# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry, 1999 # CCDC Number: 186/1562 data_alpha-mndca2 _audit_creation_method SHELXL _chemical_name_systematic ; manganese bis(dicyanamide) ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C4 Mn N6' _chemical_formula_weight 187.04 _chemical_melting_point ? _chemical_compound_source ? 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' 'N' 'N' 0.0061 0.0033 '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 Orthorhombic _symmetry_space_group_name_H-M Pnnm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x, y, -z' 'x-1/2, -y-1/2, z-1/2' '-x-1/2, y-1/2, z-1/2' _cell_length_a 7.2723(3) _cell_length_b 6.1126(3) _cell_length_c 7.5563(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 335.90(3) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour colourless _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.849 _exptl_crystal_density_method ? _exptl_crystal_F_000 182 _exptl_absorpt_coefficient_mu 1.896 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1155 _diffrn_reflns_av_R_equivalents 0.026 _diffrn_reflns_av_sigmaI/netI 0.0274 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.89 _diffrn_reflns_theta_max 28.14 _reflns_number_total 413 _reflns_number_observed 376 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0333P)^2^+0.1632P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 413 _refine_ls_number_parameters 29 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0287 _refine_ls_R_factor_obs 0.0249 _refine_ls_wR_factor_all 0.0645 _refine_ls_wR_factor_obs 0.0629 _refine_ls_goodness_of_fit_all 1.133 _refine_ls_goodness_of_fit_obs 1.161 _refine_ls_restrained_S_all 1.133 _refine_ls_restrained_S_obs 1.161 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn Mn 0.0000 0.0000 0.0000 0.0116(2) Uani 1 d S . N1 N -0.0905(2) 0.2175(2) 0.2130(2) 0.0191(3) Uani 1 d . . N2 N 0.2855(3) 0.1581(3) 0.0000 0.0164(4) Uani 1 d S . C1 C -0.1431(2) 0.2705(2) 0.3502(2) 0.0147(3) 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 Mn 0.0101(3) 0.0167(3) 0.0079(3) 0.000 0.000 -0.0005(2) N1 0.0192(7) 0.0240(8) 0.0141(7) -0.0024(6) 0.0013(6) 0.0023(5) N2 0.0165(9) 0.0234(10) 0.0095(8) 0.000 0.000 -0.0063(7) C1 0.0117(7) 0.0165(7) 0.0161(8) 0.0010(6) -0.0022(6) 0.0019(5) _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 Mn N1 2.1888(13) 5 ? Mn N1 2.1888(13) . ? Mn N1 2.1888(13) 2 ? Mn N1 2.1888(13) 6 ? Mn N2 2.290(2) . ? Mn N2 2.290(2) 5 ? N1 C1 1.152(2) . ? N2 C1 1.319(2) 4 ? N2 C1 1.319(2) 7_665 ? C1 N2 1.319(2) 7_566 ? 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 Mn N1 180.0 5 . ? N1 Mn N1 94.67(7) 5 2 ? N1 Mn N1 85.33(7) . 2 ? N1 Mn N1 85.33(7) 5 6 ? N1 Mn N1 94.67(7) . 6 ? N1 Mn N1 180.0 2 6 ? N1 Mn N2 89.07(5) 5 . ? N1 Mn N2 90.93(5) . . ? N1 Mn N2 89.07(5) 2 . ? N1 Mn N2 90.93(5) 6 . ? N1 Mn N2 90.93(5) 5 5 ? N1 Mn N2 89.07(5) . 5 ? N1 Mn N2 90.93(5) 2 5 ? N1 Mn N2 89.07(5) 6 5 ? N2 Mn N2 180.0 . 5 ? C1 N1 Mn 158.87(13) . . ? C1 N2 C1 118.1(2) 4 7_665 ? C1 N2 Mn 119.76(9) 4 . ? C1 N2 Mn 119.76(9) 7_665 . ? N1 C1 N2 174.9(2) . 7_566 ? _refine_diff_density_max 0.292 _refine_diff_density_min -0.431 _refine_diff_density_rms 0.081 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_mndca2py2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; manganese bis(dicyanamide) dipyridinate ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H10 Mn N8' _chemical_formula_weight 345.24 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' '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 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 7.5212(3) _cell_length_b 13.1458(9) _cell_length_c 8.6087(6) _cell_angle_alpha 90.00 _cell_angle_beta 115.183(9) _cell_angle_gamma 90.00 _cell_volume 770.26(8) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description rod _exptl_crystal_colour colourless _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.489 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 350 _exptl_absorpt_coefficient_mu 0.868 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 ? _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2803 _diffrn_reflns_av_R_equivalents 0.1137 _diffrn_reflns_av_sigmaI/netI 0.1237 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.04 _diffrn_reflns_theta_max 28.32 _reflns_number_total 1612 _reflns_number_gt 1002 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens 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 w=1/[\s^2^(Fo^2^)+(0.0351P)^2^+0.7114P] 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 