Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 222 _publ_requested_journal 'Dalton Trans.' _publ_section_title ; A Novel 3D Cyano-Bridged Mixed-Valence Co^II^/Co^III^ Canted Antiferromagnet Constructed from Defective Cubanes. Synthesis, X-ray Structure and Magnetic Properties. ; _publ_contact_letter ; Please consider this CIF submission as crystallographic information file for compound 1. ; _publ_contact_author_name 'Enrique Colacio' _publ_contact_author_address ; Prof. Enrique Colacio Departamento de Quimica Inorganica Facultad de Ciencias Universidad de Granada E-18071 Granada Spain ; _publ_contact_author_phone '+34 958 243236' _publ_contact_author_fax '+34 958 248526' _publ_contact_author_email ecolacio@ugr.es loop_ _publ_author_name _publ_author_address 'Antonio Rodriquez-Dieguez' ; Departamento de Quimica Inorganica Facultad de Ciencias Universidad de Granada E-18071 Granada Spain ; 'Raikko Kivekas' ; Laboratory of Inorganic Chemistry Department of Chemistry P.O.Box 55 FIN-00014 University of Helsinki Finland ; 'Hiroshi Sakiyama' ; Departament of Material and Biological Chemistry Faculty of Science Yamagata University Kojirakawa, 1-4-12 Yamagata 990-8560 Japan ; 'Abderrahmane Debdoudi' ; Unite Calorimetrie et Materiaux Universite Abdelmalek Essaadi Facultes des Sciencias P.O. Box 2121 Tetouan 93002 Morocco ; 'Enrique Colacio' ; Departamento de Quimica Inorganica Facultad de Ciencias Universidad de Granada E-18071 Granada Spain ; data_ab677_b _database_code_depnum_ccdc_archive 'CCDC 631319' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety "'C8 H4 Co3 N6 O6, K, O H2" _chemical_formula_sum 'C8 H6 Co3 K N6 O7' _chemical_formula_weight 514.08 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' 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' K K 0.2009 0.2494 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P n m a' _symmetry_space_group_name_Hall '-P 2ac 2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 23.065(5) _cell_length_b 7.4423(15) _cell_length_c 9.846(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1690.1(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 1247 _cell_measurement_theta_min 3.258 _cell_measurement_theta_max 25.178 _exptl_crystal_description prismatic _exptl_crystal_colour red _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 2.020 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1008 _exptl_absorpt_coefficient_mu 3.200 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS, Sheldrick, G.M., 2003' _exptl_absorpt_correction_T_min 0.443374 _exptl_absorpt_correction_T_max 1.000000 _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 'CCD area detector' _diffrn_measurement_method 'omega/2theta scans' _diffrn_detector_area_resol_mean 