# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/2177 data_M(apo)(N(CN)2)2 #(M=Co Ni Mn)_Number_B005612J _audit_creation_method SHELXL-97 # SUBMISSION DETAILS _publ_contact_author_name 'Prof. Song Gao' _publ_contact_author_address ; State Key Laboratory of Rare Earth Materials Chemistry and Applications & PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry Peking University - Nonius. B. V. Demo Lab For X-Ray Diffaraction Department of Chemistry Peking University Beijing 100871 People's Republic of China ; _publ_contact_author_email Gaosong@chemms.chem.pku.edu.cn _publ_contact_author_phone '86-(10)-62756320' _publ_contact_author_fax '86-(10)-62754179' _publ_requested_journal 'J. Chem. Soc. dalton Trans' _publ_requested_category FM# ################### data_Co(apo)(N(CN)2)2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H6 Co N8 O' _chemical_formula_weight 301.15 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' 'Co' 'Co' 0.3494 0.9721 '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(1)/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 9.8222(3) _cell_length_b 11.8553(4) _cell_length_c 10.4718(4) _cell_angle_alpha 90.00 _cell_angle_beta 94.866(2) _cell_angle_gamma 90.00 _cell_volume 1214.99(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 22597 _cell_measurement_theta_min 2.60 _cell_measurement_theta_max 27.85 _exptl_crystal_description 'polyhedral' _exptl_crystal_colour 'mauve' _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.646 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 604 _exptl_absorpt_coefficient_mu 1.418 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.712 _exptl_absorpt_correction_T_max 0.759 _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 22597 _diffrn_reflns_av_R_equivalents 0.0408 _diffrn_reflns_av_sigmaI/netI 0.0255 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.60 _diffrn_reflns_theta_max 27.85 _reflns_number_total 2879 _reflns_number_gt 2441 _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, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL V5.1 (Sheldrick, 1998)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _publ_section_references ; collect: "Collect" data collection software, Nonius B.V., Delft, The Netherlands, 1998. HKL Scalepack & HKL Denzo: Z. Otwinowski and W. Minor, " Processing of X-ray Diffraction Data Collected in Oscillation Mode ", Methods in Enzymology, Volume 276: Macromolecular Crystallography, part A, p.307-326, 1997,C.W. Carter, Jr. & R.M. Sweet, Eds., Academic Press. absorption correction: R.H. Blessing (1995) Acta Cryst. A51, 33-37. R.H. Blessing (1997) J.Appl. Cryst. 