1612 _refine_ls_number_parameters 106 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1034 _refine_ls_R_factor_gt 0.0509 _refine_ls_wR_factor_ref 0.1200 _refine_ls_wR_factor_gt 0.1053 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.067 _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 0.0000 0.5000 0.0188(2) Uani 1 d S . . N1 N 0.1426(4) 0.0067(2) 0.7899(3) 0.0218(6) Uani 1 d . . . C1 C 0.1462(5) -0.0753(3) 0.8838(5) 0.0249(8) Uani 1 d . . . H1A H 0.0807 -0.1352 0.8259 0.030 Uiso 1 calc R . . C2 C 0.2406(5) -0.0766(3) 1.0605(5) 0.0280(8) Uani 1 d . . . H2A H 0.2387 -0.1362 1.1223 0.034 Uiso 1 calc R . . C3 C 0.3374(5) 0.0089(3) 1.1465(4) 0.0273(8) Uani 1 d . . . H3A H 0.4051 0.0093 1.2682 0.033 Uiso 1 calc R . . C4 C 0.3341(5) 0.0944(3) 1.0521(5) 0.0270(8) Uani 1 d . . . H4A H 0.3992 0.1550 1.1077 0.032 Uiso 1 calc R . . C5 C 0.2344(5) 0.0904(3) 0.8750(5) 0.0254(8) Uani 1 d . . . H5A H 0.2309 0.1498 0.8109 0.031 Uiso 1 calc R . . N11 N 0.2044(4) -0.1238(2) 0.5070(4) 0.0259(7) Uani 1 d . . . C11 C 0.3430(5) -0.1570(2) 0.4996(5) 0.0220(8) Uani 1 d . . . N12 N 0.7835(4) -0.1130(2) 0.5059(4) 0.0242(7) Uani 1 d . . . C12 C 0.6419(5) -0.1513(2) 0.4992(4) 0.0211(8) Uani 1 d . . . N13 N 0.4908(4) -0.2033(2) 0.4893(5) 0.0379(8) 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 0.0127(3) 0.0233(4) 0.0222(4) -0.0010(4) 0.0093(3) -0.0007(3) N1 0.0192(13) 0.0230(15) 0.0250(15) -0.0012(15) 0.0109(11) -0.0011(13) C1 0.0217(16) 0.024(2) 0.026(2) 0.0005(17) 0.0080(14) -0.0033(15) C2 0.0279(18) 0.027(2) 0.026(2) 0.0046(17) 0.0080(15) -0.0034(15) C3 0.0285(17) 0.030(2) 0.0219(18) -0.0037(19) 0.0091(14) 0.0024(17) C4 0.0270(17) 0.0237(19) 0.029(2) -0.0052(17) 0.0103(15) -0.0012(15) C5 0.0260(17) 0.023(2) 0.029(2) 0.0013(17) 0.0138(15) 0.0016(15) N11 0.0194(15) 0.0278(17) 0.0324(19) -0.0029(14) 0.0129(13) 0.0005(12) C11 0.0218(17) 0.0186(18) 0.025(2) 0.0001(16) 0.0097(14) -0.0065(14) N12 0.0218(15) 0.0250(16) 0.0279(18) -0.0012(14) 0.0124(13) -0.0011(12) C12 0.0188(16) 0.0198(18) 0.027(2) -0.0003(16) 0.0117(14) 0.0019(14) N13 0.0261(15) 0.0194(15) 0.082(3) -0.0069(19) 0.0358(17) -0.0028(14) _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 N12 2.220(3) 3_656 ? Mn1 N12 2.220(3) 1_455 ? Mn1 N11 2.222(3) 3_556 ? Mn1 N11 2.222(3) . ? Mn1 N1 2.260(3) 3_556 ? Mn1 N1 2.260(3) . ? N1 C5 1.340(4) . ? N1 C1 1.341(4) . ? C1 C2 1.378(5) . ? C2 C3 1.373(5) . ? C3 C4 1.381(5) . ? C4 C5 1.384(5) . ? N11 C11 1.156(4) . ? C11 N13 1.303(4) . ? N12 C12 1.157(4) . ? N12 Mn1 2.220(3) 1_655 ? C12 N13 1.297(4) . ? 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 N12 Mn1 N12 180.0 3_656 1_455 ? N12 Mn1 N11 90.86(10) 3_656 3_556 ? N12 Mn1 N11 89.15(10) 1_455 3_556 ? N12 Mn1 N11 89.14(10) 3_656 . ? N12 Mn1 N11 90.85(10) 1_455 . ? N11 Mn1 N11 180.0 3_556 . ? N12 Mn1 N1 90.51(10) 3_656 3_556 ? N12 Mn1 N1 89.49(10) 1_455 3_556 ? N11 Mn1 N1 90.04(11) 3_556 3_556 ? N11 Mn1 N1 89.96(11) . 3_556 ? N12 Mn1 N1 89.49(10) 3_656 . ? N12 Mn1 N1 90.51(10) 1_455 . ? N11 Mn1 N1 89.96(11) 3_556 . ? N11 Mn1 N1 90.04(11) . . ? N1 Mn1 N1 180.0 3_556 . ? C5 N1 C1 117.2(3) . . ? C5 N1 Mn1 121.9(2) . . ? C1 N1 Mn1 120.9(2) . . ? N1 C1 C2 123.0(3) . . ? C3 C2 C1 119.4(4) . . ? C2 C3 C4 118.5(3) . . ? C3 C4 C5 118.8(3) . . ? N1 C5 C4 123.1(3) . . ? C11 N11 Mn1 154.7(3) . . ? N11 C11 N13 174.2(4) . . ? C12 N12 Mn1 163.4(3) . 1_655 ? N12 C12 N13 174.0(4) . . ? C12 N13 C11 119.9(3) . . ? _diffrn_measured_fraction_theta_max 0.808 _diffrn_reflns_theta_full 28.32 _diffrn_measured_fraction_theta_full 0.808 _refine_diff_density_max 0.792 _refine_diff_density_min -0.426 _refine_diff_density_rms 0.085 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_mndca2dmf2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; manganese bis(dicyanamide) bis(N,N'-dimethylforamide) ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C10 H14 Mn N8 O2' _chemical_formula_weight 333.23 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.4242(3) _cell_length_b 7.4907(4) _cell_length_c 8.4034(4) _cell_angle_alpha 103.021(3) _cell_angle_beta 106.485(4) _cell_angle_gamma 99.390(4) _cell_volume 366.46(3) _cell_formula_units_Z 1 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description rod _exptl_crystal_colour colourless _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.510 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 171 _exptl_absorpt_coefficient_mu 0.918 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 ? _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3174 _diffrn_reflns_av_R_equivalents 0.023 _diffrn_reflns_av_sigmaI/netI 0.0479 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.55 _diffrn_reflns_theta_max 28.28 _reflns_number_total 1460 _reflns_number_gt 1316 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens 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 w=1/[\s^2^(Fo^2^)+(0.0799P)^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 1460 _refine_ls_number_parameters 97 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0464 _refine_ls_R_factor_gt 0.0415 _refine_ls_wR_factor_ref 0.1289 _refine_ls_wR_factor_gt 0.1268 _refine_ls_goodness_of_fit_ref 1.234 _refine_ls_restrained_S_all 1.234 _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 1.0000 0.0000 0.5000 0.0161(2) Uani 1 d S . . N1 N 0.7954(4) -0.1869(3) 0.5988(3) 0.0222(5) Uani 1 d . . . C1 C 0.7639(4) -0.3323(4) 0.6250(3) 0.0175(5) Uani 1 d . . . N2 N 0.8190(4) -0.7786(3) 0.5470(3) 0.0228(5) Uani 1 d . . . C2 C 0.7775(4) -0.6371(4) 0.5990(3) 0.0182(5) Uani 1 d . . . N3 N 0.7213(4) -0.4870(3) 0.6688(3) 0.0248(5) Uani 1 d . . . O11 O 0.7534(3) -0.1281(3) 0.2385(2) 0.0223(4) Uani 1 d . . . C12 C 0.5519(4) -0.1272(4) 0.2082(3) 0.0190(5) Uani 1 d . . . H12A H 0.5094 -0.0645 0.3012 0.023 Uiso 1 calc R . . N13 N 0.3941(3) -0.2069(3) 0.0568(3) 0.0199(5) Uani 1 d . . . C14 C 0.4407(5) -0.3106(4) -0.0931(3) 0.0284(6) Uani 1 d . . . H14A H 0.6002 -0.3091 -0.0605 0.043 Uiso 1 calc R . . H14B H 0.4014 -0.2508 -0.1863 0.043 Uiso 1 calc R . . H14C H 0.3517 -0.4415 -0.1331 0.043 Uiso 1 calc R . . C15 C 0.1640(4) -0.1942(4) 0.0321(4) 0.0279(6) Uani 1 d . . . H15A H 0.1540 -0.1217 0.1412 0.042 Uiso 1 calc R . . H15B H 0.0665 -0.3215 -0.0043 0.042 Uiso 1 calc R . . H15C H 0.1167 -0.1308 -0.0573 0.042 Uiso 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 Mn1 0.0158(3) 0.0139(3) 0.0194(3) 0.0050(2) 0.0058(2) 0.0052(2) N1 0.0236(11) 0.0203(12) 0.0255(12) 0.0071(9) 0.0117(10) 0.0054(9) C1 0.0148(11) 0.0210(14) 0.0170(12) 0.0016(10) 0.0080(10) 0.0056(10) N2 0.0239(11) 0.0201(12) 0.0284(12) 0.0090(9) 0.0102(10) 0.0106(9) C2 0.0161(11) 0.0214(14) 0.0165(12) 0.0081(10) 0.0032(10) 0.0032(10) N3 0.0383(13) 0.0171(11) 0.0275(12) 0.0075(9) 0.0210(11) 0.0101(10) O11 0.0177(9) 0.0266(10) 0.0212(9) 0.0046(8) 0.0062(8) 0.0052(7) C12 0.0214(12) 0.0185(13) 0.0182(12) 0.0057(10) 0.0081(11) 0.0044(10) N13 0.0203(11) 0.0221(11) 0.0167(10) 0.0046(9) 0.0052(9) 0.0060(9) C14 0.0354(15) 0.0308(15) 0.0187(13) 0.0032(11) 0.0098(12) 0.0113(12) C15 0.0182(12) 0.0362(16) 0.0248(14) 0.0062(12) 0.0021(11) 0.0071(11) _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 O11 2.1994(18) 2_756 ? Mn1 O11 2.1994(18) . ? Mn1 N2 2.203(2) 1_565 ? Mn1 N2 2.203(2) 2_746 ? Mn1 N1 2.218(2) . ? Mn1 N1 2.218(2) 2_756 ? N1 C1 1.156(3) . ? C1 N3 1.303(4) . ? N2 C2 1.155(3) . ? N2 Mn1 2.203(2) 1_545 ? C2 N3 1.302(3) . ? O11 C12 1.248(3) . ? C12 N13 1.316(3) . ? N13 C15 1.455(3) . ? N13 C14 1.459(3) . ? 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 O11 Mn1 O11 180.0 2_756 . ? O11 Mn1 N2 89.85(8) 2_756 1_565 ? O11 Mn1 N2 90.15(8) . 1_565 ? O11 Mn1 N2 90.15(8) 2_756 2_746 ? O11 Mn1 N2 89.85(8) . 2_746 ? N2 Mn1 N2 180.0 1_565 2_746 ? O11 Mn1 N1 90.86(7) 2_756 . ? O11 Mn1 N1 89.14(7) . . ? N2 Mn1 N1 91.64(8) 1_565 . ? N2 Mn1 N1 88.36(8) 2_746 . ? O11 Mn1 N1 89.14(7) 2_756 2_756 ? O11 Mn1 N1 90.86(7) . 2_756 ? N2 Mn1 N1 88.36(8) 1_565 2_756 ? N2 Mn1 N1 91.64(8) 2_746 2_756 ? N1 Mn1 N1 180.0 . 2_756 ? C1 N1 Mn1 144.80(18) . . ? N1 C1 N3 173.5(3) . . ? C2 N2 Mn1 162.7(2) . 1_545 ? N2 C2 N3 173.5(3) . . ? C2 N3 C1 120.6(2) . . ? C12 O11 Mn1 121.36(16) . . ? O11 C12 N13 124.7(2) . . ? C12 N13 C15 120.9(2) . . ? C12 N13 C14 122.0(2) . . ? C15 N13 C14 117.1(2) . . ? _diffrn_measured_fraction_theta_max 0.806 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.806 _refine_diff_density_max 1.076 _refine_diff_density_min -1.171 _refine_diff_density_rms 0.404 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_mndca2meoh2 _audit_creation_method SHELXL _chemical_name_systematic ; manganese bis(dicyanamide) dimethanolate ; _chemical_name_common ? _chemical_formula_moiety 'C6 H8 Mn N6 O2' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C6 H8 Mn N6 O2' _chemical_formula_weight 251.12 _chemical_melting_point ? _chemical_compound_source ; 'metathesis and recrystallisation in methanol' ; 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' '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' 'H' 'H' 0.0000 0.0000 '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 