# Electronic Supplementary Material for CrystEngComm # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_coden_Cambridge 1350 _journal_volume ? _journal_page_first ? _journal_year ? loop_ _publ_author_name _publ_author_address 'Keith Murray' ;School of Chemistry Monash University Clayton VIC 3800 Australia ; 'Stuart R. Batten' ;School of Chemistry Monash University Clayton VIC 3800 Australia ; 'Paul Jensen' ;School of Chemistry Monash University Clayton VIC 3800 Australia ; 'Boujemaa Moubaraki' ;School of Chemistry Monash University Clayton VIC 3800 Australia ; 'David Turner' ;School of Chemistry Monash University Clayton VIC 3800 Australia ; _publ_contact_author_name 'Keith Murray' _publ_contact_author_email KEITH.MURRAY@SCI.MONASH.EDU.AU _publ_section_title ; Coordination Polymers of Nitrocyanamide, O2NNCN-. Synthesis, Structure and Magnetism ; _publ_contact_author_address ;School of Chemistry Monash University Clayton VIC 3800 Australia ; _publ_requested_journal CrystEngComm # Attachment 'AnnaCh6_CIF.CIF' data_1 _database_code_depnum_ccdc_archive 'CCDC 725137' _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena[bis(nitrocyanamide)(pyrazine)Copper(II)] ; _chemical_name_common '[Cu(CAN)2(pyz)]' _chemical_melting_point ? _chemical_formula_moiety 'C6 H4 Cu N8 O4' _chemical_formula_sum 'C6 H4 Cu N8 O4' _chemical_formula_weight 315.71 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' Cu Cu 0.3201 1.2651 '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 6.3272(2) _cell_length_b 6.8535(2) _cell_length_c 6.9057(2) _cell_angle_alpha 112.863(2) _cell_angle_beta 102.779(2) _cell_angle_gamma 103.167(2) _cell_volume 252.161(13) _cell_formula_units_Z 1 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 2087 _cell_measurement_theta_min 3.41 _cell_measurement_theta_max 27.49 _exptl_crystal_description block _exptl_crystal_colour blue _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.079 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 157 _exptl_absorpt_coefficient_mu 2.196 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.3983 _exptl_absorpt_correction_T_max 0.7194 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2087 _diffrn_reflns_av_R_equivalents 0.0424 _diffrn_reflns_av_sigmaI/netI 0.0468 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.41 _diffrn_reflns_theta_max 27.49 _reflns_number_total 1096 _reflns_number_gt 1038 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_extinction_expression ? _refine_ls_number_reflns 1096 _refine_ls_number_parameters 88 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0379 _refine_ls_R_factor_gt 0.0335 _refine_ls_wR_factor_ref 0.0886 _refine_ls_wR_factor_gt 0.0863 _refine_ls_goodness_of_fit_ref 1.136 _refine_ls_restrained_S_all 1.136 _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 Cu1 Cu 0.5000 0.5000 0.5000 0.00683(18) Uani 1 2 d S . . O1 O -0.0990(3) 0.6651(3) 0.7333(3) 0.0120(4) Uani 1 1 d . . . N1 N 0.4981(4) 0.7984(3) 0.5021(3) 0.0067(4) Uani 1 1 d . . . N2 N 0.3719(4) 0.5658(4) 0.7437(4) 0.0098(5) Uani 1 1 d . . . O2 O -0.1091(3) 0.8100(3) 1.0735(3) 0.0160(4) Uani 1 1 d . . . C1 C 0.3298(5) 0.8802(4) 0.5377(4) 0.0082(5) Uani 1 1 d . . . H1 H 0.2066 0.7988 0.5650 0.010 Uiso 1 1 calc R . . N4 N -0.0125(4) 0.7334(4) 0.9412(4) 0.0101(5) Uani 1 1 d . . . N3 N 0.1968(4) 0.7228(4) 1.0266(4) 0.0124(5) Uani 1 1 d . . . C2 C 0.6677(5) 0.9183(4) 0.4647(4) 0.0080(5) Uani 1 1 d . . . H2 H 0.7896 0.8642 0.4392 0.010 Uiso 1 1 calc R . . C3 C 0.2808(4) 0.6372(4) 0.8679(4) 0.0088(5) 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 Cu1 0.0089(3) 0.0077(2) 0.0092(3) 0.00560(19) 0.00637(18) 0.00596(18) O1 0.0089(10) 0.0180(10) 0.0088(9) 0.0062(8) 0.0024(8) 0.0049(8) N1 0.0076(11) 0.0075(10) 0.0049(10) 0.0028(8) 0.0013(8) 0.0037(8) N2 0.0103(12) 0.0117(11) 0.0101(11) 0.0061(9) 0.0042(9) 0.0057(9) O2 0.0136(11) 0.0219(11) 0.0163(10) 0.0062(8) 0.0117(8) 0.0111(9) C1 0.0081(13) 0.0105(12) 0.0075(12) 0.0045(10) 0.0032(10) 0.0048(10) N4 0.0083(11) 0.0111(10) 0.0109(11) 0.0050(9) 0.0037(9) 0.0029(9) N3 0.0103(12) 0.0210(12) 0.0082(11) 0.0060(10) 0.0048(9) 0.0093(10) C2 0.0070(13) 0.0100(12) 0.0082(12) 0.0039(10) 0.0037(10) 0.0047(10) C3 0.0082(13) 0.0102(12) 0.0084(12) 0.0057(10) 0.0015(10) 0.0027(10) _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 Cu1 N2 1.968(2) 2_666 ? Cu1 N2 1.968(2) . ? Cu1 N1 2.042(2) . ? Cu1 N1 2.042(2) 2_666 ? Cu1 O1 2.4043(19) 1_655 ? Cu1 O1 2.4043(19) 2_566 ? O1 N4 1.262(3) . ? O1 Cu1 2.4043(19) 1_455 ? N1 C2 1.334(3) . ? N1 C1 1.338(3) . ? N2 C3 1.152(3) . ? O2 N4 1.226(3) . ? C1 C2 1.384(4) 2_676 ? N4 N3 1.356(3) . ? N3 C3 1.315(3) . ? C2 C1 1.384(3) 2_676 ? 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 Cu1 N2 180.000(1) 2_666 . ? N2 Cu1 N1 90.04(9) 2_666 . ? N2 Cu1 N1 89.96(9) . . ? N2 Cu1 N1 89.96(9) 2_666 2_666 ? N2 Cu1 N1 90.04(9) . 2_666 ? N1 Cu1 N1 180.0 . 2_666 ? N2 Cu1 O1 83.17(8) 2_666 1_655 ? N2 Cu1 O1 96.83(8) . 1_655 ? N1 Cu1 O1 91.89(8) . 1_655 ? N1 Cu1 O1 88.11(8) 2_666 1_655 ? N2 Cu1 O1 96.83(8) 2_666 2_566 ? N2 Cu1 O1 83.17(8) . 2_566 ? N1 Cu1 O1 88.11(8) . 2_566 ? N1 Cu1 O1 91.89(8) 2_666 2_566 ? O1 Cu1 O1 180.0 1_655 2_566 ? N4 O1 Cu1 128.64(16) . 1_455 ? C2 N1 C1 117.5(2) . . ? C2 N1 Cu1 120.03(17) . . ? C1 N1 Cu1 122.47(17) . . ? C3 N2 Cu1 163.9(2) . . ? N1 C1 C2 121.0(2) . 