2) 0.085(2) Uani 1 d . . . H12A H -0.0727 0.3131 0.3911 0.127 Uiso 1 calc R . . H12B H -0.0940 0.3681 0.4588 0.127 Uiso 1 calc R . . H12C H -0.0144 0.4173 0.4351 0.127 Uiso 1 calc R . . C13 C -0.0920(3) 1.0902(7) 0.2322(3) 0.0672(16) Uani 1 d . . . H13 H -0.1378 1.1204 0.2487 0.081 Uiso 1 calc R . . C14 C -0.0322(2) 1.0556(6) 0.2741(2) 0.0495(13) Uani 1 d . . . H14 H -0.0377 1.0638 0.3170 0.059 Uiso 1 calc R . . C15 C 0.0368(2) 1.0079(7) 0.25019(19) 0.0411(10) Uani 1 d . . . C16 C 0.0409(2) 1.0041(7) 0.18611(19) 0.0521(12) Uani 1 d . . . H16 H 0.0860 0.9756 0.1680 0.062 Uiso 1 calc R . . C17 C -0.0227(3) 1.0431(7) 0.1491(2) 0.0631(16) Uani 1 d . . . H17 H -0.0185 1.0406 0.1060 0.076 Uiso 1 calc R . . C18 C 0.1008(2) 0.9611(6) 0.29281(19) 0.0382(12) Uani 1 d . . . C19 C 0.1834(2) 0.9429(6) 0.38300(19) 0.0432(12) Uani 1 d . . . C20 C 0.2083(2) 0.8033(6) 0.33405(18) 0.0394(11) Uani 1 d . . . C21 C 0.2343(3) 1.1070(7) 0.3920(2) 0.0730(16) Uani 1 d . . . H21A H 0.2486 1.1502 0.3519 0.110 Uiso 1 calc R . . H21B H 0.2786 1.0736 0.4168 0.110 Uiso 1 calc R . . H21C H 0.2079 1.2012 0.4129 0.110 Uiso 1 calc R . . C22 C 0.1669(3) 0.8621(7) 0.4462(2) 0.0745(17) Uani 1 d . . . H22A H 0.1533 0.9573 0.4742 0.112 Uiso 1 calc R . . H22B H 0.2109 0.8007 0.4632 0.112 Uiso 1 calc R . . H22C H 0.1260 0.7773 0.4412 0.112 Uiso 1 calc R . . C23 C 0.1917(3) 0.6058(6) 0.3490(2) 0.0597(14) Uani 1 d . . . H23A H 0.1402 0.5942 0.3599 0.090 Uiso 1 calc R . . H23B H 0.2243 0.5666 0.3835 0.090 Uiso 1 calc R . . H23C H 0.2002 0.5321 0.3130 0.090 Uiso 1 calc R . . C24 C 0.2895(2) 0.8201(7) 0.3157(2) 0.0589(15) Uani 1 d . . . H24A H 0.2980 0.7394 0.2815 0.088 Uiso 1 calc R . . H24B H 0.3227 0.7888 0.3508 0.088 Uiso 1 calc R . . H24C H 0.2992 0.9427 0.3032 0.088 Uiso 1 calc R . . C25 C 0.1126(3) 0.1545(8) 0.0305(2) 0.0373(12) Uani 1 d . . . C26 C 0.1136(3) -0.1505(8) 0.0237(2) 0.0424(13) Uani 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 Mn1 0.0493(6) 0.0265(5) 0.0342(5) -0.0004(6) 0.0057(4) -0.0011(6) N1 0.042(2) 0.047(3) 0.0337(19) 0.0008(19) 0.0014(16) -0.001(2) N2 0.036(2) 0.065(3) 0.0344(18) 0.001(2) 0.0037(16) -0.001(2) N3 0.028(2) 0.064(3) 0.044(2) 0.000(2) 0.0029(18) -0.001(2) N4 0.049(3) 0.070(3) 0.079(3) 0.011(3) -0.011(2) -0.003(3) N5 0.052(2) 0.059(3) 0.047(2) -0.012(3) 0.0059(19) 0.012(3) N6 0.041(2) 0.050(3) 0.038(2) -0.001(2) 0.0009(18) 0.006(2) N7 0.041(2) 0.031(2) 0.107(3) -0.006(3) -0.007(2) 0.000(3) N8 0.061(3) 0.036(3) 0.049(2) -0.004(2) 0.003(2) 0.005(2) N9 0.059(3) 0.034(3) 0.069(3) -0.005(2) -0.006(2) -0.006(2) O1 