C2/m _symmetry_Int_Tables_number 12 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 12.409(1) _cell_length_b 7.481(1) _cell_length_c 6.528(1) _cell_angle_alpha 90.00 _cell_angle_beta 119.979(3) _cell_angle_gamma 90.00 _cell_volume 524.93(11) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1186 _cell_measurement_theta_min 3.32 _cell_measurement_theta_max 26.30 _exptl_crystal_description 'Transparent blocks' _exptl_crystal_colour clear _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.25 _exptl_crystal_density_method 'not measured' _exptl_crystal_density_diffrn 1.589 _exptl_crystal_F_000 254 _exptl_absorpt_coefficient_mu 1.248 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 1.0 _exptl_absorpt_correction_T_max 1.0 _exptl_special_details ; ? ; _diffrn_ambient_environment ; 'In thin film of perfluorpolyether oil on mohair fibre' ; _diffrn_crystal_treatment 'Flash cooled in nitrogen stream' _diffrn_ambient_temperature 150(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 'Enraf-Nonius DIP2000 diffractometer' _diffrn_detector 'Eu/Ba image plate' _diffrn_measurement_method 'Ninety 2-degree oscillations in phi' _diffrn_standards_decay_% 0 _diffrn_reflns_number 1764 _diffrn_reflns_av_R_equivalents 0.022 _diffrn_reflns_av_sigmaI/netI 0.0236 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 3.32 _diffrn_reflns_theta_max 26.30 _reflns_number_total 538 _reflns_number_observed 537 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'XPRESS (MAC Science, 1989)' _computing_cell_refinement 'HKL (Otwinowski & Minor, 1996)' _computing_data_reduction 'HKL (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'XPMA/ZORTEP' _computing_publication_material 'CIFTAB' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating -R-factor-obs 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^)+(0.0246P)^2^+0.3168P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 538 _refine_ls_number_parameters 51 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0238 _refine_ls_R_factor_obs 0.0237 _refine_ls_wR_factor_all 0.0578 _refine_ls_wR_factor_obs 0.0577 _refine_ls_goodness_of_fit_all 1.257 _refine_ls_goodness_of_fit_obs 1.255 _refine_ls_restrained_S_all 1.257 _refine_ls_restrained_S_obs 1.255 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn1 Mn 0.0000 0.0000 0.0000 0.0141(2) Uani 1 d S . N1 N 0.05705(13) 0.2117(2) 0.2713(2) 0.0239(3) Uani 1 d . . C1 C 0.08663(12) 0.3496(2) 0.3610(2) 0.0164(3) Uani 1 d . . N2 N 0.1259(2) 0.5000 0.4792(3) 0.0199(4) Uani 1 d S . O1 O -0.18609(15) 0.0000 -0.0473(3) 0.0273(4) Uani 1 d S . H1 H -0.2422(34) 0.0000 -0.1819(70) 0.047(10) Uiso 1 d S . C2 C -0.2279(3) 0.0000 0.1191(5) 0.0298(5) Uani 1 d S . H2A H -0.1611(38) 0.0000 0.2698(79) 0.066(12) Uiso 1 d S . H2B H -0.2770(24) -0.1053(37) 0.1051(45) 0.060(8) Uiso 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 0.0173(3) 0.0102(3) 0.0141(2) 0.000 0.0073(2) 0.000 N1 0.0336(7) 0.0166(7) 0.0191(7) -0.0022(5) 0.0112(6) -0.0020(5) C1 0.0176(7) 0.0174(7) 0.0129(7) 0.0035(6) 0.0067(6) 0.0019(5) N2 0.0245(9) 0.0132(9) 0.0143(8) 0.000 0.0041(7) 0.000 O1 0.0165(7) 0.0503(11) 0.0136(8) 0.000 0.0064(7) 0.000 C2 0.0328(13) 0.037(2) 0.0272(13) 0.000 0.0204(12) 0.000 _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 O1 2.172(2) 5 ? Mn1 O1 2.172(2) . ? Mn1 N1 2.2119(13) 6 ? Mn1 N1 2.2120(13) 5 ? Mn1 N1 2.2120(13) 2 ? Mn1 N1 2.2120(13) . ? N1 C1 1.152(2) . ? C1 N2 1.312(2) . ? N2 C1 1.313(2) 6_565 ? O1 C2 1.418(3) . ? O1 H1 0.80(4) . ? C2 H2A 0.92(4) . ? C2 H2B 0.97(3) . ? 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 Mn1 O1 180.0 5 . ? O1 Mn1 N1 89.66(5) 5 6 ? O1 Mn1 N1 90.34(5) . 6 ? O1 Mn1 N1 90.34(5) 5 5 ? O1 Mn1 N1 89.66(5) . 5 ? N1 Mn1 N1 88.57(7) 6 5 ? O1 Mn1 N1 90.34(5) 5 2 ? O1 Mn1 N1 89.66(5) . 2 ? N1 Mn1 N1 180.0 6 2 ? N1 Mn1 N1 91.43(7) 5 2 ? O1 Mn1 N1 89.66(5) 5 . ? O1 Mn1 N1 90.34(5) . . ? N1 Mn1 N1 91.43(7) 6 . ? N1 Mn1 N1 180.0 5 . ? N1 Mn1 N1 88.57(7) 2 . ? C1 N1 Mn1 160.27(12) . . ? N1 C1 N2 175.42(15) . . ? C1 N2 C1 118.0(2) . 