2_676 ? O2 N4 O1 123.1(2) . . ? O2 N4 N3 117.2(2) . . ? O1 N4 N3 119.7(2) . . ? C3 N3 N4 111.1(2) . . ? N1 C2 C1 121.5(2) . 2_676 ? N2 C3 N3 173.9(3) . . ? _diffrn_measured_fraction_theta_max 0.954 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.954 _refine_diff_density_max 0.512 _refine_diff_density_min -1.436 _refine_diff_density_rms 0.200 data_2Co _database_code_depnum_ccdc_archive 'CCDC 725138' _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena[bis(aqua)bis(nitrocyanamide)(pyrazine)copper(II)] dihydrate ; _chemical_name_common {[Cu(CAN)2(pyz)(H2O)2].2H2O} _chemical_melting_point ? _chemical_formula_moiety 'C6 H8 Co N8 O6, 2(H2 O)' _chemical_formula_sum 'C6 H12 Co N8 O8' _chemical_formula_weight 383.17 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 triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.7301(1) _cell_length_b 7.0910(1) _cell_length_c 8.6218(2) _cell_angle_alpha 109.184(1) _cell_angle_beta 90.647(1) _cell_angle_gamma 107.858(1) _cell_volume 367.001(11) _cell_formula_units_Z 1 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 6753 _cell_measurement_theta_min 3.33 _cell_measurement_theta_max 27.50 _exptl_crystal_description needle _exptl_crystal_colour pink _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.734 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 195 _exptl_absorpt_coefficient_mu 1.227 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.6396 _exptl_absorpt_correction_T_max 0.8568 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 'Bruker X8 Apex II CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6753 _diffrn_reflns_av_R_equivalents 0.0407 _diffrn_reflns_av_sigmaI/netI 0.0360 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.33 _diffrn_reflns_theta_max 27.50 _reflns_number_total 1680 _reflns_number_gt 1497 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART (Bruker)' _computing_cell_refinement 'Bruker SMART (Bruker)' _computing_data_reduction 'Bruker SAINT (Bruker)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^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_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1680 _refine_ls_number_parameters 122 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0313 _refine_ls_R_factor_gt 0.0250 _refine_ls_wR_factor_ref 0.0565 _refine_ls_wR_factor_gt 0.0548 _refine_ls_goodness_of_fit_ref 1.075 _refine_ls_restrained_S_all 1.075 _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 0.5000 0.5000 0.5000 0.01063(10) Uani 1 2 d S . . O1 O 0.18205(18) 0.41596(18) 0.51128(17) 0.0155(2) Uani 1 1 d . . . N1 N 0.5038(2) 0.80471(18) 0.50002(16) 0.0116(3) Uani 1 1 d . . . N2 N 0.4320(2) 0.37233(19) 0.23977(16) 0.0147(3) Uani 1 1 d . . . O3 O 0.1924(2) -0.09267(17) -0.03427(15) 0.0251(3) Uani 1 1 d . . . N4 N 0.2032(2) 0.0174(2) -0.12194(16) 0.0181(3) Uani 1 1 d . . . N3 N 0.2971(2) 0.2300(2) -0.05824(16) 0.0183(3) Uani 1 1 d . . . C11 C 0.6329(2) 0.9869(2) 0.60885(19) 0.0134(3) Uani 1 1 d . . . H11 H 0.7296 0.9829 0.6878 0.016 Uiso 1 1 calc R . . O4 O 0.1293(2) -0.05600(19) -0.26952(15) 0.0281(3) Uani 1 1 d . . . C10 C 0.3718(2) 0.8199(2) 0.39145(19) 0.0132(3) Uani 1 1 d . . . H10 H 0.2786 0.6942 0.3121 0.016 Uiso 1 1 calc R . . C12 C 0.3653(2) 0.2940(2) 0.10178(19) 0.0137(3) Uani 1 1 d . . . O2 O 0.07090(19) 0.4553(2) 0.81246(15) 0.0202(3) Uani 1 1 d . . . H3 H 0.140(4) 0.428(4) 0.601(3) 0.041(7) Uiso 1 1 d . . . H4 H 0.097(4) 0.329(4) 0.441(3) 0.041(7) Uiso 1 1 d . . . H5 H 0.143(4) 0.404(4) 0.856(3) 0.047(7) Uiso 1 1 d . . . H6 H 0.107(4) 0.574(4) 0.865(3) 0.055(8) Uiso 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 0.01269(17) 0.00774(15) 0.01087(17) 0.00249(11) -0.00135(11) 0.00347(11) O1 0.0132(6) 0.0164(6) 0.0132(7) 0.0020(5) -0.0008(5) 0.0034(5) N1 0.0126(6) 0.0093(6) 0.0129(7) 0.0036(5) 0.0006(5) 0.0040(5) N2 0.0190(7) 0.0112(6) 0.0135(7) 0.0043(5) 0.0005(6) 0.0046(5) O3 0.0359(7) 0.0150(6) 0.0209(7) 0.0047(5) 0.0023(5) 0.0056(5) N4 0.0182(7) 0.0165(7) 0.0138(7) 0.0010(6) 0.0024(6) 0.0021(5) N3 0.0249(8) 0.0137(6) 0.0104(7) 0.0022(5) -0.0024(6) 0.0005(5) C11 0.0134(8) 0.0121(7) 0.0134(8) 0.0031(6) -0.0032(6) 0.0038(6) O4 0.0297(7) 0.0284(7) 0.0114(6) -0.0022(5) -0.0037(5) -0.0008(5) C10 0.0129(8) 0.0117(7) 0.0132(8) 0.0032(6) -0.0019(6) 0.0028(6) C12 0.0152(8) 0.0108(7) 0.0161(9) 0.0063(6) 0.0026(6) 0.0039(6) O2 0.0191(6) 0.0198(6) 0.0175(6) 0.0035(5) -0.0011(5) 0.0040(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 Co1 O1 2.0504(11) . ? Co1 O1 2.0504(11) 2_666 ? Co1 N2 2.1097(13) 2_666 ? Co1 N2 2.1097(13) . ? Co1 N1 2.1530(12) . ? Co1 N1 2.1530(12) 2_666 ? O1 H3 0.81(3) . ? O1 H4 0.78(2) . ? N1 C10 1.3352(19) . ? N1 C11 1.3420(19) . ? N2 C12 1.1516(19) . ? O3 N4 1.2409(18) . ? N4 O4 1.2364(17) . ? N4 N3 1.3556(18) . ? N3 C12 1.329(2) . ? C11 C10 1.381(2) 2_676 ? C11 H11 0.9500 . ? C10 C11 1.381(2) 2_676 ? C10 H10 0.9500 . ? O2 H5 0.84(3) . ? O2 H6 0.77(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 Co1 O1 180.00(8) . 2_666 ? O1 Co1 N2 92.11(5) . 2_666 ? O1 Co1 N2 87.89(5) 2_666 2_666 ? O1 Co1 N2 87.89(5) . . ? O1 Co1 N2 92.11(5) 2_666 . ? N2 Co1 N2 180.0 2_666 . ? O1 Co1 N1 89.85(4) . . ? O1 Co1 N1 90.15(4) 2_666 . ? N2 Co1 N1 89.19(5) 2_666 . ? N2 Co1 N1 90.81(5) . . ? O1 Co1 N1 90.15(4) . 2_666 ? O1 Co1 N1 89.85(4) 2_666 2_666 ? N2 Co1 N1 90.81(5) 2_666 2_666 ? N2 Co1 N1 89.19(5) . 