30, 421-426. maXus: S.Mackay, C.J.Gilmore, C.Edwards, M. Tremayne, N. Stuart, K.Shankland "maXus: a computer program for the solution and refinement of crystal structures from diffraction data", University of Glasgow, Scotland, UK, Nonius BV, Delft, The Netherlands and MacScience Co. Ltd., Yokohama, Japan (1998). Sheldrick, G. M. (1998). SHELXTL Version 5.1. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1997). SHELX-97. PC Version. University of Goettingen, Germany. ; _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^)+(0.0949P)^2^+0.0715P] 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 SHELXL _refine_ls_extinction_coef 0.113(8) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2879 _refine_ls_number_parameters 173 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0687 _refine_ls_R_factor_gt 0.0500 _refine_ls_wR_factor_ref 0.1516 _refine_ls_wR_factor_gt 0.1281 _refine_ls_goodness_of_fit_ref 1.243 _refine_ls_restrained_S_all 1.243 _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 Co1 Co 0.01385(3) 0.02880(3) 0.34023(3) 0.0326(2) Uani 1 1 d . . . O1 O -0.0552(2) 0.09348(14) 0.51473(18) 0.0383(4) Uani 1 1 d . . . N1 N -0.0858(2) 0.20160(18) 0.5378(2) 0.0360(5) Uani 1 1 d . . . N2 N -0.3082(3) 0.1601(3) 0.4937(4) 0.0731(10) Uani 1 1 d . . . H1 H -0.3973 0.1791 0.4862 0.080 Uiso 1 1 d R . . H2 H -0.2829 0.0889 0.4775 0.080 Uiso 1 1 d R . . N3 N -0.0375(3) 0.1773(2) 0.2432(3) 0.0480(6) Uani 1 1 d . . . N4 N -0.0892(3) 0.3780(2) 0.2175(3) 0.0588(8) Uani 1 1 d . . . N5 N -0.3146(3) 0.4635(2) 0.2053(3) 0.0492(7) Uani 1 1 d . . . N6 N 0.0855(3) -0.0791(2) 0.2022(2) 0.0459(6) Uani 1 1 d . . . N7 N 0.1057(3) -0.2582(3) 0.0877(3) 0.0612(8) Uani 1 1 d . . . N8 N 0.2899(2) -0.3972(2) 0.1145(2) 0.0448(6) Uani 1 1 d . . . C1 C -0.2166(3) 0.2352(3) 0.5277(3) 0.0504(8) Uani 1 1 d . . . C2 C -0.2426(4) 0.3519(3) 0.5565(4) 0.0630(10) Uani 1 1 d . . . H3 H -0.3341 0.3810 0.5488 0.080 Uiso 1 1 d R . . C3 C -0.1364(5) 0.4182(3) 0.5949(4) 0.0688(11) Uani 1 1 d . . . H4 H -0.1539 0.4953 0.6165 0.080 Uiso 1 1 d R . . C4 C -0.0042(5) 0.3816(3) 0.6039(4) 0.0681(10) Uani 1 1 d . . . H5 H 0.0695 0.4320 0.6298 0.080 Uiso 1 1 d R . . C5 C 0.0202(4) 0.2739(3) 0.5759(3) 0.0521(8) Uani 1 1 d . . . H6 H 0.1123 0.2459 0.5819 0.080 Uiso 1 1 d R . . C6 C -0.0684(3) 0.2702(2) 0.2314(3) 0.0415(6) Uani 1 1 d . . . C7 C -0.2121(3) 0.4187(2) 0.2115(3) 0.0394(6) Uani 1 1 d . . . C8 C 0.1035(3) -0.1633(3) 0.1521(3) 0.0430(7) Uani 1 1 d . . . C9 C 0.2080(3) -0.3283(2) 0.1069(3) 0.0403(6) 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 Co1 