0.0438(19) 0.124(4) 0.0513(19) -0.012(2) 0.0010(15) -0.022(2) O2 0.067(2) 0.102(3) 0.058(2) -0.004(2) 0.0036(19) -0.021(2) O3 0.080(3) 0.122(4) 0.075(3) -0.041(3) -0.007(2) 0.046(3) O4 0.068(2) 0.090(3) 0.047(2) -0.018(2) -0.0037(17) 0.029(2) C1 0.042(3) 0.067(4) 0.035(2) 0.001(2) -0.006(2) -0.003(3) C2 0.038(3) 0.066(4) 0.039(3) 0.005(2) 0.008(2) 0.004(2) C3 0.040(3) 0.033(3) 0.031(2) 0.0005(19) 0.001(2) -0.003(2) C4 0.037(2) 0.058(4) 0.034(2) -0.002(2) -0.0013(19) 0.000(2) C5 0.036(2) 0.049(3) 0.041(2) -0.001(3) 0.007(2) 0.003(3) C6 0.035(3) 0.048(3) 0.035(2) 0.000(2) -0.001(2) -0.002(2) C7 0.045(3) 0.074(4) 0.029(2) 0.001(3) 0.007(2) 0.006(3) C8 0.046(3) 0.071(4) 0.028(2) 0.001(3) 0.005(2) 0.005(3) C9 0.073(4) 0.105(5) 0.077(4) -0.020(4) -0.010(3) 0.042(4) C10 0.070(4) 0.119(6) 0.057(3) 0.017(3) 0.019(3) -0.014(4) C11 0.063(4) 0.132(6) 0.055(3) -0.040(4) -0.007(3) 0.004(4) C12 0.082(4) 0.110(5) 0.064(4) 0.040(4) 0.020(3) 0.037(4) C13 0.037(3) 0.071(4) 0.093(4) 0.004(4) 0.001(3) 0.007(3) C14 0.047(3) 0.049(4) 0.053(3) 0.000(2) 0.003(2) 0.007(2) C15 0.038(2) 0.033(2) 0.052(3) 0.003(3) 0.000(2) -0.002(3) C16 0.039(3) 0.062(3) 0.055(3) 0.015(3) -0.003(2) 0.001(3) C17 0.058(3) 0.071(5) 0.060(3) 0.015(3) -0.007(3) -0.004(3) C18 0.040(3) 0.034(3) 0.040(2) 0.002(2) 0.005(2) 0.003(2) C19 0.044(3) 0.046(3) 0.040(3) 0.002(2) -0.003(2) -0.002(2) C20 0.039(3) 0.045(3) 0.034(2) -0.002(2) -0.003(2) 0.001(2) C21 0.078(4) 0.063(4) 0.078(4) -0.014(3) -0.003(3) -0.015(3) C22 0.105(4) 0.079(4) 0.041(3) 0.006(3) 0.016(3) 0.014(4) C23 0.074(4) 0.037(3) 0.067(3) 0.004(3) -0.007(3) 0.008(3) C24 0.040(3) 0.080(4) 0.057(3) 0.006(3) 0.001(2) 0.007(3) C25 0.038(3) 0.035(3) 0.039(3) -0.001(3) 0.003(2) -0.010(3) C26 0.039(3) 0.042(4) 0.046(3) 0.001(3) -0.002(3) 0.012(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 Mn1 N9 2.204(4) . ? Mn1 N9 2.204(4) 3_565 ? Mn1 N8 2.221(4) . ? Mn1 N8 2.221(4) 3_565 ? Mn1 N1 2.277(3) 3_565 ? Mn1 N1 2.277(3) . ? N1 C5 1.329(5) . ? N1 C1 1.335(5) . ? N2 O1 1.274(4) . ? N2 C6 1.355(5) . ? N2 C7 1.508(5) . ? N3 O2 1.271(4) . ? N3 C6 1.318(5) . ? N3 C8 1.496(5) . ? N4 C13 1.321(6) . ? N4 C17 1.334(6) . ? N5 O3 1.282(4) . ? N5 C18 1.338(5) . ? N5 C19 1.496(5) . ? N6 O4 1.266(4) . ? N6 C18 1.339(5) . ? N6 C20 1.510(5) . ? N7 C25 1.295(6) . ? N7 C26 1.313(6) . ? N8 C25 1.131(6) . ? N9 C26 1.133(6) 1_565 ? C1 C2 1.370(5) . ? C2 C3 1.387(5) . ? C3 C4 1.389(5) . ? C3 C6 1.456(5) . ? C4 C5 1.374(5) . ? C7 C8 1.516(6) . ? C7 C10 1.516(6) . ? C7 C9 1.542(7) . ? C8 C11 1.505(6) . ? C8 C12 1.546(6) . ? C13 C14 1.381(6) . ? C14 C15 1.396(5) . ? C15 C16 1.377(5) . ? C15 C18 1.464(5) . ? C16 C17 1.378(5) . ? C19 C22 1.520(6) . ? C19 C21 1.517(6) . ? C19 C20 1.548(6) . ? C20 C23 1.522(6) . ? C20 C24 1.519(5) . ? C26 N9 1.133(6) 1_545 ? 