2_666 ? N1 Co1 N1 180.0 . 2_666 ? Co1 O1 H3 119.0(16) . . ? Co1 O1 H4 124.6(17) . . ? H3 O1 H4 110(2) . . ? C10 N1 C11 116.69(12) . . ? C10 N1 Co1 120.58(9) . . ? C11 N1 Co1 122.72(10) . . ? C12 N2 Co1 170.20(12) . . ? O4 N4 O3 123.37(13) . . ? O4 N4 N3 115.83(13) . . ? O3 N4 N3 120.80(13) . . ? C12 N3 N4 111.27(13) . . ? N1 C11 C10 121.45(14) . 2_676 ? N1 C11 H11 119.3 . . ? C10 C11 H11 119.3 2_676 . ? N1 C10 C11 121.87(13) . 2_676 ? N1 C10 H10 119.1 . . ? C11 C10 H10 119.1 2_676 . ? N2 C12 N3 172.21(15) . . ? H5 O2 H6 105(2) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H3 O2 0.81(3) 1.85(3) 2.6601(18) 174(2) . O1 H4 O4 0.78(2) 2.12(3) 2.8941(17) 170(2) 2 O2 H5 N3 0.84(3) 2.13(3) 2.9556(19) 172(2) 1_556 O2 H6 O3 0.77(3) 2.11(3) 2.8763(17) 169(3) 1_566 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.280 _refine_diff_density_min -0.459 _refine_diff_density_rms 0.061 data_2Fe _database_code_depnum_ccdc_archive 'CCDC 725139' _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena[bis(aqua)bis(nitrocyanamide)(pyrazine)iron(II)] dihydrate ; _chemical_name_common {[Fe(CAN)2(pyz)(H2O)2].2H2O} _chemical_melting_point ? _chemical_formula_moiety 'C6 H8 Fe N8 O6, 2 (H2 O)' _chemical_formula_sum 'C6 H12 Fe N8 O8' _chemical_formula_weight 380.09 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _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 6.7652(1) _cell_length_b 7.1822(1) _cell_length_c 8.6218(2) _cell_angle_alpha 109.404(1) _cell_angle_beta 90.408(1) _cell_angle_gamma 108.002(1) _cell_volume 372.961(11) _cell_formula_units_Z 1 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 6688 _cell_measurement_theta_min 3.69 _cell_measurement_theta_max 27.49 _exptl_crystal_description rods _exptl_crystal_colour yellow _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.692 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 194 _exptl_absorpt_coefficient_mu 1.068 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.5912 _exptl_absorpt_correction_T_max 0.8736 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6688 _diffrn_reflns_av_R_equivalents 0.0282 _diffrn_reflns_av_sigmaI/netI 0.0320 _diffrn_reflns_limit_h_min -8 _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 11 _diffrn_reflns_theta_min 3.69 _diffrn_reflns_theta_max 27.49 _reflns_number_total 1706 _reflns_number_gt 1552 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^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_extinction_expression ? _refine_ls_number_reflns 1706 _refine_ls_number_parameters 122 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0299 _refine_ls_R_factor_gt 0.0244 _refine_ls_wR_factor_ref 0.0579 _refine_ls_wR_factor_gt 0.0561 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _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 Fe1 Fe 0.5000 0.5000 0.5000 0.01175(10) Uani 1 2 d S . . O1 O 0.17946(16) 0.41483(17) 0.51096(15) 0.0175(2) Uani 1 1 d . . . O2 O 0.06931(17) 0.45923(19) 0.81240(14) 0.0226(2) Uani 1 1 d . . . N1 N 0.50397(18) 0.80725(17) 0.50045(14) 0.0138(2) Uani 1 1 d . . . O3 O 0.19300(19) -0.09039(16) -0.03919(14) 0.0277(3) Uani 1 1 d . . . N2 N 0.43115(19) 0.37130(17) 0.23587(15) 0.0173(3) Uani 1 1 d . . . N4 N 0.19846(19) 0.01923(19) -0.12542(15) 0.0203(3) Uani 1 1 d . . . N3 N 0.2883(2) 0.22991(19) -0.06024(15) 0.0210(3) Uani 1 1 d . . . O4 O 0.12285(19) -0.05288(18) -0.27225(14) 0.0320(3) Uani 1 1 d . . . C11 C 0.6301(2) 0.9874(2) 0.60980(17) 0.0158(3) Uani 1 1 d . . . H11 H 0.7250 0.9839 0.6897 0.019 Uiso 1 1 calc R . . C10 C 0.3739(2) 0.8214(2) 0.39024(17) 0.0154(3) Uani 1 1 d . . . H10 H 0.2821 0.6969 0.3101 0.018 Uiso 1 1 calc R . . C12 C 0.3611(2) 0.2933(2) 0.09853(18) 0.0156(3) Uani 1 1 d . . . H3 H 0.134(3) 0.424(3) 0.603(3) 0.041(6) Uiso 1 1 d . . . H4 H 0.095(4) 0.331(4) 0.442(3) 0.042(6) Uiso 1 1 d . . . H5 H 0.132(4) 0.407(4) 0.851(3) 0.049(7) Uiso 1 1 d . . . H6 H 0.115(4) 0.587(4) 0.864(3) 0.054(7) Uiso 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 Fe1 0.01463(16) 0.00899(14) 0.01053(16) 0.00233(11) -0.00207(10) 0.00367(10) O1 0.0157(5) 0.0186(5) 0.0138(6) 0.0022(4) -0.0020(5) 0.0038(4) O2 0.0221(6) 0.0226(6) 0.0180(6) 0.0040(5) -0.0017(4) 0.0037(5) N1 0.0166(6) 0.0107(5) 0.0140(6) 0.0043(5) -0.0007(5) 0.0046(4) O3 0.0395(7) 0.0156(5) 0.0238(6) 0.0046(5) 0.0014(5) 0.0059(5) N2 0.0238(7) 0.0126(5) 0.0138(6) 0.0036(5) -0.0011(5) 0.0052(5) N4 0.0204(6) 0.0190(6) 0.0131(7) -0.0004(5) 0.0015(5) 0.0017(5) N3 0.0280(7) 0.0167(6) 0.0112(6) 0.0028(5) -0.0043(5) -0.0001(5) O4 0.0342(7) 0.0319(6) 0.0122(6) -0.0028(5) -0.0046(5) -0.0014(5) C11 0.0179(7) 0.0133(6) 0.0146(7) 0.0036(5) -0.0048(5) 0.0045(5) C10 0.0176(7) 0.0112(6) 0.0143(7) 0.0021(5) -0.0037(5) 0.0031(5) C12 0.0172(7) 0.0124(6) 0.0170(8) 0.0057(6) 0.0022(6) 0.0040(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 Fe1 O1 2.0753(10) 2_666 ? Fe1 O1 2.0753(10) . ? Fe1 N2 2.1395(12) . ? Fe1 N2 2.1395(12) 2_666 ? Fe1 N1 2.1973(10) 2_666 ? Fe1 N1 2.1973(11) . ? O1 H3 0.84(2) . ? O1 H4 0.77(2) . ? O2 H5 0.78(2) . ? O2 H6 0.83(3) . ? N1 C11 1.3367(18) . ? N1 C10 1.3400(17) . ? O3 N4 1.2431(17) . ? N2 C12 1.1522(18) . ? N4 O4 1.2344(16) . ? N4 N3 1.3552(17) . ? N3 C12 1.3272(19) . ? C11 C10 1.3815(18) 2_676 ? C11 H11 0.9500 . ? C10 C11 1.3815(18) 2_676 ? C10 H10 0.9500 . ? 