0.0343(3) 0.0213(3) 0.0423(3) -0.00068(12) 0.00373(17) 0.00040(12) O1 0.0494(11) 0.0212(9) 0.0453(10) -0.0005(7) 0.0093(8) 0.0056(8) N1 0.0448(13) 0.0223(10) 0.0416(11) 0.0007(9) 0.0084(10) 0.0058(9) N2 0.0508(17) 0.060(2) 0.108(3) -0.0117(19) 0.0015(17) 0.0061(15) N3 0.0549(15) 0.0346(13) 0.0548(15) 0.0100(11) 0.0057(12) 0.0076(12) N4 0.0454(14) 0.0325(13) 0.098(2) 0.0052(14) 0.0025(14) 0.0049(12) N5 0.0474(15) 0.0385(14) 0.0600(16) 0.0053(11) -0.0051(13) 0.0057(12) N6 0.0531(14) 0.0348(13) 0.0505(14) -0.0043(11) 0.0086(11) 0.0060(11) N7 0.0639(17) 0.0516(16) 0.0648(17) -0.0207(14) -0.0137(14) 0.0218(14) N8 0.0430(13) 0.0399(13) 0.0518(13) -0.0045(11) 0.0065(11) 0.0092(11) C1 0.0483(16) 0.0519(18) 0.0518(17) 0.0062(14) 0.0087(14) 0.0126(15) C2 0.079(2) 0.0486(19) 0.065(2) 0.0086(16) 0.0261(19) 0.0248(19) C3 0.098(3) 0.0388(18) 0.073(2) -0.0003(17) 0.029(2) 0.011(2) C4 0.099(3) 0.0346(17) 0.072(2) -0.0097(17) 0.013(2) -0.013(2) C5 0.070(2) 0.0347(15) 0.0519(17) -0.0016(13) 0.0083(15) -0.0064(15) C6 0.0420(15) 0.0381(15) 0.0438(14) 0.0029(12) 0.0012(12) 0.0040(12) C7 0.0433(15) 0.0277(13) 0.0460(14) 0.0009(11) -0.0035(11) 0.0005(12) C8 0.0453(16) 0.0436(17) 0.0400(14) -0.0005(12) 0.0038(12) 0.0103(13) C9 0.0457(16) 0.0361(14) 0.0390(14) -0.0046(11) 0.0033(12) 0.0062(12) _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 Co1 N3 2.074(2) . y Co1 N6 2.097(2) . y Co1 O1 2.1140(18) 3_556 y Co1 N5 2.121(3) 2_445 y Co1 N8 2.134(2) 2 y Co1 O1 2.1443(18) . ? O1 N1 1.343(3) . ? O1 Co1 2.1140(18) 3_556 ? N1 C1 1.341(4) . y N1 C5 1.381(4) . y N2 C1 1.294(5) . y N3 C6 1.146(4) . y N4 C7 1.296(4) . y N4 C6 1.301(4) . ? N5 C7 1.135(4) . ? N5 Co1 2.121(3) 2_455 ? N6 C8 1.147(4) . ? N7 C9 1.307(4) . ? N7 C8 1.312(4) . ? N8 C9 1.144(4) . ? N8 Co1 2.134(2) 2_545 ? C1 C2 1.444(5) . ? C2 C3 1.340(6) . ? C3 C4 1.365(6) . ? C4 C5 1.337(5) . ? 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 N3 Co1 N6 105.21(11) . . y N3 Co1 O1 163.39(9) . 3_556 y N6 Co1 O1 91.23(9) . 3_556 y N3 Co1 N5 91.04(11) . 2_445 y N6 Co1 N5 88.82(11) . 2_445 y O1 Co1 N5 91.65(9) 3_556 2_445 y N3 Co1 N8 86.40(11) . 2 y N6 Co1 N8 93.13(10) . 2 y O1 Co1 N8 90.43(9) 3_556 2 y N5 Co1 N8 177.12(10) 2_445 2 y N3 Co1 O1 91.87(9) . . y N6 Co1 O1 162.72(9) . . y O1 Co1 O1 71.84(7) 3_556 . y N5 Co1 O1 88.26(10) 2_445 . y N8 Co1 O1 90.50(9) 2 . y N1 O1 Co1 123.89(16) . 3_556 y N1 O1 Co1 125.89(15) . . y Co1 O1 Co1 108.16(7) 3_556 . y C1 N1 O1 119.8(3) . . y C1 N1 C5 122.2(3) . . ? O1 N1 C5 118.0(2) . . ? C6 N3 Co1 156.9(3) . . y C7 N4 C6 120.5(3) . . y C7 N5 Co1 168.7(3) . 