6_565 ? C2 O1 Mn1 131.4(2) . . ? C2 O1 H1 112.9(26) . . ? Mn1 O1 H1 115.7(26) . . ? O1 C2 H2A 110.0(26) . . ? O1 C2 H2B 112.3(16) . . ? H2A C2 H2B 106.8(20) . . ? _refine_diff_density_max 0.172 _refine_diff_density_min -0.253 _refine_diff_density_rms 0.060 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_fedca2meoh2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; iron bis(dicyanamide) dimethanolate ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C6 H8 Fe N6 O2' _chemical_formula_weight 252.03 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'Fe' 'Fe' 0.3463 0.8444 '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' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' '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' _symmetry_cell_setting ? _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 12.2247(7) _cell_length_b 7.3921(5) _cell_length_c 6.4610(4) _cell_angle_alpha 90.00 _cell_angle_beta 120.1190(10) _cell_angle_gamma 90.00 _cell_volume 505.03(5) _cell_formula_units_Z 2 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prismatic _exptl_crystal_colour colourless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.657 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 256 _exptl_absorpt_coefficient_mu 1.484 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 'phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3366 _diffrn_reflns_av_R_equivalents 0.057 _diffrn_reflns_av_sigmaI/netI 0.0457 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.65 _diffrn_reflns_theta_max 28.26 _reflns_number_total 664 _reflns_number_gt 584 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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^)+(0.0396P)^2^+1.0619P] 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 664 _refine_ls_number_parameters 51 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0555 _refine_ls_R_factor_gt 0.0424 _refine_ls_wR_factor_ref 0.0926 _refine_ls_wR_factor_gt 0.0874 _refine_ls_goodness_of_fit_ref 1.089 _refine_ls_restrained_S_all 1.089 _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 Fe1 Fe 0.0000 0.0000 0.0000 0.0197(3) Uani 1 d S . . O1 O -0.1820(3) 0.0000 -0.0475(5) 0.0295(6) Uani 1 d S . . N1 N 0.0545(2) 0.2098(3) 0.2642(4) 0.0251(5) Uani 1 d . . . N2 N 0.1269(3) 0.5000 0.4787(5) 0.0229(7) Uani 1 d S . . C1 C 0.0855(2) 0.3480(3) 0.3573(4) 0.0204(5) Uani 1 d . . . C2 C -0.2244(4) 0.0000 0.1218(8) 0.0314(9) Uani 1 d S . . H2A H -0.153(5) 0.0000 0.287(10) 0.053(15) Uiso 1 d S . . H2B H -0.276(3) -0.094(5) 0.101(6) 0.040(9) Uiso 1 d . . . H1 H -0.241(5) 0.0000 -0.177(9) 0.038(14) Uiso 1 d S . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Fe1 0.0217(4) 0.0153(4) 0.0187(4) 0.000 0.0076(3) 0.000 O1 0.0211(14) 0.0475(18) 0.0157(13) 0.000 0.0060(12) 0.000 N1 0.0320(12) 0.0202(12) 0.0198(11) -0.0001(9) 0.0105(10) 0.0010(9) N2 0.0257(16) 0.0181(15) 0.0165(14) 0.000 0.0043(13) 0.000 C1 0.0203(12) 0.0232(14) 0.0158(11) 0.0040(10) 0.0077(10) 0.0030(10) C2 0.030(2) 0.037(2) 0.030(2) 0.000 0.0173(19) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe1 O1 2.088(3) . ? Fe1 O1 2.088(3) 5 ? Fe1 N1 2.150(2) 6 ? Fe1 N1 2.150(2) . ? Fe1 N1 2.150(2) 5 ? Fe1 N1 2.150(2) 2 ? O1 C2 1.426(5) . ? N1 C1 1.149(3) . ? N2 C1 1.317(3) . ? N2 C1 1.317(3) 6_565 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Fe1 O1 180.0 . 5 ? O1 Fe1 N1 89.96(8) . 6 ? O1 Fe1 N1 90.04(8) 5 6 ? O1 Fe1 N1 89.96(8) . . ? O1 Fe1 N1 90.04(8) 5 . ? N1 Fe1 N1 92.35(11) 6 . ? O1 Fe1 N1 90.04(8) . 5 ? O1 Fe1 N1 89.96(8) 5 5 ? N1 Fe1 N1 87.65(11) 6 5 ? N1 Fe1 N1 180.0 . 5 ? O1 Fe1 N1 90.04(8) . 2 ? O1 Fe1 N1 89.96(8) 5 2 ? N1 Fe1 N1 180.0 6 2 ? N1 Fe1 N1 87.65(11) . 2 ? N1 Fe1 N1 92.35(11) 5 2 ? C2 O1 Fe1 131.2(3) . . ? C1 N1 Fe1 161.1(2) . . ? C1 N2 C1 117.0(3) . 6_565 ? N1 C1 N2 175.7(3) . . ? _diffrn_measured_fraction_theta_max 0.492 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.498 _refine_diff_density_max 0.358 _refine_diff_density_min -0.377 _refine_diff_density_rms 0.095 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_mndca2etoh2me2co _audit_creation_method SHELXL _chemical_name_systematic ; manganese bis(dicyanamide) diethanolate acetone solvate ; _chemical_name_common ? _chemical_formula_moiety 'C8 H12 Mn N6 O2, C3 H6 O' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C11 H18 Mn N6 O3' _chemical_formula_weight 337.25 _chemical_melting_point ? _chemical_compound_source ; 'metathesis and recrystallisation in an ethanol and acetone mixture' ; 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' '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' 'H' 'H' 0.0000 0.0000 '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 C2/c _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 11.316(1) _cell_length_b 11.358(1) _cell_length_c 12.488(1) _cell_angle_alpha 90.00 _cell_angle_beta 96.918(3) _cell_angle_gamma 90.00 _cell_volume 1593.4(2) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 3827 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 26.30 _exptl_crystal_description 'Transparent blocks' _exptl_crystal_colour clear _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_method 'not measured' _exptl_crystal_density_diffrn 1.406 _exptl_crystal_F_000 700 _exptl_absorpt_coefficient_mu 0.847 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 1.0 _exptl_absorpt_correction_T_max 1.0 _exptl_special_details ; ? ; _diffrn_ambient_environment ; 'In thin film of perfluorpolyether oil on mohair fibre' ; _diffrn_crystal_treatment 'Flash cooled in nitrogen stream' _diffrn_ambient_temperature 150(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 'Enraf-Nonius DIP2000 diffractometer' _diffrn_detector 'Eu/Ba image plate' _diffrn_measurement_method 'Ninety 2-degree oscillations in phi' _diffrn_standards_decay_% 0 _diffrn_reflns_number 5757 _diffrn_reflns_av_R_equivalents 0.026 _diffrn_reflns_av_sigmaI/netI 0.0253 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 26.30 _reflns_number_total 1567 _reflns_number_observed 1562 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'XPRESS (MAC Science, 1989)' _computing_cell_refinement 'HKL (Otwinowski & Minor, 1996)' _computing_data_reduction 'HKL (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'XPMA/ZORTEP' _computing_publication_material 'CIFTAB' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating -R-factor-obs 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. The ethylene section of the ethanol molecule (atoms C3 and C4) is disordered over two positions and was modelled by the combination of an anisotropic, 90%-occupied fragment with fully-refined hydrogen atoms and an isotropic, 10%-occupied fragment without hydrogen atoms. Splitting the atom N(2) into two or three isotropically-modelled, partially- occupied positions provided no significant reduction of the agreement indices. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+3.0333P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1567 _refine_ls_number_parameters 142 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0437 _refine_ls_R_factor_obs 0.0433 _refine_ls_wR_factor_all 0.0855 _refine_ls_wR_factor_obs 0.0854 _refine_ls_goodness_of_fit_all 1.445 _refine_ls_goodness_of_fit_obs 1.446 _refine_ls_restrained_S_all 1.445 _refine_ls_restrained_S_obs 1.446 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn1 Mn 0.2500 0.2500 0.5000 0.0185(2) Uani 1 d S . N1 N 0.2946(2) 0.3224(2) 0.3475(2) 0.0260(5) Uani 1 d . . N2 N 0.3049(3) 0.3835(2) 0.1613(2) 0.0489(8) Uani 1 d . . N3 N 0.2494(2) 0.5698(2) 0.0713(2) 0.0283(5) Uani 1 d . . C1 C 0.2971(2) 0.3572(2) 0.2615(2) 0.0243(5) Uani 1 d . . C2 C 0.2738(2) 0.4850(2) 0.1188(2) 0.0239(5) Uani 1 d . . O1 O 0.4388(2) 0.2322(2) 0.5644(2) 0.0276(4) Uani 1 d . . H1 H 0.4519(28) 0.1987(28) 0.6176(27) 0.034(9) Uiso 1 d . . C3 C 0.5416(3) 0.2969(3) 0.5407(2) 0.0284(7) Uani 0.90 d P 1 H3A H 0.5131(27) 0.3407(28) 0.4747(26) 0.027(8) Uiso 0.90 d P 1 H3B H 0.6083(30) 0.2423(30) 0.5270(26) 0.033(9) Uiso 0.90 d P 1 C4 C 0.5865(3) 0.3805(3) 0.6301(3) 0.0332(7) Uani 0.90 d P 1 H4A H 0.5242(33) 0.4322(31) 0.6452(28) 0.038(9) Uiso 0.90 d P 1 H4B H 0.6136(30) 0.3359(30) 0.6971(29) 0.035(9) Uiso 0.90 d P 1 H4C H 0.6551(32) 0.4215(31) 0.6079(27) 0.037(9) Uiso 0.90 d P 1 C3B C 0.5151(28) 0.3458(29) 0.5581(25) 0.028(7) Uiso 0.10 d P 2 C4B C 0.6359(37) 0.3214(38) 0.6023(33) 0.058(9) Uiso 0.10 d P 2 O11 O 0.0000 0.4017(2) 0.2500 0.0296(6) Uani 1 d S . C11 C 0.0000 0.5095(3) 0.2500 0.0235(7) Uani 1 d S . C12 C 0.0496(3) 0.5772(3) 0.3470(3) 0.0370(7) Uani 1 d . . H12A H 0.0919(34) 0.5287(33) 0.4014(30) 0.057(11) Uiso 1 d . . H12B H -0.0151(42) 0.6146(40) 0.3823(36) 0.086(14) Uiso 1 d . . H12C H 0.1017(35) 0.6335(36) 0.3253(32) 0.064(12) Uiso 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 0.0271(3) 0.0159(2) 0.0120(2) 0.0002(2) 0.0004(2) -0.0050(2) N1 0.0353(12) 0.0230(10) 0.0199(11) 0.0038(8) 0.0046(9) -0.0022(9) N2 0.098(2) 0.0290(13) 0.0250(12) 0.0126(10) 0.0287(14) 0.0265(14) N3 0.0420(13) 0.0214(11) 0.0207(11) 0.0045(8) 0.0009(9) 0.0043(9) C1 0.0345(14) 0.0161(11) 0.0229(13) 0.0016(9) 0.0059(10) 0.0042(10) C2 0.0330(13) 0.0238(12) 0.0156(11) -0.0009(9) 0.0060(10) 0.0005(10) O1 0.0288(10) 0.0283(10) 0.0240(10) 0.0082(8) -0.0039(7) -0.0083(8) C3 0.027(2) 0.034(2) 0.024(2) -0.0016(14) 0.0044(13) -0.0088(15) C4 0.030(2) 0.029(2) 0.040(2) -0.0053(14) 0.0030(14) -0.0102(14) O11 0.0378(15) 0.0223(13) 0.0267(13) 0.000 -0.0042(11) 0.000 C11 0.020(2) 0.027(2) 0.025(2) 0.000 0.0049(13) 0.000 C12 0.042(2) 0.0296(15) 0.038(2) -0.0071(12) 0.0000(14) -0.0046(13) _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 N1 2.189(2) . ? Mn1 N1 2.189(2) 7_556 ? Mn1 O1 2.200(2) . ? Mn1 O1 2.200(2) 7_556 ? Mn1 N3 2.233(2) 4_545 ? Mn1 N3 2.233(2) 6_566 ? N1 C1 1.148(3) . ? N2 C2 1.300(3) . ? N2 C1 1.300(3) . ? N3 C2 1.147(3) . ? N3 Mn1 2.233(2) 4 ? O1 C3 1.437(3) . ? O1 C3B 1.56(3) . ? O1 H1 0.76(3) . ? C3 C4 1.506(4) . ? C3 H3A 0.98(3) . ? C3 H3B 1.01(3) . ? C4 H4A 0.95(4) . ? C4 H4B 0.99(4) . ? C4 H4C 0.97(4) . ? C3B C4B 1.44(5) . ? O11 C11 1.224(4) . ? C11 C12 1.487(3) . ? C11 C12 1.487(3) 2 ? C12 H12A 0.96(4) . ? C12 H12B 0.99(5) . ? C12 H12C 0.93(4) . ? 