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 2_666 . ? O1 Fe1 N2 92.38(5) 2_666 . ? O1 Fe1 N2 87.62(5) . . ? O1 Fe1 N2 87.62(5) 2_666 2_666 ? O1 Fe1 N2 92.38(5) . 2_666 ? N2 Fe1 N2 180.0 . 2_666 ? O1 Fe1 N1 89.90(4) 2_666 2_666 ? O1 Fe1 N1 90.10(4) . 2_666 ? N2 Fe1 N1 89.21(4) . 2_666 ? N2 Fe1 N1 90.79(4) 2_666 2_666 ? O1 Fe1 N1 90.10(4) 2_666 . ? O1 Fe1 N1 89.90(4) . . ? N2 Fe1 N1 90.79(4) . . ? N2 Fe1 N1 89.21(4) 2_666 . ? N1 Fe1 N1 180.0 2_666 . ? Fe1 O1 H3 119.4(15) . . ? Fe1 O1 H4 125.8(17) . . ? H3 O1 H4 109(2) . . ? H5 O2 H6 108(2) . . ? C11 N1 C10 116.59(11) . . ? C11 N1 Fe1 122.92(9) . . ? C10 N1 Fe1 120.48(9) . . ? C12 N2 Fe1 169.02(11) . . ? O4 N4 O3 123.45(12) . . ? O4 N4 N3 115.83(12) . . ? O3 N4 N3 120.72(12) . . ? C12 N3 N4 111.55(11) . . ? N1 C11 C10 121.77(12) . 2_676 ? N1 C11 H11 119.1 . . ? C10 C11 H11 119.1 2_676 . ? N1 C10 C11 121.65(12) . 2_676 ? N1 C10 H10 119.2 . . ? C11 C10 H10 119.2 2_676 . ? N2 C12 N3 172.11(14) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H3 O2 0.84(2) 1.81(2) 2.6523(16) 173(2) . O1 H4 O4 0.77(2) 2.12(2) 2.8767(16) 168(2) 2 O2 H5 N3 0.78(2) 2.19(3) 2.9667(18) 174(2) 1_556 O2 H6 O3 0.83(3) 2.07(3) 2.8918(16) 170(2) 1_566 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.295 _refine_diff_density_min -0.488 _refine_diff_density_rms 0.084 data_3Co _database_code_depnum_ccdc_archive 'CCDC 725140' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Co(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy ; _chemical_name_common "[Co(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy" _chemical_melting_point ? _chemical_formula_moiety 'C12 H12 Co N8 O6, C10 H8 N2' _chemical_formula_sum 'C22 H20 Co N10 O6' _chemical_formula_weight 579.41 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/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' _cell_length_a 7.2816(2) _cell_length_b 11.3892(2) _cell_length_c 15.2587(5) _cell_angle_alpha 90.00 _cell_angle_beta 102.407(1) _cell_angle_gamma 90.00 _cell_volume 1235.88(6) _cell_formula_units_Z 2 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 14072 _cell_measurement_theta_min 3.83 _cell_measurement_theta_max 27.50 _exptl_crystal_description rods _exptl_crystal_colour pink _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.557 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 594 _exptl_absorpt_coefficient_mu 0.755 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.8337 _exptl_absorpt_correction_T_max 0.9455 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14072 _diffrn_reflns_av_R_equivalents 0.0879 _diffrn_reflns_av_sigmaI/netI 0.0824 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.83 _diffrn_reflns_theta_max 27.50 _reflns_number_total 2826 _reflns_number_gt 2021 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^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_extinction_expression ? _refine_ls_number_reflns 2826 _refine_ls_number_parameters 187 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1000 _refine_ls_R_factor_gt 0.0594 _refine_ls_wR_factor_ref 0.0899 _refine_ls_wR_factor_gt 0.0801 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.062 _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 0.5000 0.34170(5) 0.2500 0.00869(15) Uani 1 2 d S . . O10 O 0.9892(3) 0.08870(19) 0.38836(16) 0.0320(6) Uani 1 1 d . . . N10 N 0.7951(3) 0.3347(2) 0.30641(15) 0.0144(5) Uani 1 1 d . . . O11 O 1.2700(3) 0.12619(19) 0.46649(15) 0.0285(6) Uani 1 1 d . . . N11 N 1.0994(3) 0.2752(2) 0.40291(16) 0.0164(6) Uani 1 1 d . . . C11 C 0.9329(4) 0.3011(2) 0.35085(19) 0.0122(6) Uani 1 1 d . . . N12 N 1.1173(4) 0.1571(2) 0.41882(16) 0.0207(6) Uani 1 1 d . . . O20 O 0.4559(3) 0.35011(17) 0.37988(13) 0.0119(4) Uani 1 1 d . . . N20 N 0.5000 0.5294(3) 0.2500 0.0115(7) Uani 1 2 d S . . N21 N 0.5000 1.1526(3) 0.2500 0.0120(7) Uani 1 2 d S . . C21 C 0.5942(4) 0.5906(2) 0.32073(19) 0.0115(6) Uani 1 1 d . . . H21 H 0.6621 0.5486 0.3711 0.014 Uiso 1 1 calc R . . C22 C 0.5970(4) 0.7112(2) 0.32376(19) 0.0117(6) Uani 1 1 d . . . H22 H 0.6645 0.7507 0.3756 0.014 Uiso 1 1 calc R . . C23 C 0.5000 0.7755(3) 0.2500 0.0109(9) Uani 1 2 d S . . C24 C 0.5000 0.9058(3) 0.2500 0.0101(9) Uani 1 2 d S . . C25 C 0.5461(4) 0.9703(2) 0.32923(19) 0.0158(7) Uani 1 1 d . . . H25 H 0.5775 0.9309 0.3854 0.019 Uiso 1 1 calc R . . C26 C 0.5460(4) 1.0907(2) 0.32615(19) 0.0163(7) Uani 1 1 d . . . H26 H 0.5805 1.1324 0.3811 0.020 Uiso 1 1 calc R . . N30 N 0.2709(3) 0.7086(2) 0.47389(16) 0.0170(6) Uani 1 1 d . . . C31 C 0.1937(4) 0.8065(3) 0.4345(2) 0.0190(7) Uani 1 1 d . . . H31 H 0.2133 0.8777 0.4677 0.023 Uiso 1 1 calc R . . C32 C 0.0861(4) 0.8100(2) 0.3478(2) 0.0163(7) Uani 1 1 d . . . H32 H 0.0336 0.8822 0.3230 0.020 Uiso 1 1 calc R . . C33 C 0.0553(4) 0.7076(2) 0.29722(19) 0.0129(6) Uani 1 1 d . . . C34 C 0.1323(4) 0.6047(3) 0.33875(19) 0.0146(6) Uani 1 1 d . . . H34 H 0.1128 0.5319 0.3078 0.018 Uiso 1 1 calc R . . C35 C 0.2378(4) 0.6097(3) 0.4258(2) 0.0174(7) Uani 1 1 d . . . H35 H 0.2898 0.5387 0.4530 0.021 Uiso 1 1 calc R . . H2A H 0.537(5) 0.318(3) 0.424(2) 0.031(10) Uiso 1 1 d . . . H2B H 0.350(6) 0.327(3) 0.391(2) 0.044(12) Uiso 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 0.0092(3) 0.0066(3) 0.0091(3) 0.000 -0.0006(2) 0.000 O10 0.0237(14) 0.0172(13) 0.0500(17) 0.0007(11) -0.0033(12) -0.0015(10) N10 0.0107(12) 0.0139(13) 0.0166(13) 0.0001(11) -0.0012(10) -0.0005(11) O11 