2_455 y C8 N6 Co1 156.9(3) . . y C9 N7 C8 120.8(3) . . ? C9 N8 Co1 157.7(2) . 2_545 y N2 C1 N1 117.2(3) . . ? N2 C1 C2 125.8(3) . . ? N1 C1 C2 117.0(3) . . ? C3 C2 C1 118.6(4) . . ? C2 C3 C4 123.1(3) . . ? C5 C4 C3 118.5(4) . . ? C4 C5 N1 120.7(4) . . ? N3 C6 N4 173.7(3) . . ? N5 C7 N4 173.9(3) . . ? N6 C8 N7 171.7(3) . . ? N8 C9 N7 172.7(3) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.85 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.976 _refine_diff_density_min -1.222 _refine_diff_density_rms 0.343 #===END data_Ni(apo)(N(CN)2)2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H6 N8 Ni O' _chemical_formula_weight 300.93 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' 'Ni' 'Ni' 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M ' P 2(1)/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 9.7889(5) _cell_length_b 11.7071(6) _cell_length_c 10.5283(4) _cell_angle_alpha 90.00 _cell_angle_beta 94.610(3) _cell_angle_gamma 90.00 _cell_volume 1202.64(10) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21191 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 27.85 _exptl_crystal_description 'polyhedral' _exptl_crystal_colour 'green' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.662 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 608 _exptl_absorpt_coefficient_mu 1.619 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.689 _exptl_absorpt_correction_T_max 0.729 _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 21191 _diffrn_reflns_av_R_equivalents 0.0780 _diffrn_reflns_av_sigmaI/netI 0.0495 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.61 _diffrn_reflns_theta_max 27.85 _reflns_number_total 2847 _reflns_number_gt 2034 _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^)+(0.1103P)^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 SHELXL _refine_ls_extinction_coef 0.110(8) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2847 _refine_ls_number_parameters 173 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0995 _refine_ls_R_factor_gt 0.0594 _refine_ls_wR_factor_ref 0.1814 _refine_ls_wR_factor_gt 0.1377 _refine_ls_goodness_of_fit_ref 1.138 _refine_ls_restrained_S_all 1.138 _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 Ni1 Ni 0.01299(5) 0.02761(4) 0.34385(5) 0.0328(3) Uani 1 1 d . . . O1 O -0.0569(3) 0.0930(2) 0.5134(3) 0.0370(7) Uani 1 1 d . . . N1 N -0.0880(4) 0.2028(3) 0.5364(3) 0.0370(8) Uani 1 1 d . . . N2 N -0.3096(5) 0.1607(4) 0.4928(6) 0.0777(15) Uani 1 1 d . . . H1 H -0.3987 0.1796 0.4853 0.080 Uiso 1 1 d R . . H2 H -0.2842 0.0895 0.4766 0.080 Uiso 1 1 d R . . N3 N -0.0389(4) 0.1718(3) 0.2418(4) 0.0481(10) Uani 