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 N9 Mn1 N9 180.0 . 3_565 ? N9 Mn1 N8 89.02(13) . . ? N9 Mn1 N8 90.98(13) 3_565 . ? N9 Mn1 N8 90.98(13) . 3_565 ? N9 Mn1 N8 89.02(13) 3_565 3_565 ? N8 Mn1 N8 180.0 . 3_565 ? N9 Mn1 N1 89.47(14) . 3_565 ? N9 Mn1 N1 90.53(14) 3_565 3_565 ? N8 Mn1 N1 88.54(13) . 3_565 ? N8 Mn1 N1 91.46(13) 3_565 3_565 ? N9 Mn1 N1 90.53(14) . . ? N9 Mn1 N1 89.47(14) 3_565 . ? N8 Mn1 N1 91.46(13) . . ? N8 Mn1 N1 88.54(13) 3_565 . ? N1 Mn1 N1 180.0 3_565 . ? C5 N1 C1 116.0(3) . . ? C5 N1 Mn1 122.0(3) . . ? C1 N1 Mn1 121.9(3) . . ? O1 N2 C6 126.6(3) . . ? O1 N2 C7 122.6(3) . . ? C6 N2 C7 110.7(3) . . ? O2 N3 C6 127.3(4) . . ? O2 N3 C8 119.1(3) . . ? C6 N3 C8 113.2(4) . . ? C13 N4 C17 115.0(4) . . ? O3 N5 C18 126.7(4) . . ? O3 N5 C19 119.7(3) . . ? C18 N5 C19 113.5(4) . . ? O4 N6 C18 126.5(3) . . ? O4 N6 C20 120.8(4) . . ? C18 N6 C20 112.4(3) . . ? C25 N7 C26 119.4(3) . . ? C25 N8 Mn1 155.4(4) . . ? C26 N9 Mn1 161.0(4) 1_565 . ? N1 C1 C2 124.0(4) . . ? C1 C2 C3 119.3(4) . . ? C2 C3 C4 117.4(4) . . ? C2 C3 C6 121.1(4) . . ? C4 C3 C6 121.5(4) . . ? C5 C4 C3 118.5(4) . . ? N1 C5 C4 124.7(4) . . ? N3 C6 N2 108.2(4) . . ? N3 C6 C3 126.7(4) . . ? N2 C6 C3 125.0(4) . . ? N2 C7 C8 101.3(3) . . ? N2 C7 C10 109.5(4) . . ? C8 C7 C10 117.1(4) . . ? N2 C7 C9 105.3(4) . . ? C8 C7 C9 113.6(4) . . ? C10 C7 C9 109.0(4) . . ? N3 C8 C11 110.5(4) . . ? N3 C8 C7 100.7(3) . . ? C11 C8 C7 117.3(4) . . ? N3 C8 C12 105.4(4) . . ? C11 C8 C12 109.5(4) . . ? C7 C8 C12 112.6(4) . . ? N4 C13 C14 125.7(5) . . ? C13 C14 C15 118.0(4) . . ? C16 C15 C14 117.4(4) . . ? C16 C15 C18 122.6(4) . . ? C14 C15 C18 120.0(4) . . ? C15 C16 C17 119.1(4) . . ? N4 C17 C16 124.8(5) . . ? N5 C18 N6 108.8(4) . . ? N5 C18 C15 126.8(4) . . ? N6 C18 C15 124.3(4) . . ? N5 C19 C22 108.5(4) . . ? N5 C19 C21 106.5(4) . . ? C22 C19 C21 109.8(4) . . ? N5 C19 C20 101.3(3) . . ? C22 C19 C20 114.6(4) . . ? C21 C19 C20 115.3(4) . . ? N6 C20 C23 106.0(4) . . ? N6 C20 C24 108.4(3) . . ? C23 C20 C24 109.2(4) . . ? N6 C20 C19 101.7(3) . . ? C23 C20 C19 115.4(4) . . ? C24 C20 C19 115.3(4) . . ? N8 C25 N7 173.9(5) . . ? N9 C26 N7 176.3(5) 1_545 . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.96 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.291 _refine_diff_density_min -0.465 _refine_diff_density_rms 0.061