0.0218(13) 0.0370(14) 0.0238(13) 0.0128(10) -0.0015(10) 0.0118(10) N11 0.0100(13) 0.0171(15) 0.0203(15) 0.0057(10) -0.0009(11) 0.0012(10) C11 0.0154(16) 0.0100(15) 0.0124(16) -0.0016(11) 0.0052(13) -0.0046(12) N12 0.0177(14) 0.0255(15) 0.0187(14) 0.0061(12) 0.0034(11) 0.0074(13) O20 0.0119(11) 0.0141(11) 0.0090(11) 0.0009(8) 0.0008(9) 0.0007(9) N20 0.0114(19) 0.0103(18) 0.012(2) 0.000 0.0013(15) 0.000 N21 0.0105(17) 0.0120(17) 0.0118(18) 0.000 -0.0013(14) 0.000 C21 0.0117(16) 0.0106(16) 0.0115(16) 0.0015(11) 0.0008(12) -0.0013(11) C22 0.0090(15) 0.0122(16) 0.0130(16) -0.0025(11) 0.0000(12) -0.0020(11) C23 0.012(2) 0.007(2) 0.016(2) 0.000 0.0060(18) 0.000 C24 0.008(2) 0.005(2) 0.017(2) 0.000 0.0026(17) 0.000 C25 0.0270(18) 0.0095(16) 0.0099(16) 0.0035(11) 0.0012(13) -0.0002(13) C26 0.0219(17) 0.0125(16) 0.0114(16) -0.0008(12) -0.0032(13) 0.0011(13) N30 0.0148(14) 0.0226(14) 0.0124(14) 0.0002(11) 0.0002(11) 0.0015(11) C31 0.0188(17) 0.0194(17) 0.0177(17) -0.0046(12) 0.0014(13) -0.0011(13) C32 0.0151(16) 0.0153(17) 0.0164(17) 0.0010(12) -0.0011(13) 0.0012(12) C33 0.0075(15) 0.0174(15) 0.0141(16) 0.0007(12) 0.0030(12) -0.0008(12) C34 0.0131(16) 0.0163(16) 0.0139(16) -0.0005(12) 0.0019(13) -0.0010(12) C35 0.0194(17) 0.0164(16) 0.0154(17) 0.0038(13) 0.0019(13) 0.0032(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 Co1 O20 2.0770(19) . ? Co1 O20 2.0770(19) 2_655 ? Co1 N20 2.137(3) . ? Co1 N10 2.138(2) . ? Co1 N10 2.138(2) 2_655 ? Co1 N21 2.154(3) 1_545 ? O10 N12 1.228(3) . ? N10 C11 1.149(3) . ? O11 N12 1.242(3) . ? N11 C11 1.332(4) . ? N11 N12 1.367(3) . ? O20 H2A 0.87(4) . ? O20 H2B 0.87(4) . ? N20 C21 1.343(3) . ? N20 C21 1.343(3) 2_655 ? N21 C26 1.339(3) 2_655 ? N21 C26 1.339(3) . ? N21 Co1 2.154(3) 1_565 ? C21 C22 1.374(4) . ? C21 H21 0.9500 . ? C22 C23 1.400(3) . ? C22 H22 0.9500 . ? C23 C22 1.400(3) 2_655 ? C23 C24 1.484(5) . ? C24 C25 1.392(3) . ? C24 C25 1.392(3) 2_655 ? C25 C26 1.372(4) . ? C25 H25 0.9500 . ? C26 H26 0.9500 . ? N30 C31 1.333(4) . ? N30 C35 1.337(4) . ? C31 C32 1.386(4) . ? C31 H31 0.9500 . ? C32 C33 1.390(4) . ? C32 H32 0.9500 . ? C33 C34 1.392(4) . ? C33 C33 1.492(6) 2 ? C34 C35 1.386(4) . ? C34 H34 0.9500 . ? C35 H35 0.9500 . ? 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 O20 Co1 O20 174.71(11) . 2_655 ? O20 Co1 N20 87.35(6) . . ? O20 Co1 N20 87.35(6) 2_655 . ? O20 Co1 N10 88.04(9) . . ? O20 Co1 N10 92.16(9) 2_655 . ? N20 Co1 N10 92.14(7) . . ? O20 Co1 N10 92.16(9) . 2_655 ? O20 Co1 N10 88.04(9) 2_655 2_655 ? N20 Co1 N10 92.14(6) . 2_655 ? N10 Co1 N10 175.72(13) . 2_655 ? O20 Co1 N21 92.65(6) . 1_545 ? O20 Co1 N21 92.65(6) 2_655 1_545 ? N20 Co1 N21 180.000(1) . 1_545 ? N10 Co1 N21 87.86(6) . 1_545 ? N10 Co1 N21 87.86(6) 2_655 1_545 ? C11 N10 Co1 157.7(2) . . ? C11 N11 N12 111.3(2) . . ? N10 C11 N11 173.3(3) . . ? O10 N12 O11 123.6(3) . . ? O10 N12 N11 121.4(2) . . ? O11 N12 N11 115.0(3) . . ? Co1 O20 H2A 120(2) . . ? Co1 O20 H2B 120(2) . . ? H2A O20 H2B 101(3) . . ? C21 N20 C21 117.4(3) . 2_655 ? C21 N20 Co1 121.31(17) . . ? C21 N20 Co1 121.31(17) 2_655 . ? C26 N21 C26 116.4(4) 2_655 . ? C26 N21 Co1 121.79(18) 2_655 1_565 ? C26 N21 Co1 121.79(18) . 1_565 ? N20 C21 C22 123.2(3) . . ? N20 C21 H21 118.4 . . ? C22 C21 H21 118.4 . . ? C21 C22 C23 119.6(3) . . ? C21 C22 H22 120.2 . . ? C23 C22 H22 120.2 . . ? C22 C23 C22 116.9(3) 2_655 . ? C22 C23 C24 121.55(17) 2_655 . ? C22 C23 C24 121.55(17) . . ? C25 C24 C25 116.4(4) . 2_655 ? C25 C24 C23 121.81(18) . . ? C25 C24 C23 121.81(18) 2_655 . ? C26 C25 C24 119.9(3) . . ? C26 C25 H25 120.0 . . ? C24 C25 H25 120.0 . . ? N21 C26 C25 123.7(3) . . ? N21 C26 H26 118.2 . . ? C25 C26 H26 118.2 . . ? C31 N30 C35 116.7(2) . . ? N30 C31 C32 123.5(3) . . ? N30 C31 H31 118.3 . . ? C32 C31 H31 118.3 . . ? C31 C32 C33 119.8(3) . . ? C31 C32 H32 120.1 . . ? C33 C32 H32 120.1 . . ? C32 C33 C34 116.9(3) . . ? C32 C33 C33 121.70(17) . 2 ? C34 C33 C33 121.38(17) . 2 ? C35 C34 C33 119.2(3) . . ? C35 C34 H34 120.4 . . ? C33 C34 H34 120.4 . . ? N30 C35 C34 123.9(3) . . ? N30 C35 H35 118.0 . . ? C34 C35 H35 118.0 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O20 H2A N30 0.87(4) 1.88(4) 2.734(3) 164(3) 3_666 O20 H2B N11 0.87(4) 1.96(4) 2.825(3) 174(4) 1_455 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.489 _refine_diff_density_min -0.560 _refine_diff_density_rms 0.098 data_3Fe _database_code_depnum_ccdc_archive 'CCDC 725141' _audit_creation_method SHELXL-97 _chemical_name_systematic ; {[Fe(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy} ; _chemical_name_common {[Fe(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy} _chemical_melting_point ? _chemical_formula_moiety 'C12 H12 Fe N8 O6, C10 H8 N2' _chemical_formula_sum 'C22 H20 Fe N10 O6' _chemical_formula_weight 576.33 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' _cell_length_a 7.2742(1) _cell_length_b 11.4850(2) _cell_length_c 15.2616(3) _cell_angle_alpha 90.00 _cell_angle_beta 102.364(1) _cell_angle_gamma 90.00 _cell_volume 1245.45(4) _cell_formula_units_Z 2 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 14407 _cell_measurement_theta_min 3.80 _cell_measurement_theta_max 27.50 _exptl_crystal_description rods _exptl_crystal_colour yellow _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.537 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 592 _exptl_absorpt_coefficient_mu 