66.06 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 8968 _diffrn_reflns_av_R_equivalents 0.0988 _diffrn_reflns_av_sigmaI/netI 0.0777 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 25.99 _reflns_number_total 1782 _reflns_number_gt 1140 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SMART' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Mercury 1.4.1' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and Rfactors 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^)+(0.1061P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3 ; _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1782 _refine_ls_number_parameters 133 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.1113 _refine_ls_R_factor_gt 0.0639 _refine_ls_wR_factor_ref 0.1858 _refine_ls_wR_factor_gt 0.1693 _refine_ls_goodness_of_fit_ref 1.091 _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 Co1 Co 0.12297(6) 0.2500 0.36806(15) 0.0152(4) Uani 1 d S . . Co2 Co -0.00785(6) 0.7500 0.18982(16) 0.0166(4) Uani 1 d S . . Co3 Co 0.25881(6) 0.7500 0.43236(15) 0.0179(4) Uani 1 d S . . O1 O 0.3255(2) 0.5696(7) 0.3783(6) 0.0268(13) Uani 1 d . . . O2 O 0.4231(2) 0.5696(7) 0.3602(6) 0.0247(13) Uani 1 d . . . N1 N 0.0487(3) 0.5432(9) 0.2402(7) 0.0207(15) Uani 1 d . . . C1 C 0.0775(3) 0.4323(11) 0.2874(8) 0.0204(18) Uani 1 d . . . N2 N 0.2011(3) 0.5442(9) 0.4794(7) 0.0210(15) Uani 1 d . . . C2 C 0.1693(3) 0.4307(10) 0.4446(8) 0.0219(18) Uani 1 d . . . N3 N 0.0428(4) 0.2500 0.6134(11) 0.022(2) Uani 1 d S . . C3 C 0.0725(4) 0.2500 0.5187(12) 0.018(2) Uani 1 d S . . N4 N 0.2052(4) 0.2500 0.1275(11) 0.026(2) Uani 1 d S . . C4 C 0.1736(4) 0.2500 0.2203(11) 0.019(2) Uani 1 d SU . . C5 C 0.3741(3) 0.6475(11) 0.3698(8) 0.0216(18) Uani 1 d . . . K K 0.33898(16) 0.2500 0.2357(4) 0.0573(10) Uani 1 d S . . O1W O 0.0194(4) 0.7500 -0.0137(10) 0.041(2) Uani 1 d S . . O2W O 0.2264(4) 0.7500 0.2236(10) 0.054(3) Uani 1 d S . . O3W O 0.4374(5) 0.210(3) 0.1006(15) 0.052(8) Uani 0.50 d P . . 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 0.0124(7) 0.0155(8) 0.0175(9) 0.000 0.0002(6) 0.000 Co2 0.0137(8) 0.0147(8) 0.0213(9) 0.000 0.0000(6) 0.000 Co3 0.0147(8) 0.0176(8) 0.0214(9) 0.000 -0.0008(6) 0.000 O1 0.017(3) 0.026(3) 0.038(4) 0.001(3) 0.009(2) 0.000(2) O2 0.018(3) 0.018(3) 0.038(4) -0.002(3) 0.003(2) -0.001(2) N1 0.023(4) 0.019(3) 0.020(4) 0.005(3) 0.005(3) 0.000(3) C1 0.016(4) 0.026(4) 0.019(5) -0.008(4) 0.001(3) -0.002(3) N2 0.019(3) 0.015(3) 0.029(4) -0.003(3) -0.001(3) 0.001(3) C2 0.017(4) 0.022(4) 0.027(5) 0.004(4) 0.004(3) 0.006(3) N3 0.020(5) 0.016(5) 0.031(6) 0.000 -0.005(4) 0.000 C3 0.015(6) 0.011(5) 0.028(7) 0.000 0.002(5) 0.000 N4 0.023(5) 0.019(5) 0.035(7) 0.000 0.001(5) 0.000 C4 0.008(5) 0.027(5) 0.020(6) 0.000 -0.005(4) 