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 Mn1 N1 179.999(1) . 7_556 ? N1 Mn1 O1 92.14(8) . . ? N1 Mn1 O1 87.86(8) 7_556 . ? N1 Mn1 O1 87.86(8) . 7_556 ? N1 Mn1 O1 92.14(8) 7_556 7_556 ? O1 Mn1 O1 180.0 . 7_556 ? N1 Mn1 N3 89.16(8) . 4_545 ? N1 Mn1 N3 90.84(8) 7_556 4_545 ? O1 Mn1 N3 90.70(8) . 4_545 ? O1 Mn1 N3 89.30(8) 7_556 4_545 ? N1 Mn1 N3 90.84(8) . 6_566 ? N1 Mn1 N3 89.16(8) 7_556 6_566 ? O1 Mn1 N3 89.30(8) . 6_566 ? O1 Mn1 N3 90.70(8) 7_556 6_566 ? N3 Mn1 N3 180.0 4_545 6_566 ? C1 N1 Mn1 167.9(2) . . ? C2 N2 C1 123.4(2) . . ? C2 N3 Mn1 164.6(2) . 4 ? N1 C1 N2 172.8(3) . . ? N3 C2 N2 172.8(3) . . ? C3 O1 Mn1 130.7(2) . . ? C3B O1 Mn1 115.1(12) . . ? C3 O1 H1 110.9(24) . . ? C3B O1 H1 113.9(27) . . ? Mn1 O1 H1 116.2(24) . . ? O1 C3 C4 112.3(3) . . ? O1 C3 H3A 103.8(18) . . ? C4 C3 H3A 110.5(18) . . ? O1 C3 H3B 111.2(19) . . ? C4 C3 H3B 108.8(19) . . ? H3A C3 H3B 110.3(25) . . ? C3 C4 H4A 110.1(21) . . ? C3 C4 H4B 110.1(20) . . ? H4A C4 H4B 107.9(28) . . ? C3 C4 H4C 107.4(20) . . ? H4A C4 H4C 113.3(29) . . ? H4B C4 H4C 107.9(28) . . ? C4B C3B O1 109.1(26) . . ? O11 C11 C12 121.1(2) . . ? O11 C11 C12 121.1(2) . 2 ? C12 C11 C12 117.7(3) . 2 ? C11 C12 H12A 112.8(22) . . ? C11 C12 H12B 110.8(26) . . ? H12A C12 H12B 105.3(32) . . ? C11 C12 H12C 107.9(24) . . ? H12A C12 H12C 108.8(32) . . ? H12B C12 H12C 111.2(35) . . ? _refine_diff_density_max 0.268 _refine_diff_density_min -0.284 _refine_diff_density_rms 0.047 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END data_mndca2trihydrate _audit_creation_method SHELXL _chemical_name_systematic ; manganese bis(dicyanamide) dihydrate water solvate ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C4 H6 Mn N6 O3' _chemical_formula_weight 241.09 _chemical_melting_point ? _chemical_compound_source ? 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' 'N' 'N' 0.0061 0.0033 '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' 'O' 'O' 0.0106 0.0060 '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' _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 7.3165(2) _cell_length_b 11.6229(5) _cell_length_c 11.3590(5) _cell_angle_alpha 90.00 _cell_angle_beta 103.241(5) _cell_angle_gamma 90.00 _cell_volume 940.28(6) _cell_formula_units_Z 4 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour colourless _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.23 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.703 _exptl_crystal_density_method ? _exptl_crystal_F_000 484 _exptl_absorpt_coefficient_mu 1.397 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3453 _diffrn_reflns_av_R_equivalents 0.031 _diffrn_reflns_av_sigmaI/netI 0.0328 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 3.50 _diffrn_reflns_theta_max 28.19 _reflns_number_total 1787 _reflns_number_observed 1417 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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^)+(0.0576P)^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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1787 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0440 _refine_ls_R_factor_obs 0.0313 _refine_ls_wR_factor_all 0.0992 _refine_ls_wR_factor_obs 0.0926 _refine_ls_goodness_of_fit_all 1.175 _refine_ls_goodness_of_fit_obs 1.246 _refine_ls_restrained_S_all 1.175 _refine_ls_restrained_S_obs 1.246 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Mn1 Mn 0.0000 0.0000 1.0000 0.0138(2) Uani 1 d S . Mn2 Mn 0.0000 0.0000 0.5000 0.0164(2) Uani 1 d S . N3 N -0.4775(3) -0.1505(2) 0.6972(2) 0.0234(5) Uani 1 d . . C1 C -0.3293(3) -0.1121(2) 0.7754(2) 0.0196(5) Uani 1 d . . N1 N -0.2067(3) -0.0709(2) 0.8450(2) 0.0242(5) Uani 1 d . . C2 C -0.4665(3) -0.2479(2) 0.6418(2) 0.0171(5) Uani 1 d . . N2 N -0.4728(2) -0.3318(2) 0.5870(2) 0.0212(5) Uani 1 d . . O1 O 0.2394(2) -0.0341(2) 0.9141(2) 0.0208(4) Uani 1 d . . H11 H 0.3126(42) -0.0791(27) 0.9593(28) 0.041(9) Uiso 