1 1 d . . . N4 N -0.0912(4) 0.3749(3) 0.2153(5) 0.0586(11) Uani 1 1 d . . . N5 N -0.3182(4) 0.4602(3) 0.1974(4) 0.0480(10) Uani 1 1 d . . . N6 N 0.0841(4) -0.0772(3) 0.2067(4) 0.0452(9) Uani 1 1 d . . . N7 N 0.1092(5) -0.2568(4) 0.0901(4) 0.0664(14) Uani 1 1 d . . . N8 N 0.2948(4) -0.3963(3) 0.1143(4) 0.0447(9) Uani 1 1 d . . . C1 C -0.2169(5) 0.2360(4) 0.5266(5) 0.0516(12) Uani 1 1 d . . . C2 C -0.2446(7) 0.3544(5) 0.5559(5) 0.0665(16) Uani 1 1 d . . . H3 H -0.3362 0.3835 0.5481 0.080 Uiso 1 1 d R . . C3 C -0.1398(8) 0.4203(5) 0.5954(6) 0.0738(18) Uani 1 1 d . . . H4 H -0.1572 0.4974 0.6170 0.080 Uiso 1 1 d R . . C4 C -0.0055(7) 0.3837(5) 0.6045(6) 0.0709(17) Uani 1 1 d . . . H5 H 0.0682 0.4341 0.6304 0.080 Uiso 1 1 d R . . C5 C 0.0213(6) 0.2764(4) 0.5751(5) 0.0554(13) Uani 1 1 d . . . H6 H 0.1134 0.2485 0.5811 0.080 Uiso 1 1 d R . . C6 C -0.0695(5) 0.2657(4) 0.2302(4) 0.0422(10) Uani 1 1 d . . . C7 C -0.2144(5) 0.4154(4) 0.2075(4) 0.0410(10) Uani 1 1 d . . . C8 C 0.1046(5) -0.1607(4) 0.1553(4) 0.0435(11) Uani 1 1 d . . . C9 C 0.2134(5) -0.3265(4) 0.1083(4) 0.0410(10) 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 Ni1 0.0338(4) 0.0210(3) 0.0439(4) -0.0010(2) 0.0050(2) 0.0005(2) O1 0.0482(17) 0.0192(13) 0.0444(15) -0.0006(12) 0.0084(12) 0.0057(11) N1 0.046(2) 0.0230(16) 0.0424(18) 0.0009(15) 0.0102(15) 0.0080(15) N2 0.056(3) 0.058(3) 0.118(4) -0.013(3) 0.001(3) 0.009(2) N3 0.052(2) 0.036(2) 0.057(2) 0.0084(18) 0.0073(18) 0.0102(18) N4 0.042(2) 0.033(2) 0.100(3) 0.005(2) 0.002(2) 0.0048(18) N5 0.044(2) 0.035(2) 0.064(2) 0.0041(18) -0.0042(18) 0.0072(18) N6 0.056(2) 0.0326(19) 0.048(2) -0.0039(17) 0.0098(17) 0.0055(18) N7 0.070(3) 0.057(3) 0.068(3) -0.025(2) -0.018(2) 0.030(2) N8 0.042(2) 0.041(2) 0.052(2) -0.0034(18) 0.0082(16) 0.0057(18) C1 0.051(3) 0.048(3) 0.057(3) 0.004(2) 0.011(2) 0.013(2) C2 0.087(4) 0.050(3) 0.066(3) 0.008(3) 0.025(3) 0.021(3) C3 0.098(5) 0.041(3) 0.085(4) -0.003(3) 0.030(4) 0.012(3) C4 0.097(5) 0.039(3) 0.078(4) -0.009(3) 0.015(3) -0.015(3) C5 0.082(4) 0.032(2) 0.053(3) -0.001(2) 0.011(2) -0.005(2) C6 0.040(2) 0.039(2) 0.047(2) 0.004(2) 0.0012(18) 0.0049(19) C7 0.048(3) 0.026(2) 0.048(2) 0.0023(18) 0.0000(19) 0.001(2) C8 0.046(3) 0.043(3) 0.042(2) 0.002(2) 0.0059(19) 0.012(2) C9 0.047(3) 0.039(2) 0.038(2) -0.0056(19) 0.0065(18) 0.006(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 Ni1 N3 2.043(4) . y Ni1 N6 2.058(4) . y Ni1 N5 2.077(4) 2_445 y Ni1 O1 2.082(3) 3_556 y Ni1 N8 2.096(4) 2 y Ni1 O1 2.107(3) . y O1 N1 1.347(4) . y O1 Ni1 2.082(3) 3_556 y N1 C1 1.316(6) . y N1 C5 1.409(6) . y N2 C1 1.294(7) . y N3 C6 1.143(6) . y N4 C7 1.293(6) . y N4 C6 1.303(6) . y N5 C7 1.141(6) . y N5 Ni1 2.077(4) 2_455 y N6 C8 1.143(6) . y N7 C9 1.308(6) . y N7 C8 1.320(6) . y N8 C9 1.140(6) . y N8 Ni1 2.096(4) 2_545 ? C1 C2 1.450(8) . ? C2 C3 1.324(9) . ? C3 C4 1.378(9) . ? C4 C5 1.324(7) . ? 