0.000 C5 0.015(4) 0.027(4) 0.022(5) -0.006(4) 0.000(3) 0.000(3) K 0.065(2) 0.0409(19) 0.066(3) 0.000 -0.0032(19) 0.000 O1W 0.050(6) 0.035(5) 0.038(6) 0.000 0.003(5) 0.000 O2W 0.065(7) 0.063(7) 0.033(6) 0.000 -0.004(5) 0.000 O3W 0.027(6) 0.06(2) 0.070(9) 0.015(9) 0.005(6) 0.000(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 Co1 C4 1.866(11) . ? Co1 C2 1.876(8) . ? Co1 C2 1.876(8) 7_565 ? Co1 C3 1.886(11) . ? Co1 C1 1.890(8) 7_565 ? Co1 C1 1.890(8) . ? Co2 N1 2.078(7) 7_575 ? Co2 N1 2.078(7) . ? Co2 N3 2.099(11) 5_566 ? Co2 O1W 2.100(10) . ? Co2 O2 2.141(5) 6_556 ? Co2 O2 2.141(5) 4_465 ? Co3 N2 2.081(7) . ? Co3 N2 2.081(7) 7_575 ? Co3 N4 2.093(11) 2_565 ? Co3 O1 2.110(5) . ? Co3 O1 2.110(5) 7_575 ? Co3 O2W 2.187(10) . ? Co3 K 3.743(4) 2_565 ? O1 C5 1.265(9) . ? O1 K 2.780(6) . ? O2 C5 1.274(8) . ? O2 Co2 2.141(5) 6_656 ? O2 K 3.305(6) . ? N1 C1 1.157(10) . ? N2 C2 1.170(10) . ? N2 K 3.093(7) 2_565 ? N3 C3 1.156(14) . ? N3 Co2 2.099(11) 5_566 ? N4 C4 1.169(14) . ? N4 Co3 2.093(11) 2_564 ? N4 K 3.265(10) . ? C5 C5 1.526(16) 7_575 ? C5 K 3.339(8) . ? K O3W 2.647(12) . ? K O3W 2.647(13) 7_565 ? K O1 2.780(6) 7_565 ? K N2 3.093(7) 8_655 ? K N2 3.093(7) 2_564 ? K O2 3.305(6) 7_565 ? K C5 3.339(8) 7_565 ? K Co3 3.743(4) 2_564 ? O3W O3W 0.59(5) 7_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 C4 Co1 C2 87.5(3) . . ? C4 Co1 C2 87.5(3) . 7_565 ? C2 Co1 C2 91.6(5) . 7_565 ? C4 Co1 C3 179.4(5) . . ? C2 Co1 C3 92.0(3) . . ? C2 Co1 C3 92.0(3) 7_565 . ? C4 Co1 C1 91.1(3) . 7_565 ? C2 Co1 C1 178.6(3) . 7_565 ? C2 Co1 C1 88.3(3) 7_565 7_565 ? C3 Co1 C1 89.3(3) . 7_565 ? C4 Co1 C1 91.1(3) . . ? C2 Co1 C1 88.3(3) . . ? C2 Co1 C1 178.6(3) 7_565 . ? C3 Co1 C1 89.3(3) . . ? C1 Co1 C1 91.8(5) 7_565 . ? N1 Co2 N1 95.6(4) 7_575 . ? N1 Co2 N3 91.2(2) 7_575 5_566 ? N1 Co2 N3 91.2(2) . 5_566 ? N1 Co2 O1W 92.3(3) 7_575 . ? N1 Co2 O1W 92.3(3) . . ? N3 Co2 O1W 174.8(3) 5_566 . ? N1 Co2 O2 170.7(2) 7_575 6_556 ? N1 Co2 O2 93.3(2) . 6_556 ? N3 Co2 O2 85.8(2) 5_566 6_556 ? O1W Co2 O2 90.2(3) . 6_556 ? N1 Co2 O2 93.3(2) 7_575 4_465 ? N1 Co2 O2 170.7(2) . 4_465 ? N3 Co2 O2 85.8(2) 5_566 4_465 ? O1W Co2 O2 90.2(3) . 4_465 ? O2 Co2 O2 77.7(3) 6_556 4_465 ? N2 Co3 N2 94.8(3) . 7_575 ? N2 Co3 N4 92.8(3) . 2_565 ? N2 Co3 N4 92.8(3) 7_575 2_565 ? N2 Co3 O1 93.1(2) . . ? N2 Co3 O1 172.1(2) 7_575 . ? N4 Co3 O1 86.7(3) 2_565 . ? N2 Co3 O1 172.1(2) . 7_575 ? N2 Co3 O1 93.1(2) 7_575 7_575 ? N4 Co3 O1 86.7(3) 2_565 7_575 ? O1 Co3 O1 79.1(3) . 7_575 ? N2 Co3 O2W 89.5(3) . . ? N2 Co3 O2W 89.5(3) 7_575 . ? N4 Co3 O2W 176.6(4) 2_565 . ? O1 Co3 O2W 90.7(3) . . ? O1 Co3 O2W 90.7(3) 7_575 . ? N2 Co3 K 55.74(18) . 2_565 ? N2 Co3 K 55.74(18) 7_575 2_565 ? N4 Co3 K 60.4(3) 2_565 2_565 ? O1 Co3 K 129.83(16) . 