0.666 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.8783 _exptl_absorpt_correction_T_max 0.9364 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14407 _diffrn_reflns_av_R_equivalents 0.0454 _diffrn_reflns_av_sigmaI/netI 0.0374 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.80 _diffrn_reflns_theta_max 27.50 _reflns_number_total 2848 _reflns_number_gt 2425 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^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_extinction_expression ? _refine_ls_number_reflns 2848 _refine_ls_number_parameters 187 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0519 _refine_ls_R_factor_gt 0.0391 _refine_ls_wR_factor_ref 0.0733 _refine_ls_wR_factor_gt 0.0698 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.068 _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 Fe1 Fe 0.5000 0.34115(3) 0.2500 0.00958(10) Uani 1 2 d S . . N20 N 0.5000 0.53080(18) 0.2500 0.0123(4) Uani 1 2 d S . . C21 C 0.5936(2) 0.59217(15) 0.32059(12) 0.0127(4) Uani 1 1 d . . . H21 H 0.6615 0.5506 0.3711 0.015 Uiso 1 1 calc R . . N21 N 0.5000 1.14965(18) 0.2500 0.0131(4) Uani 1 2 d S . . C23 C 0.5000 0.7758(2) 0.2500 0.0122(5) Uani 1 2 d S . . C24 C 0.5000 0.9049(2) 0.2500 0.0120(5) Uani 1 2 d S . . C25 C 0.5435(3) 0.96831(16) 0.32954(12) 0.0180(4) Uani 1 1 d . . . H25 H 0.5732 0.9292 0.3857 0.022 Uiso 1 1 calc R . . C22 C 0.5965(2) 0.71227(15) 0.32371(12) 0.0129(4) Uani 1 1 d . . . H22 H 0.6637 0.7515 0.3756 0.016 Uiso 1 1 calc R . . C26 C 0.5433(3) 1.08817(16) 0.32612(12) 0.0174(4) Uani 1 1 d . . . H26 H 0.5757 1.1297 0.3811 0.021 Uiso 1 1 calc R . . O20 O 0.4567(2) 0.34898(11) 0.38116(8) 0.0133(3) Uani 1 1 d . . . H2B H 0.358(4) 0.328(2) 0.3881(16) 0.030(7) Uiso 1 1 d . . . H2A H 0.546(4) 0.322(2) 0.4281(19) 0.048(8) Uiso 1 1 d . . . N10 N 0.7985(2) 0.33329(13) 0.30644(10) 0.0161(3) Uani 1 1 d . . . N11 N 1.1011(2) 0.27256(14) 0.40378(11) 0.0184(4) Uani 1 1 d . . . C11 C 0.9360(2) 0.29901(15) 0.35122(12) 0.0141(4) Uani 1 1 d . . . N12 N 1.1186(2) 0.15490(15) 0.41925(11) 0.0202(4) Uani 1 1 d . . . O11 O 1.2705(2) 0.12380(13) 0.46653(10) 0.0303(4) Uani 1 1 d . . . O10 O 0.9898(2) 0.08791(12) 0.38776(11) 0.0331(4) Uani 1 1 d . . . C34 C 0.1324(2) 0.60528(16) 0.33850(12) 0.0155(4) Uani 1 1 d . . . H34 H 0.1133 0.5332 0.3073 0.019 Uiso 1 1 calc R . . C35 C 0.2375(3) 0.60991(17) 0.42535(12) 0.0179(4) Uani 1 1 d . . . H35 H 0.2892 0.5394 0.4524 0.021 Uiso 1 1 calc R . . N30 N 0.2707(2) 0.70806(14) 0.47363(10) 0.0174(3) Uani 1 1 d . . . C32 C 0.0854(3) 0.80936(16) 0.34769(12) 0.0168(4) Uani 1 1 d . . . H32 H 0.0327 0.8809 0.3230 0.020 Uiso 1 1 calc R . . C33 C 0.0548(2) 0.70763(16) 0.29708(12) 0.0133(4) Uani 1 1 d . . . C31 C 0.1933(3) 0.80584(17) 0.43440(13) 0.0196(4) Uani 1 1 d . . . H31 H 0.2132 0.8764 0.4676 0.023 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 Fe1 0.00994(18) 0.00674(18) 0.01107(18) 0.000 0.00006(13) 0.000 N20 0.0121(10) 0.0101(11) 0.0146(11) 0.000 0.0026(8) 0.000 C21 0.0130(9) 0.0110(9) 0.0134(9) 0.0015(7) 0.0016(7) 0.0008(6) N21 0.0115(10) 0.0101(11) 0.0167(11) 0.000 0.0009(8) 0.000 C23 0.0121(12) 0.0095(13) 0.0164(13) 0.000 0.0061(10) 0.000 C24 0.0106(12) 0.0082(13) 0.0170(13) 0.000 0.0024(10) 0.000 C25 0.0280(10) 0.0120(10) 0.0125(9) 0.0020(7) 0.0008(8) 0.0014(8) C22 0.0126(9) 0.0125(9) 0.0135(9) -0.0021(7) 0.0022(7) -0.0010(7) C26 0.0246(10) 0.0122(10) 0.0133(9) -0.0020(7) -0.0007(7) 0.0010(7) O20 0.0124(7) 0.0140(7) 0.0129(6) 0.0004(5) 0.0014(5) -0.0010(5) N10 0.0139(8) 0.0132(8) 0.0202(8) 0.0005(6) 0.0015(6) -0.0008(6) N11 0.0133(8) 0.0193(9) 0.0208(9) 0.0045(7) -0.0007(6) 0.0010(6) C11 0.0139(9) 0.0134(9) 0.0158(9) -0.0007(7) 0.0045(7) -0.0031(7) N12 0.0174(8) 0.0243(9) 0.0196(8) 0.0058(7) 0.0052(7) 0.0056(7) O11 0.0216(8) 0.0401(9) 0.0268(8) 0.0143(7) 0.0002(6) 0.0133(6) O10 0.0251(8) 0.0180(8) 0.0522(11) 0.0006(7) -0.0007(7) -0.0011(6) C34 0.0141(9) 0.0162(10) 0.0159(9) -0.0002(7) 0.0025(7) -0.0008(7) C35 0.0176(10) 0.0195(10) 0.0161(9) 0.0042(8) 0.0025(7) 0.0033(8) N30 0.0154(8) 0.0230(9) 0.0131(8) -0.0009(6) 0.0014(6) 0.0005(6) C32 0.0179(9) 0.0156(10) 0.0160(10) 0.0009(7) 0.0015(7) 0.0019(7) C33 0.0089(8) 0.0174(9) 0.0136(9) 0.0004(7) 0.0024(7) -0.0012(7) C31 0.0205(10) 0.0202(10) 0.0169(10) -0.0039(8) 0.0014(8) -0.0009(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 Fe1 O20 2.0938(13) . ? Fe1 O20 2.0938(13) 2_655 ? Fe1 N10 2.1593(15) 2_655 ? Fe1 N10 2.1593(15) . ? Fe1 N20 2.178(2) . ? Fe1 N21 2.199(2) 1_545 ? N20 C21 1.344(2) . ? N20 C21 1.344(2) 2_655 ? C21 C22 1.380(3) . ? C21 H21 0.9500 . ? N21 C26 1.338(2) 2_655 ? N21 C26 1.338(2) . ? N21 Fe1 2.199(2) 1_565 ? C23 C22 1.398(2) 2_655 ? C23 C22 1.398(2) . ? C23 C24 1.482(3) . ? C24 C25 1.393(2) . ? C24 C25 1.393(2) 2_655 ? C25 C26 1.378(3) . ? C25 H25 0.9500 . ? C22 H22 0.9500 . ? C26 H26 0.9500 . ? O20 H2B 0.79(3) . ? O20 H2A 0.91(3) . ? N10 C11 1.154(2) . ? N11 C11 1.328(2) . ? N11 N12 1.373(2) . ? N12 O10 1.228(2) . ? N12 O11 1.236(2) . ? C34 C35 1.382(2) . ? C34 C33 1.396(3) . ? C34 H34 0.9500 . ? C35 N30 1.340(2) . ? C35 H35 0.9500 . ? N30 C31 1.339(3) . ? C32 C31 1.387(3) . ? C32 C33 1.392(3) . ? C32 H32 0.9500 . ? C33 C33 1.487(3) 2 ? C31 H31 0.9500 . ? 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 O20 Fe1 O20 175.08(7) . 2_655 ? O20 Fe1 N10 92.23(6) . 