1 d . . H12 H 0.2969(46) 0.0273(31) 0.9158(30) 0.051(11) Uiso 1 d . . N6 N -0.4564(2) 0.1520(2) 0.6730(2) 0.0196(4) Uani 1 d . . C4 C -0.3186(3) 0.1215(2) 0.6226(2) 0.0193(5) Uani 1 d . . N4 N -0.1902(3) 0.0967(2) 0.5859(2) 0.0256(5) Uani 1 d . . C5 C -0.6277(3) 0.1413(2) 0.6078(2) 0.0181(5) Uani 1 d . . N5 N -0.7841(3) 0.1333(2) 0.5571(2) 0.0263(5) Uani 1 d . . O2 O 0.1243(2) -0.10256(15) 0.6640(2) 0.0232(4) Uani 1 d . . H21 H 0.1053(44) -0.0859(30) 0.7312(33) 0.056(11) Uiso 1 d . . H22 H 0.2425(58) -0.1045(36) 0.6711(36) 0.089(15) Uiso 1 d . . O3 O 0.5099(2) -0.1497(2) 1.0817(2) 0.0245(4) Uani 1 d . . H31 H 0.4717(53) -0.1577(33) 1.1572(36) 0.076(12) Uiso 1 d . . H32 H 0.5172(49) -0.2134(39) 1.0721(34) 0.069(14) Uiso 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 0.0148(3) 0.0128(3) 0.0123(3) 0.0001(2) 0.0001(2) -0.0006(2) Mn2 0.0104(3) 0.0194(3) 0.0194(3) 0.0018(2) 0.0033(2) 0.0011(2) N3 0.0166(9) 0.0202(11) 0.0281(11) -0.0104(9) -0.0060(8) 0.0025(8) C1 0.0229(12) 0.0138(12) 0.0203(12) -0.0003(10) 0.0014(10) 0.0051(9) N1 0.0267(10) 0.0179(11) 0.0229(11) -0.0021(9) -0.0049(9) -0.0012(8) C2 0.0121(10) 0.0205(13) 0.0161(11) 0.0010(10) -0.0022(8) 0.0005(8) N2 0.0193(10) 0.0197(12) 0.0223(11) -0.0024(9) 0.0000(8) 0.0003(8) O1 0.0174(8) 0.0223(10) 0.0222(9) 0.0025(8) 0.0033(7) 0.0011(8) N6 0.0143(9) 0.0251(11) 0.0191(10) -0.0020(8) 0.0029(8) 0.0015(8) C4 0.0189(12) 0.0197(13) 0.0171(11) 0.0004(9) -0.0002(10) -0.0019(9) N4 0.0171(10) 0.0355(13) 0.0243(11) -0.0043(10) 0.0050(9) 0.0037(8) C5 0.0205(12) 0.0139(12) 0.0218(13) 0.0017(9) 0.0092(10) 0.0003(8) N5 0.0179(10) 0.0304(12) 0.0306(12) -0.0003(9) 0.0052(9) -0.0036(8) O2 0.0217(9) 0.0287(10) 0.0188(10) 0.0015(7) 0.0038(7) 0.0040(7) O3 0.0260(9) 0.0219(11) 0.0258(10) 0.0022(8) 0.0063(7) 0.0007(7) _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 N2 2.179(2) 4_656 ? Mn1 N2 2.179(2) 2_456 ? Mn1 N1 2.202(2) 3_557 ? Mn1 N1 2.202(2) . ? Mn1 O1 2.227(2) 3_557 ? Mn1 O1 2.227(2) . ? Mn2 N4 2.184(2) 3_556 ? Mn2 N4 2.184(2) . ? Mn2 N5 2.201(2) 3_456 ? Mn2 N5 2.201(2) 1_655 ? Mn2 O2 2.223(2) . ? Mn2 O2 2.223(2) 3_556 ? N3 C2 1.307(3) . ? N3 C1 1.313(3) . ? C1 N1 1.154(3) . ? C2 N2 1.151(3) . ? N2 Mn1 2.179(2) 2_446 ? O1 H11 0.83(3) . ? O1 H12 0.83(4) . ? N6 C5 1.308(3) . ? N6 C4 1.317(3) . ? C4 N4 1.149(3) . ? C5 N5 1.161(3) . ? N5 Mn2 2.201(2) 1_455 ? O2 H21 0.83(4) . ? O2 H22 0.85(4) . ? O3 H31 0.97(4) . ? O3 H32 0.75(4) . ? 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 N2 Mn1 N2 180.0 4_656 2_456 ? N2 Mn1 N1 89.92(7) 4_656 3_557 ? N2 Mn1 N1 90.08(7) 2_456 3_557 ? N2 Mn1 N1 90.08(7) 4_656 . ? N2 Mn1 N1 89.92(7) 2_456 . ? N1 Mn1 N1 180.0 3_557 . ? N2 Mn1 O1 87.74(7) 4_656 3_557 ? N2 Mn1 O1 92.26(7) 2_456 3_557 ? N1 Mn1 O1 92.76(7) 3_557 3_557 ? N1 Mn1 O1 87.24(7) . 3_557 ? N2 Mn1 O1 92.26(7) 4_656 . ? N2 Mn1 O1 87.74(7) 2_456 . ? N1 Mn1 O1 87.24(7) 3_557 . ? N1 Mn1 O1 92.76(7) . . ? O1 Mn1 O1 180.0 3_557 . ? N4 Mn2 N4 180.0 3_556 . ? N4 Mn2 N5 89.65(8) 3_556 3_456 ? N4 Mn2 N5 90.35(8) . 3_456 ? N4 Mn2 N5 90.35(8) 3_556 1_655 ? N4 Mn2 N5 89.65(8) . 1_655 ? N5 Mn2 N5 180.0 3_456 1_655 ? N4 Mn2 O2 85.32(7) 3_556 . ? N4 Mn2 O2 94.68(7) . . ? N5 Mn2 O2 89.87(7) 3_456 . ? N5 Mn2 O2 90.13(7) 1_655 . ? N4 Mn2 O2 94.68(7) 3_556 3_556 ? N4 Mn2 O2 85.32(7) . 3_556 ? N5 Mn2 O2 90.13(7) 3_456 3_556 ? N5 Mn2 O2 89.87(7) 1_655 3_556 ? O2 Mn2 O2 180.0 . 3_556 ? C2 N3 C1 119.2(2) . . ? N1 C1 N3 174.8(2) . . ? C1 N1 Mn1 170.5(2) . . ? N2 C2 N3 173.9(2) . . ? C2 N2 Mn1 173.0(2) . 2_446 ? Mn1 O1 H11 107.5(20) . . ? Mn1 O1 H12 106.4(24) . . ? H11 O1 H12 106.0(31) . . ? C5 N6 C4 117.3(2) . . ? N4 C4 N6 175.4(2) . . ? C4 N4 Mn2 161.6(2) . . ? N5 C5 N6 175.3(2) . . ? C5 N5 Mn2 139.6(2) . 1_455 ? Mn2 O2 H21 121.5(23) . . ? Mn2 O2 H22 107.8(27) . . ? H21 O2 H22 107.5(34) . . ? H31 O3 H32 94.5(33) . . ? _refine_diff_density_max 0.381 _refine_diff_density_min -0.600 _refine_diff_density_rms 0.156 _publ_contact_author ; Prof. K.S. Murray Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_contact_author_phone ' +61 3 9905 4512 ' _publ_contact_author_fax ' +61 3 9905 4597 ' _publ_contact_author_email ' Keith.S.Murray@sci.monash.edu.au ' loop_ _publ_author_name _publ_author_address ' Murray, Keith S. ' ; Department of Chemistry Monash University Clayton, Vic. 3168 AUSTRALIA ; _publ_section_title ; Syntheses, Structures and Magnetism of alpha-Mn(dca)2, Mn(dca)2(H2O)2.H2O, Mn(dca)2(C2H5OH)2.(CH3)2CO, Fe(dca)2(CH3OH)2 and Mn(dca)2(L)2, where L=pyridine, CH3OH, DMF and dca- = Dicyanamide, N(CN)2- ; #=END