2_565 ? O1 Co3 K 129.83(16) 7_575 2_565 ? O2W Co3 K 122.9(3) . 2_565 ? C5 O1 Co3 111.8(5) . . ? C5 O1 K 105.0(5) . . ? Co3 O1 K 138.9(3) . . ? C5 O2 Co2 113.1(5) . 6_656 ? C5 O2 K 80.5(4) . . ? Co2 O2 K 143.4(3) 6_656 . ? C1 N1 Co2 170.0(6) . . ? N1 C1 Co1 178.5(7) . . ? C2 N2 Co3 150.1(6) . . ? C2 N2 K 114.1(5) . 2_565 ? Co3 N2 K 90.5(2) . 2_565 ? N2 C2 Co1 173.0(7) . . ? C3 N3 Co2 166.3(9) . 5_566 ? N3 C3 Co1 178.2(10) . . ? C4 N4 Co3 164.8(9) . 2_564 ? C4 N4 K 109.5(8) . . ? Co3 N4 K 85.7(3) 2_564 . ? N4 C4 Co1 179.8(9) . . ? O1 C5 O2 125.6(7) . . ? O1 C5 C5 117.3(4) . 7_575 ? O2 C5 C5 117.1(4) . 7_575 ? O1 C5 K 53.5(4) . . ? O2 C5 K 77.4(4) . . ? C5 C5 K 152.37(15) 7_575 . ? O3W K O3W 12.9(10) . 7_565 ? O3W K O1 116.5(5) . . ? O3W K O1 104.7(5) 7_565 . ? O3W K O1 104.7(5) . 7_565 ? O3W K O1 116.5(5) 7_565 7_565 ? O1 K O1 117.7(3) . 7_565 ? O3W K N2 77.9(4) . 8_655 ? O3W K N2 84.4(4) 7_565 8_655 ? O1 K N2 143.3(2) . 8_655 ? O1 K N2 87.42(18) 7_565 8_655 ? O3W K N2 84.4(4) . 2_564 ? O3W K N2 77.9(4) 7_565 2_564 ? O1 K N2 87.42(18) . 2_564 ? O1 K N2 143.3(2) 7_565 2_564 ? N2 K N2 59.3(3) 8_655 2_564 ? O3W K N4 130.3(4) . . ? O3W K N4 130.3(4) 7_565 . ? O1 K N4 93.38(17) . . ? O1 K N4 93.38(17) 7_565 . ? N2 K N4 56.7(2) 8_655 . ? N2 K N4 56.7(2) 2_564 . ? O3W K O2 76.3(4) . . ? O3W K O2 66.6(4) 7_565 . ? O1 K O2 42.48(14) . . ? O1 K O2 119.6(2) 7_565 . ? N2 K O2 146.6(2) 8_655 . ? N2 K O2 97.00(16) 2_564 . ? N4 K O2 132.52(11) . . ? O3W K O2 66.6(4) . 7_565 ? O3W K O2 76.3(4) 7_565 7_565 ? O1 K O2 119.6(2) . 7_565 ? O1 K O2 42.48(14) 7_565 7_565 ? N2 K O2 97.00(16) 8_655 7_565 ? N2 K O2 146.6(2) 2_564 7_565 ? N4 K O2 132.52(11) . 7_565 ? O2 K O2 92.1(2) . 7_565 ? O3W K C5 95.2(5) . . ? O3W K C5 83.8(5) 7_565 . ? O1 K C5 21.46(16) . . ? O1 K C5 125.8(2) 7_565 . ? N2 K C5 146.5(2) 8_655 . ? N2 K C5 87.51(19) 2_564 . ? N4 K C5 110.99(15) . . ? O2 K C5 22.10(14) . . ? O2 K C5 110.41(19) 7_565 . ? O3W K C5 83.8(5) . 7_565 ? O3W K C5 95.2(5) 7_565 7_565 ? O1 K C5 125.8(2) . 7_565 ? O1 K C5 21.46(16) 7_565 7_565 ? N2 K C5 87.51(19) 8_655 7_565 ? N2 K C5 146.5(2) 2_564 7_565 ? N4 K C5 110.99(15) . 7_565 ? O2 K C5 110.41(19) . 7_565 ? O2 K C5 22.10(14) 7_565 7_565 ? C5 K C5 124.7(3) . 7_565 ? O3W K Co3 96.6(3) . 2_564 ? O3W K Co3 96.6(3) 7_565 2_564 ? O1 K Co3 109.61(14) . 2_564 ? O1 K Co3 109.61(14) 7_565 2_564 ? N2 K Co3 33.77(13) 8_655 2_564 ? N2 K Co3 33.77(13) 2_564 2_564 ? N4 K Co3 33.89(19) . 2_564 ? O2 K Co3 130.52(12) . 2_564 ? O2 K Co3 130.52(12) 7_565 2_564 ? C5 K Co3 117.49(15) . 2_564 ? C5 K Co3 117.49(15) 7_565 2_564 ? O3W O3W K 83.6(5) 7_565 . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.99 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.179 _refine_diff_density_min -1.582 _refine_diff_density_rms 0.197 #===END