2_655 ? O20 Fe1 N10 87.97(6) 2_655 2_655 ? O20 Fe1 N10 87.97(6) . . ? O20 Fe1 N10 92.23(6) 2_655 . ? N10 Fe1 N10 175.21(8) 2_655 . ? O20 Fe1 N20 87.54(4) . . ? O20 Fe1 N20 87.54(4) 2_655 . ? N10 Fe1 N20 92.40(4) 2_655 . ? N10 Fe1 N20 92.40(4) . . ? O20 Fe1 N21 92.46(4) . 1_545 ? O20 Fe1 N21 92.46(4) 2_655 1_545 ? N10 Fe1 N21 87.60(4) 2_655 1_545 ? N10 Fe1 N21 87.60(4) . 1_545 ? N20 Fe1 N21 180.0 . 1_545 ? C21 N20 C21 116.8(2) . 2_655 ? C21 N20 Fe1 121.62(11) . . ? C21 N20 Fe1 121.62(11) 2_655 . ? N20 C21 C22 123.57(17) . . ? N20 C21 H21 118.2 . . ? C22 C21 H21 118.2 . . ? C26 N21 C26 116.3(2) 2_655 . ? C26 N21 Fe1 121.85(11) 2_655 1_565 ? C26 N21 Fe1 121.85(11) . 1_565 ? C22 C23 C22 117.0(2) 2_655 . ? C22 C23 C24 121.49(11) 2_655 . ? C22 C23 C24 121.49(11) . . ? C25 C24 C25 117.0(2) . 2_655 ? C25 C24 C23 121.52(11) . . ? C25 C24 C23 121.52(11) 2_655 . ? C26 C25 C24 119.42(18) . . ? C26 C25 H25 120.3 . . ? C24 C25 H25 120.3 . . ? C21 C22 C23 119.54(17) . . ? C21 C22 H22 120.2 . . ? C23 C22 H22 120.2 . . ? N21 C26 C25 123.94(18) . . ? N21 C26 H26 118.0 . . ? C25 C26 H26 118.0 . . ? Fe1 O20 H2B 116.3(17) . . ? Fe1 O20 H2A 120.7(17) . . ? H2B O20 H2A 108(2) . . ? C11 N10 Fe1 157.10(14) . . ? C11 N11 N12 111.56(15) . . ? N10 C11 N11 173.23(19) . . ? O10 N12 O11 123.99(17) . . ? O10 N12 N11 120.98(15) . . ? O11 N12 N11 115.03(16) . . ? C35 C34 C33 119.28(17) . . ? C35 C34 H34 120.4 . . ? C33 C34 H34 120.4 . . ? N30 C35 C34 123.87(17) . . ? N30 C35 H35 118.1 . . ? C34 C35 H35 118.1 . . ? C31 N30 C35 116.79(16) . . ? C31 C32 C33 119.71(17) . . ? C31 C32 H32 120.1 . . ? C33 C32 H32 120.1 . . ? C32 C33 C34 117.03(16) . . ? C32 C33 C33 121.70(11) . 2 ? C34 C33 C33 121.27(11) . 2 ? N30 C31 C32 123.30(18) . . ? N30 C31 H31 118.4 . . ? C32 C31 H31 118.4 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O20 H2B N11 0.79(3) 2.03(3) 2.822(2) 179(3) 1_455 O20 H2A N30 0.91(3) 1.82(3) 2.718(2) 171(2) 3_666 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.333 _refine_diff_density_min -0.333 _refine_diff_density_rms 0.060 data_3Mn _database_code_depnum_ccdc_archive 'CCDC 725142' _audit_creation_method SHELXL-97 _chemical_name_systematic ; {[Mn(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy} ; _chemical_name_common {[Mn(CAN)2(4,4'-bipy)(H2O)2].4,4'-bipy} _chemical_melting_point ? _chemical_formula_moiety 'C12 H12 Mn N8 O6, (C10 H8 N2)' _chemical_formula_sum 'C22 H20 Mn N10 O6' _chemical_formula_weight 575.42 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 P2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' _cell_length_a 7.3102(1) _cell_length_b 11.5900(2) _cell_length_c 15.2784(3) _cell_angle_alpha 90.00 _cell_angle_beta 101.865(1) _cell_angle_gamma 90.00 _cell_volume 1266.81(4) _cell_formula_units_Z 2 _cell_measurement_temperature 123(1) _cell_measurement_reflns_used 14237 _cell_measurement_theta_min 3.77 _cell_measurement_theta_max 27.50 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.509 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 590 _exptl_absorpt_coefficient_mu 0.580 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.8451 _exptl_absorpt_correction_T_max 0.9442 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(1) _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 and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14237 _diffrn_reflns_av_R_equivalents 0.0668 _diffrn_reflns_av_sigmaI/netI 0.0510 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.77 _diffrn_reflns_theta_max 27.50 _reflns_number_total 2899 _reflns_number_gt 2125 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Hooft, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 1999)' _computing_publication_material 'CIFTAB (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^)+(0.2000P)^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_extinction_expression ? _refine_ls_number_reflns 2899 _refine_ls_number_parameters 187 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0648 _refine_ls_R_factor_gt 0.0378 _refine_ls_wR_factor_ref 0.1013 _refine_ls_wR_factor_gt 0.0893 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _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 0.5000 0.34288(3) 0.2500 0.01332(14) Uani 1 2 d S . . N20 N 0.5000 0.53633(18) 0.2500 0.0154(5) Uani 1 2 d S . . C21 C 0.5915(2) 0.59692(16) 0.32069(12) 0.0161(4) Uani 1 1 d . . . H21 H 0.6571 0.5557 0.3712 0.019 Uiso 1 1 calc R . . N21 N 0.5000 1.14855(17) 0.2500 0.0152(5) Uani 1 2 d S . . C23 C 0.5000 0.7785(2) 0.2500 0.0133(5) Uani 1 2 d S . . C24 C 0.5000 0.9068(2) 0.2500 0.0149(5) Uani 1 2 d S . . C25 C 0.5385(3) 0.96904(16) 0.32917(12) 0.0204(4) Uani 1 1 d . . . H25 H 0.5650 0.9300 0.3850 0.025 Uiso 1 1 calc R . . C22 C 0.5948(2) 0.71575(15) 0.32355(12) 0.0153(4) Uani 1 1 d . . . H22 H 0.6610 0.7547 0.3751 0.018 Uiso 1 1 calc R . . C26 C 0.5382(3) 1.08817(16) 0.32633(12) 0.0211(4) Uani 1 1 d . . . H26 H 0.5666 1.1293 0.3812 0.025 Uiso 1 1 calc R . . O20 O 0.4553(2) 0.35111(11) 0.38644(9) 0.0169(3) Uani 1 1 d . . . H2B H 0.353(4) 0.3288(19) 0.4002(16) 0.038(7) Uiso 1 1 d . . . H2A H 0.550(3) 0.321(2) 0.4300(17) 0.045(7) Uiso 1 1 d . . . N10 N 0.8058(2) 0.33806(13) 0.30806(11) 0.0208(4) Uani 1 1 d . . . N11 N 1.1000(2) 0.27189(14) 0.40653(11) 0.0223(4) Uani 1 1 d . . . C11 C 0.9389(3) 0.30091(17) 0.35320(13) 0.0180(4) Uani 1 1 d . . . N12 N 1.1141(2) 0.15491(14) 