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 N3 Ni1 N6 101.98(16) . . y N3 Ni1 N5 91.09(16) . 2_445 y N6 Ni1 N5 89.05(16) . 2_445 y N3 Ni1 O1 165.54(14) . 3_556 y N6 Ni1 O1 92.29(13) . 3_556 y N5 Ni1 O1 91.47(14) 2_445 3_556 y N3 Ni1 N8 86.58(16) . 2 y N6 Ni1 N8 93.00(16) . 2 y N5 Ni1 N8 177.17(15) 2_445 2 y O1 Ni1 N8 90.40(13) 3_556 2 y N3 Ni1 O1 93.51(14) . . y N6 Ni1 O1 164.23(13) . . y N5 Ni1 O1 87.73(15) 2_445 . y O1 Ni1 O1 72.37(11) 3_556 . ? N8 Ni1 O1 90.81(13) 2 . ? N1 O1 Ni1 123.7(2) . 3_556 ? N1 O1 Ni1 126.3(2) . . ? Ni1 O1 Ni1 107.63(11) 3_556 . ? C1 N1 O1 119.8(4) . . ? C1 N1 C5 122.9(4) . . ? O1 N1 C5 117.2(4) . . ? C6 N3 Ni1 154.5(4) . . ? C7 N4 C6 120.6(4) . . ? C7 N5 Ni1 171.9(4) . 2_455 ? C8 N6 Ni1 157.5(4) . . ? C9 N7 C8 121.0(4) . . ? C9 N8 Ni1 158.2(4) . 2_545 ? N2 C1 N1 117.8(5) . . ? N2 C1 C2 124.8(5) . . ? N1 C1 C2 117.4(5) . . ? C3 C2 C1 118.1(6) . . ? C2 C3 C4 123.4(6) . . ? C5 C4 C3 119.0(6) . . ? C4 C5 N1 119.1(5) . . ? N3 C6 N4 174.1(5) . . ? N5 C7 N4 173.8(5) . . ? N6 C8 N7 171.7(5) . . ? N8 C9 N7 171.5(5) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.85 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 1.156 _refine_diff_density_min -1.411 _refine_diff_density_rms 0.399 #===END data_Mn(apo)(N(CN)2)2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C9 H6 Mn N8 O' _chemical_formula_weight 297.16 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 ' P 2(1)/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 9.8655(3) _cell_length_b 12.1640(4) _cell_length_c 10.5046(3) _cell_angle_alpha 90.00 _cell_angle_beta 94.795(2) _cell_angle_gamma 90.00 _cell_volume 1256.18(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 22515 _cell_measurement_theta_min 3.40 _cell_measurement_theta_max 27.84 _exptl_crystal_description 'polyhedral' _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.571 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 596 _exptl_absorpt_coefficient_mu 1.056 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.985 _exptl_absorpt_correction_T_max 0.102 _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 22515 _diffrn_reflns_av_R_equivalents 0.0300 _diffrn_reflns_av_sigmaI/netI 0.0230 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.40 _diffrn_reflns_theta_max 27.84 _reflns_number_total 2970 _reflns_number_gt 2565 _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^)+(0.0468P)^2^+0.5263P] 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 SHELXL _refine_ls_extinction_coef 0.016(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2970 _refine_ls_number_parameters 173 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0414 _refine_ls_R_factor_gt 0.0336 _refine_ls_wR_factor_ref 0.0934 _refine_ls_wR_factor_gt 0.0889 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.059 _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 Mn1 Mn 0.01568(3) 0.03119(2) 0.33364(3) 0.03595(13) Uani 1 1 d . . . O1 O -0.05337(14) 0.09406(10) 0.51631(13) 0.0408(3) Uani 1 1 d . . . N1 N -0.08165(16) 0.20038(12) 0.54006(14) 0.0361(3) Uani 1 1 d . . . N2 N -0.3047(2) 0.1609(2) 0.4944(3) 0.0792(7) Uani 1 1 d . . . H1 H -0.3938 0.1799 0.4869 0.080 Uiso 1 1 d R . . H2 H -0.2794 0.0897 0.4782 0.080 Uiso 1 1 d R . . N3 N -0.0323(2) 0.18709(15) 0.2402(2) 0.0591(5) Uani 1 1 d . . . N4 N -0.0832(2) 0.38234(15) 0.2200(2) 0.0648(6) Uani 1 1 d . . . N5 N -0.3062(2) 0.46839(16) 0.2141(2) 0.0587(5) Uani 1 1 d . . . N6 N 0.0880(2) -0.08100(15) 0.19111(19) 0.0561(5) Uani 1 1 d . . . N7 N 0.0992(2) -0.25999(17) 0.0867(2) 0.0642(6) Uani 1 1 d . . . N8 N 0.27747(19) -0.39895(16) 0.11428(19) 0.0543(5) Uani 1 1 d . . . C1 C -0.2119(2) 0.23367(19) 0.5281(2) 0.0501(5) Uani 1 1 d . . . C2 C -0.2362(3) 0.3477(2) 0.5552(2) 0.0647(7) Uani 1 1 d . . . H3 H -0.3277 0.3767 0.5475 0.080 Uiso 1 1 d R . . C3 C -0.1302(3) 0.4123(2) 0.5927(3) 0.0700(7) Uani 1 1 d . . . H4 H -0.1476 0.4894 0.6142 0.080 Uiso 1 1 d R . . C4 C 0.0003(3) 0.3752(2) 0.6036(3) 0.0713(7) Uani 1 1 d . . . H5 H 0.0740 0.4256 0.6296 0.080 Uiso 1 1 d R . . C5 C 0.0231(3) 0.26934(17) 0.5770(2) 0.0532(5) Uani 1 1 d . . . H6 H 0.1152 0.2414 0.5831 0.080 Uiso 1 1 d R . . C6 C -0.0627(2) 0.27753(17) 0.2315(2) 0.0463(5) Uani 1 1 d . . . C7 C -0.2044(2) 0.42288(16) 0.2176(2) 0.0460(5) Uani 1 1 d . . . C8 C 0.1011(2) -0.16562(17) 0.14535(19) 0.0463(5) Uani 1 1 d . . . C9 C 0.1983(2) -0.33016(17) 0.10545(18) 0.0431(4) 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 Mn1 0.03866(18) 0.02363(16) 0.04548(19) -0.00055(10) 0.00300(12) 0.00024(10) O1 0.0528(8) 0.0207(6) 0.0497(7) -0.0007(5) 0.0085(6) 0.0064(5) N1 0.0447(8) 0.0225(7) 0.0417(8) 0.0000(6) 0.0069(6) 0.0044(6) N2 0.0507(12) 0.0650(14) 0.120(2) -0.0144(14) -0.0015(12) 0.0097(10) N3 0.0712(13) 0.0394(10) 0.0667(12) 0.0126(9) 0.0060(10) 0.0119(9) N4 0.0492(10) 0.0356(9) 0.1091(17) 0.0052(10) 0.0024(10) 0.0062(8) N5 0.0502(11) 0.0497(11) 0.0739(13) 0.0066(9) -0.0085(9) 0.0096(9) N6 0.0668(12) 0.0413(10) 