Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Christian Nather' _publ_contact_author_address ; Olshausenstr. 40 (Otto-Hahn-Platz 6 ; _publ_contact_author_email cnaether@ac.uni-kiel.de loop_ _publ_author_name 'Christian Nather' M.Wriedt # Attachment 'compound-1-2.CIF' data_Compound_1 _database_code_depnum_ccdc_archive 'CCDC 767242' #TrackingRef 'compound-1-2.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; poly[bis(isoselenocyanato-N)-bis(\m2-pyrazine-N,N')-manganese(II)] ; _chemical_name_common ;poly(bis(isoselenocyanato-N)-bis(mu2-pyrazine-N,N')- manganese(ii)) ; _chemical_melting_point ? _chemical_formula_moiety 'C10 H8 Mn N6 Se2' _chemical_formula_sum 'C10 H8 Mn N6 Se2' _chemical_formula_weight 425.08 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' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/m' _symmetry_space_group_name_Hall '-C 2y' 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 10.4442(10) _cell_length_b 10.5411(9) _cell_length_c 7.2533(7) _cell_angle_alpha 90.00 _cell_angle_beta 117.571(7) _cell_angle_gamma 90.00 _cell_volume 707.86(11) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5828 _cell_measurement_theta_min 2.93 _cell_measurement_theta_max 29.22 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.994 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 406 _exptl_absorpt_coefficient_mu 6.068 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.347 _exptl_absorpt_correction_T_max 0.691 _exptl_absorpt_process_details 'X-Shape and X-Red32 (Stoe, 2008)' _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 'Stoe IPDS-2' _diffrn_measurement_method 'Phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% NONE _diffrn_reflns_number 5828 _diffrn_reflns_av_R_equivalents 0.0425 _diffrn_reflns_av_sigmaI/netI 0.0203 _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 -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 2.93 _diffrn_reflns_theta_max 29.22 _reflns_number_total 1009 _reflns_number_gt 917 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-Area (Stoe, 2008)' _computing_cell_refinement 'X-Area (Stoe, 2008)' _computing_data_reduction 'X-Area (Stoe, 2008)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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 _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0277P)^2^+2.0882P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1009 _refine_ls_number_parameters 50 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0487 _refine_ls_R_factor_gt 0.0433 _refine_ls_wR_factor_ref 0.0965 _refine_ls_wR_factor_gt 0.0942 _refine_ls_goodness_of_fit_ref 1.222 _refine_ls_restrained_S_all 1.222 _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 0.0000 0.0000 0.5000 0.0304(2) Uani 1 4 d S . . Se11 Se 0.36521(7) 0.0000 1.23749(10) 0.0678(3) Uani 1 2 d S . . C11 C 0.2057(5) 0.0000 0.9968(8) 0.0394(10) Uani 1 2 d S . . N11 N 0.1060(4) 0.0000 0.8346(7) 0.0439(9) Uani 1 2 d S . . N1 N 0.1577(3) 0.1563(3) 0.5068(5) 0.0379(6) Uani 1 1 d . . . C1 C 0.2877(4) 0.1767(4) 0.6651(6) 0.0509(9) Uani 1 1 d . . . H1 H 0.3184 0.1271 0.7841 0.061 Uiso 1 1 calc R . . C2 C 0.1211(4) 0.2300(4) 0.3422(6) 0.0504(9) Uani 1 1 d . . . H2 H 0.0311 0.2189 0.2275 0.061 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Mn1 0.0263(4) 0.0265(4) 0.0400(5) 0.000 0.0168(4) 0.000 Se11 0.0468(3) 0.0963(6) 0.0456(4) 0.000 0.0089(3) 0.000 C11 0.038(2) 0.040(2) 0.045(3) 0.000 0.023(2) 0.000 N11 0.040(2) 0.047(2) 0.043(2) 0.000 0.0180(18) 0.000 N1 0.0317(12) 0.0342(13) 0.0484(16) 0.0030(12) 0.0189(12) -0.0023(10) C1 0.0413(18) 0.050(2) 0.054(2) 0.0102(17) 0.0155(16) -0.0095(15) C2 0.0392(17) 0.051(2) 0.053(2) 0.0103(18) 0.0148(15) -0.0091(15) _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 N11 2.151(4) . ? Mn1 N11 2.151(4) 5_556 ? Mn1 N1 2.314(2) 5_556 ? Mn1 N1 2.314(2) . ? Mn1 N1 2.314(2) 2_556 ? Mn1 N1 2.314(2) 6 ? Se11 C11 1.769(5) . ? C11 N11 1.155(6) . ? N1 C2 1.324(4) . ? N1 C1 1.329(4) . ? C1 C2 1.387(5) 7_556 ? C1 H1 0.9300 . ? C2 C1 1.387(5) 7_556 ? C2 H2 0.9300 . ? 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 N11 Mn1 N11 180.0 . 5_556 ? N11 Mn1 N1 90.79(11) . 