0.41973(11) 0.0236(4) Uani 1 1 d . . . O11 O 1.2621(2) 0.12197(14) 0.46767(10) 0.0350(4) Uani 1 1 d . . . O10 O 0.9856(2) 0.09028(13) 0.38576(11) 0.0376(4) Uani 1 1 d . . . C34 C 0.1309(2) 0.60987(17) 0.33786(12) 0.0184(4) Uani 1 1 d . . . H34 H 0.1117 0.5385 0.3068 0.022 Uiso 1 1 calc R . . C35 C 0.2348(3) 0.61456(17) 0.42412(13) 0.0206(4) Uani 1 1 d . . . H35 H 0.2861 0.5446 0.4510 0.025 Uiso 1 1 calc R . . N30 N 0.2677(2) 0.71159(14) 0.47225(10) 0.0215(4) Uani 1 1 d . . . C32 C 0.0846(3) 0.81215(17) 0.34767(13) 0.0208(4) Uani 1 1 d . . . H32 H 0.0323 0.8831 0.3233 0.025 Uiso 1 1 calc R . . C33 C 0.0544(2) 0.71146(16) 0.29692(12) 0.0158(4) Uani 1 1 d . . . C31 C 0.1910(3) 0.80843(18) 0.43360(13) 0.0221(4) Uani 1 1 d . . . H31 H 0.2106 0.8782 0.4669 0.027 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 0.0158(2) 0.0081(2) 0.0147(2) 0.000 -0.00004(16) 0.000 N20 0.0202(11) 0.0102(11) 0.0162(11) 0.000 0.0049(9) 0.000 C21 0.0196(9) 0.0129(10) 0.0151(10) -0.0001(7) 0.0017(8) -0.0007(7) N21 0.0180(11) 0.0098(11) 0.0167(11) 0.000 0.0009(9) 0.000 C23 0.0152(12) 0.0102(13) 0.0154(13) 0.000 0.0051(10) 0.000 C24 0.0137(12) 0.0131(13) 0.0174(14) 0.000 0.0022(10) 0.000 C25 0.0322(10) 0.0132(10) 0.0139(10) 0.0017(8) 0.0001(8) 0.0003(8) C22 0.0169(9) 0.0133(10) 0.0148(10) -0.0012(7) 0.0008(8) -0.0017(7) C26 0.0333(11) 0.0133(10) 0.0146(10) -0.0022(8) 0.0001(8) 0.0003(8) O20 0.0168(7) 0.0175(7) 0.0152(7) 0.0011(6) 0.0004(6) -0.0003(6) N10 0.0166(8) 0.0193(9) 0.0250(9) 0.0011(7) 0.0007(7) -0.0014(7) N11 0.0172(8) 0.0224(9) 0.0251(9) 0.0041(7) -0.0009(7) 0.0008(7) C11 0.0195(10) 0.0164(10) 0.0189(10) -0.0003(8) 0.0059(8) -0.0041(8) N12 0.0231(9) 0.0252(10) 0.0227(9) 0.0050(8) 0.0050(8) 0.0040(7) O11 0.0285(8) 0.0438(10) 0.0303(9) 0.0158(7) 0.0002(7) 0.0157(7) O10 0.0333(9) 0.0214(8) 0.0538(11) 0.0000(8) -0.0011(8) 0.0002(7) C34 0.0187(10) 0.0161(10) 0.0193(10) -0.0003(8) 0.0011(8) -0.0001(8) C35 0.0210(10) 0.0209(10) 0.0182(10) 0.0039(8) 0.0002(8) 0.0033(8) N30 0.0207(8) 0.0252(10) 0.0173(9) 0.0006(7) 0.0008(7) 0.0004(7) C32 0.0224(10) 0.0181(10) 0.0206(11) -0.0001(8) 0.0010(8) 0.0013(8) C33 0.0143(9) 0.0185(10) 0.0147(10) -0.0001(8) 0.0035(8) -0.0023(8) C31 0.0231(10) 0.0228(10) 0.0195(10) -0.0048(9) 0.0021(8) -0.0009(9) _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 O20 2.1775(13) 2_655 ? Mn1 O20 2.1775(13) . ? Mn1 N10 2.2298(15) . ? Mn1 N10 2.2298(15) 2_655 ? Mn1 N20 2.242(2) . ? Mn1 N21 2.252(2) 1_545 ? N20 C21 1.345(2) . ? N20 C21 1.345(2) 2_655 ? C21 C22 1.378(3) . ? C21 H21 0.9500 . ? N21 C26 1.339(2) 2_655 ? N21 C26 1.339(2) . ? N21 Mn1 2.252(2) 1_565 ? C23 C22 1.397(2) 2_655 ? C23 C22 1.397(2) . ? C23 C24 1.487(4) . ? C24 C25 1.387(2) . ? C24 C25 1.387(2) 2_655 ? C25 C26 1.381(3) . ? C25 H25 0.9500 . ? C22 H22 0.9500 . ? C26 H26 0.9500 . ? O20 H2B 0.86(3) . ? O20 H2A 0.92(2) . ? N10 C11 1.154(2) . ? N11 C11 1.330(2) . ? N11 N12 1.371(2) . ? N12 O10 1.230(2) . ? N12 O11 1.236(2) . ? C34 C35 1.380(3) . ? C34 C33 1.395(3) . ? C34 H34 0.9500 . ? C35 N30 1.338(3) . ? C35 H35 0.9500 . ? N30 C31 1.337(2) . ? C32 C31 1.382(3) . ? C32 C33 1.393(3) . ? C32 H32 0.9500 . ? C33 C33 1.490(4) 2 ? C31 H31 0.9500 . ? 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 O20 Mn1 O20 174.98(7) 2_655 . ? O20 Mn1 N10 92.66(6) 2_655 . ? O20 Mn1 N10 87.47(6) . . ? O20 Mn1 N10 87.47(6) 2_655 2_655 ? O20 Mn1 N10 92.66(6) . 2_655 ? N10 Mn1 N10 177.13(8) . 2_655 ? O20 Mn1 N20 87.49(3) 2_655 . ? O20 Mn1 N20 87.49(3) . . ? N10 Mn1 N20 91.43(4) . . ? N10 Mn1 N20 91.43(4) 2_655 . ? O20 Mn1 N21 92.51(3) 2_655 1_545 ? O20 Mn1 N21 92.51(3) . 1_545 ? N10 Mn1 N21 88.57(4) . 1_545 ? N10 Mn1 N21 88.57(4) 2_655 1_545 ? N20 Mn1 N21 180.0 . 1_545 ? C21 N20 C21 117.1(2) . 2_655 ? C21 N20 Mn1 121.47(11) . . ? C21 N20 Mn1 121.47(11) 2_655 . ? N20 C21 C22 123.35(17) . . ? N20 C21 H21 118.3 . . ? C22 C21 H21 118.3 . . ? C26 N21 C26 117.0(2) 2_655 . ? C26 N21 Mn1 121.50(11) 2_655 1_565 ? C26 N21 Mn1 121.50(11) . 1_565 ? C22 C23 C22 117.3(2) 2_655 . ? C22 C23 C24 121.37(11) 2_655 . ? C22 C23 C24 121.37(11) . . ? C25 C24 C25 117.3(2) . 2_655 ? C25 C24 C23 121.35(12) . . ? C25 C24 C23 121.35(12) 2_655 . ? C26 C25 C24 119.60(18) . . ? C26 C25 H25 120.2 . . ? C24 C25 H25 120.2 . . ? C21 C22 C23 119.48(17) . . ? C21 C22 H22 120.3 . . ? C23 C22 H22 120.3 . . ? N21 C26 C25 123.24(18) . . ? N21 C26 H26 118.4 . . ? C25 C26 H26 118.4 . . ? Mn1 O20 H2B 122.1(16) . . ? Mn1 O20 H2A 115.9(15) . . ? H2B O20 H2A 106(2) . . ? C11 N10 Mn1 154.17(15) . . ? C11 N11 N12 111.74(16) . . ? N10 C11 N11 172.7(2) . . ? O10 N12 O11 124.16(18) . . ? O10 N12 N11 120.82(16) . . ? O11 N12 N11 115.02(16) . . ? C35 C34 C33 119.08(18) . . ? C35 C34 H34 120.5 . . ? C33 C34 H34 120.5 . . ? N30 C35 C34 124.00(18) . . ? N30 C35 H35 118.0 . . ? C34 C35 H35 118.0 . . ? C31 N30 C35 116.83(17) . . ? C31 C32 C33 119.76(18) . . ? C31 C32 H32 120.1 . . ? C33 C32 H32 120.1 . . ? C34 C33 C32 117.02(17) . . ? C34 C33 C33 121.13(11) . 2 ? C32 C33 C33 121.86(11) . 2 ? N30 C31 C32 123.28(19) . . ? N30 C31 H31 118.4 . . ? C32 C31 H31 118.4 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O20 H2B N11 0.86(3) 1.98(3) 2.830(2) 169(2) 1_455 O20 H2A N30 0.92(2) 1.83(3) 2.737(2) 169(2) 3_666 _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.472 _refine_diff_density_min -0.520 _refine_diff_density_rms 0.105