0.0611(11) -0.0079(8) 0.0099(9) 0.0073(9) N7 0.0640(12) 0.0502(11) 0.0744(13) -0.0206(10) -0.0177(10) 0.0213(9) N8 0.0490(10) 0.0502(10) 0.0640(11) -0.0056(9) 0.0067(8) 0.0143(8) C1 0.0493(11) 0.0491(12) 0.0526(11) 0.0039(9) 0.0081(9) 0.0116(9) C2 0.0774(17) 0.0571(14) 0.0623(14) 0.0089(11) 0.0230(12) 0.0284(13) C3 0.108(2) 0.0376(12) 0.0681(15) -0.0020(11) 0.0270(15) 0.0044(14) C4 0.101(2) 0.0393(12) 0.0741(16) -0.0111(11) 0.0131(15) -0.0149(13) C5 0.0706(14) 0.0365(10) 0.0528(11) -0.0023(9) 0.0078(10) -0.0114(10) C6 0.0483(11) 0.0421(11) 0.0481(11) 0.0050(8) 0.0022(9) 0.0055(9) C7 0.0517(11) 0.0328(9) 0.0519(11) 0.0010(8) -0.0064(9) -0.0003(9) C8 0.0490(11) 0.0443(11) 0.0453(10) -0.0018(8) 0.0022(8) 0.0095(9) C9 0.0449(10) 0.0419(10) 0.0425(10) -0.0070(8) 0.0035(8) 0.0051(8) _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 N3 2.1692(18) . y Mn1 N6 2.1889(18) . y Mn1 O1 2.2014(13) 3_556 y Mn1 N5 2.2212(19) 2_445 y Mn1 O1 2.2248(13) . y Mn1 N8 2.2359(18) 2 y O1 N1 1.3507(18) . y O1 Mn1 2.2014(13) 3_556 y N1 C1 1.343(3) . y N1 C5 1.362(3) . y N2 C1 1.301(3) . y N3 C6 1.142(3) . y N4 C7 1.292(3) . y N4 C6 1.295(3) . y N5 C7 1.144(3) . y N5 Mn1 2.2212(19) 2_455 y N6 C8 1.148(3) . y N7 C9 1.300(3) . y N7 C8 1.302(3) . y N8 C9 1.143(3) . y N8 Mn1 2.2359(18) 2_545 y C1 C2 1.440(3) . y C2 C3 1.341(4) . y C3 C4 1.359(4) . y C4 C5 1.341(3) . y 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 N3 Mn1 N6 107.87(8) . . y N3 Mn1 O1 161.15(7) . 3_556 y N6 Mn1 O1 90.75(6) . 3_556 y N3 Mn1 N5 91.99(8) . 2_445 y N6 Mn1 N5 88.93(8) . 2_445 y O1 Mn1 N5 91.26(6) 3_556 2_445 y N3 Mn1 O1 91.07(7) . . y N6 Mn1 O1 160.92(6) . . y O1 Mn1 O1 70.48(5) 3_556 . y N5 Mn1 O1 88.10(7) 2_445 . y N3 Mn1 N8 86.49(8) . 2 y N6 Mn1 N8 93.52(8) . 2 y O1 Mn1 N8 89.53(6) 3_556 2 y N5 Mn1 N8 177.42(7) 2_445 2 y O1 Mn1 N8 89.85(6) . 2 y N1 O1 Mn1 123.75(11) . 3_556 y N1 O1 Mn1 124.84(10) . . y Mn1 O1 Mn1 109.52(5) 3_556 . y C1 N1 O1 118.83(16) . . y C1 N1 C5 122.57(18) . . y O1 N1 C5 118.60(17) . . y C6 N3 Mn1 157.6(2) . . y C7 N4 C6 120.9(2) . . y C7 N5 Mn1 166.13(19) . 2_455 y C8 N6 Mn1 154.16(19) . . y C9 N7 C8 121.7(2) . . y C9 N8 Mn1 154.35(18) . 2_545 y N2 C1 N1 117.8(2) . . y N2 C1 C2 125.7(2) . . ? N1 C1 C2 116.5(2) . . ? C3 C2 C1 118.9(2) . . ? C2 C3 C4 122.7(2) . . ? C5 C4 C3 118.4(3) . . ? C4 C5 N1 120.9(2) . . ? N3 C6 N4 173.6(3) . . ? N5 C7 N4 173.4(2) . . ? N6 C8 N7 172.3(2) . . ? N8 C9 N7 173.1(2) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.84 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.537 _refine_diff_density_min -0.245 _refine_diff_density_rms 0.050 #===END