5_556 ? N11 Mn1 N1 89.21(11) 5_556 5_556 ? N11 Mn1 N1 89.21(11) . . ? N11 Mn1 N1 90.79(11) 5_556 . ? N1 Mn1 N1 180.00(13) 5_556 . ? N11 Mn1 N1 90.79(11) . 2_556 ? N11 Mn1 N1 89.21(11) 5_556 2_556 ? N1 Mn1 N1 90.81(13) 5_556 2_556 ? N1 Mn1 N1 89.19(13) . 2_556 ? N11 Mn1 N1 89.21(11) . 6 ? N11 Mn1 N1 90.79(11) 5_556 6 ? N1 Mn1 N1 89.19(13) 5_556 6 ? N1 Mn1 N1 90.81(13) . 6 ? N1 Mn1 N1 180.0 2_556 6 ? N11 C11 Se11 176.5(4) . . ? C11 N11 Mn1 154.1(4) . . ? C2 N1 C1 115.9(3) . . ? C2 N1 Mn1 119.6(2) . . ? C1 N1 Mn1 124.5(2) . . ? N1 C1 C2 121.8(3) . 7_556 ? N1 C1 H1 119.1 . . ? C2 C1 H1 119.1 7_556 . ? N1 C2 C1 122.3(3) . 7_556 ? N1 C2 H2 118.9 . . ? C1 C2 H2 118.9 7_556 . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 29.22 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.359 _refine_diff_density_min -0.664 _refine_diff_density_rms 0.080 #END #============================================================================= data_mwp3 _database_code_depnum_ccdc_archive 'CCDC 767243' #TrackingRef 'compound-1-2.CIF' #============================================================================= # 5. CHEMICAL DATA _chemical_name_systematic ; poly[bis(\m2-selenocyanato-N,S)-(\m2-pyrazine-N,N')-manganese(II)] ; _chemical_name_common ;poly(bis(mu2-selenocyanato-N,S)-(mu2-pyrazine-N,N')- manganese(ii)) ; _chemical_formula_moiety 'C6 H4 Mn N4 Se2' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_iupac ? _chemical_formula_sum 'C6 H4 Mn N4 Se2' _chemical_formula_weight 344.98 _chemical_melting_point ? _chemical_compound_source ? # for minerals and # natural products loop_ _atom_type_symbol _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source mn 11.28190 5.34090 7.35730 0.34320 3.01930 17.86740 2.24410 83.75430 1.08960 -0.56800 2.80800 International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5 se 17.00060 2.40980 5.81960 0.27260 3.97310 15.23720 4.35430 43.81630 2.84090 -0.87900 1.13900 International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5 c 2.31000 20.84390 1.02000 10.20750 1.58860 0.56870 0.86500 51.65120 0.21560 0.01700 0.00900 International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5 n 12.21260 0.00570 3.13220 9.89330 2.01250 28.99750 1.16630 0.58260 -11.52900 0.02900 0.01800 International_Tables_for_Crystallography_Vol.C(1991)_Tables_6.1.1.4_and_6.1.1.5 #============================================================================= # 6. POWDER SPECIMEN AND CRYSTAL DATA _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'C 2/m' _symmetry_space_group_name_Hall '-C 2y' loop_ _symmetry_equiv_pos_as_xyz #<--must include 'x,y,z' x,y,z -x,y,-z -x,-y,-z x,-y,z x+1/2,y+1/2,z -x+1/2,y+1/2,-z -x+1/2,-y+1/2,-z x+1/2,-y+1/2,z _cell_length_a 10.9748(3) _cell_length_b 7.47768(19) _cell_length_c 5.88895(16) _cell_angle_alpha 90.00000 _cell_angle_beta 94.9325(8) _cell_angle_gamma 90.00000 _cell_volume 481.49(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293 _cell_special_details ; ? ; # The next three fields give the specimen dimensions in mm. The equatorial # plane contains the incident and diffracted beam. _pd_spec_size_axial ? # perpendicular to # equatorial plane _pd_spec_size_equat ? # parallel to # scattering vector # in transmission _pd_spec_size_thick ? # parallel to # scattering vector # in reflection # The next five fields are character fields that describe the specimen. _pd_spec_mounting # This field should be # used to give details of the # container. ; ? ; _pd_spec_mount_mode transmission _pd_spec_shape flat_sheet _pd_char_particle_morphology ? _pd_char_colour 'light grey' # The following three fields describe the preparation of the specimen. # The cooling rate is in K/min. The pressure at which the sample was # prepared is in kPa. The temperature of preparation is in K. _pd_prep_cool_rate ? _pd_prep_pressure ? _pd_prep_temperature ? # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu ? _exptl_absorpt_correction_type NONE _exptl_absorpt_process_details ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_crystal_density_diffrn 2.352 #============================================================================= # 7. EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; ? ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; ? ; _diffrn_ambient_temperature 293 _diffrn_source ? _diffrn_radiation_type 'Cu K\a' _diffrn_source_target Cu # Put here the chemical symbol of the anode _diffrn_radiation_monochromator ? _diffrn_radiation_wavelength 1.540560 _diffrn_measurement_device_type 'STOE Stadi P' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? # Not in version 2.0.1 _diffrn_detector ? _diffrn_detector_type ? # make or model of detector _pd_meas_scan_method ? # options are 'step', 'cont', # 'tof', 'fixed' or # 'disp' (= dispersive) _pd_meas_special_details ; ? ; # The following four items give details of the measured (not processed) # powder pattern. Angles are in degrees. _pd_meas_number_of_points 9995 _pd_meas_2theta_range_min 10.03200 _pd_meas_2theta_range_max 79.99000 _pd_meas_2theta_range_inc 0.007000 #============================================================================= # 8. REFINEMENT DATA _refine_special_details ; ? ; # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ? _pd_proc_ls_background_function ? _pd_proc_ls_pref_orient_corr ; ? ; # The following profile R-factors are NOT CORRECTED for background # The sum is extended to all non-excluded points. # These are the current CIF standard _pd_proc_ls_prof_R_factor 2.1382 _pd_proc_ls_prof_wR_factor 2.9794 _pd_proc_ls_prof_wR_expected 1.2363 # The following profile R-factors are CORRECTED for background # The sum is extended to all non-excluded points. # These items are not in the current CIF standard, but are defined above _pd_proc_ls_prof_cR_factor 13.7295 _pd_proc_ls_prof_cwR_factor 11.7651 _pd_proc_ls_prof_cwR_expected 4.8821 # The following items are not in the CIF standard, but are defined above _pd_proc_ls_prof_chi2 5.8073 _pd_proc_ls_prof_echi2 5.9795 # Items related to LS refinement _refine_ls_R_I_factor 5.7706 _refine_ls_number_reflns 189 _refine_ls_number_parameters 27 _refine_ls_number_restraints 1 _refine_ls_hydrogen_treatment undef _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 # The following four items apply to angular dispersive measurements. # 2theta minimum, maximum and increment (in degrees) are for the # intensities used in the refinement. _pd_proc_2theta_range_min 10.1152 _pd_proc_2theta_range_max 80.0732 _pd_proc_2theta_range_inc 0.007000 _pd_proc_wavelength 1.540560 _pd_block_diffractogram_id ? # The id used for the block containing # the powder pattern profile (section 11) # Give appropriate details in the next two text fields. _pd_proc_info_excluded_regions ? _pd_proc_info_data_reduction ? # The following items are used to identify the programs used. _computing_data_collection ? _computing_structure_solution ? _computing_structure_refinement FULLPROF _computing_molecular_graphics ? _computing_publication_material ? #============================================================================= # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type # Not in version 2.0.1 _atom_site_type_symbol MN1 0.00000 0.50000 0.00000 0.0449(10) 1.00000 Uiso Mn Se11 0.22142(9) 0.50000 0.2780(2) 0.0464(5) 1.00000 Uiso Se C11 0.1567(7) 0.50000 0.5421(13) 0.021(2) 1.00000 Uiso C N11 0.1103(6) 0.50000 0.7122(11) 0.043(2) 1.00000 Uiso N N1 0.00000 0.1825(4) 0.00000 0.043(2) 1.00000 Uiso N C1 0.0475(3) 0.0958(5) 0.1865(6) 0.021(2) 1.00000 Uiso C # Note: if the displacement parameters were refined anisotropically # the U matrices should be given as for single-crystal studies. #============================================================================= # 10. DISTANCES AND ANGLES / MOLECULAR GEOMETRY _geom_special_details ? 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 N11 2.166(7) 1_554 ? Mn1 N1 2.374(3) . ? Mn1 Se11 2.8109(11) . ? Se11 C11 1.765(8) . ? C11 N11 1.162(10) . ? N11 Mn1 2.166(7) 1_556 ? N1 C1 1.342(4) 2 ? N1 C1 1.342(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 N11 Mn1 N1 90.0 1_554 . ? N11 Mn1 Se11 86.70(17) 1_554 . ? N1 Mn1 Se11 90.00(1) . . ? C11 Se11 Mn1 96.9(3) . . ? N11 C11 Se11 177.8(7) . . ? C11 N11 Mn1 172.(6) . 1_556 ? C1 N1 C1 122.04(8) 2 . ? C1 N1 Mn1 118.90(19) . . ? #