# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_contact_author_name 'Edurne S. Larrea' _publ_contact_author_address ; Dpto. Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; _publ_contact_author_email edurne.serrano@ehu.es _publ_contact_author_phone 0034946015984 _publ_contact_author_fax 0034946013500 loop_ _publ_author_name _publ_author_address 'E.S. Larrea' ;Dpto. Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; J.L.Mesa ;Dpto. Qu\'imica Inorg\'anica Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; J.L.Pizarro ;Dpto. Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; 'R.Fernandez de Luis' ;Dpto. Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; ; J.Rodriguez Fernandez ; ;Dpto. CITIMAC Universidad de Cantabria 39005 Santander Spain ; T.Rojo ;Dpto. Qu\'imica Inorg\'anica Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; M.I.Arriortua ;Dpto. MIneralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco/Euskal Herriko Unibertsitatea, UPV/EHU Sarriena s/n 48940 Leioa, Bizkaia Spain ; _publ_requested_category FM data_covpym _database_code_depnum_ccdc_archive 'CCDC 888694' #TrackingRef '- archive_CoVPym.cif' #------------------ AUDIT DETAILS -------------------------------------------# _audit_creation_date 2012-09-05 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.4 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic _audit_update_record ? #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_sum 'C4 H4 Co N2 O6 V2' _chemical_formula_weight 336.9 #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _space_group_crystal_system monoclinic _space_group_name_H-M_alt C2/c _space_group_name_Hall -C2yc _space_group_IT_number 15 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 12.899(5) _cell_length_b 9.8587(17) _cell_length_c 7.0513(10) _cell_angle_alpha 90 _cell_angle_beta 111.41(3) _cell_angle_gamma 90 _cell_volume 834.8(4) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2036 _cell_measurement_theta_min 2.8899 _cell_measurement_theta_max 32.0926 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description twin _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.018 _exptl_crystal_size_min 0.017 _exptl_crystal_density_meas 2.640(10) _exptl_crystal_density_diffrn 2.681 _exptl_crystal_density_method flotation _exptl_crystal_F_000 652 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 4.164 _exptl_absorpt_correction_T_min 0.684 _exptl_absorpt_correction_T_max 0.920 _exptl_absorpt_correction_type analytical _exptl_absorpt_process_details ; Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.7107 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed X-ray tube' _diffrn_radiation_monochromator graphite _diffrn_detector_area_resol_mean 8.3504 _diffrn_orient_matrix_ub_11 -0.0180695683 _diffrn_orient_matrix_ub_12 -0.0278261743 _diffrn_orient_matrix_ub_13 0.0095869976 _diffrn_orient_matrix_ub_21 0.0071600023 _diffrn_orient_matrix_ub_22 -0.0654994704 _diffrn_orient_matrix_ub_23 -0.0197318667 _diffrn_orient_matrix_ub_31 0.0031923401 _diffrn_orient_matrix_ub_32 -0.0105336894 _diffrn_orient_matrix_ub_33 0.0982698434 _diffrn_measurement_device 'Oxford Diffractio Xcalibur2' _diffrn_measurement_method '\w scans' _diffrn_reflns_av_R_equivalents 0.1168 _diffrn_reflns_av_unetI/netI 0.0473 _diffrn_reflns_number 2722 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.39 _diffrn_reflns_theta_max 32.22 _diffrn_reflns_theta_full 25 _diffrn_measured_fraction_theta_full 0.949 _diffrn_measured_fraction_theta_max 0.843 _reflns_number_total 2722 _reflns_number_gt 2158 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_structure_solution 'SHELXS 97' _computing_structure_refinement 'SHELXlL 97' _computing_molecular_graphics 'PLATON (Spek, 1990), (Spek, 1998)' _computing_publication_material 'ATOMS 6.2' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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. The crystal is twinned.The .HKLF5 file was generated with the program CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 taking into account the twin law: 1 0 0, 0 -1 0, -0.666 0 -1 This twin law corresponds to a 180,0 defree rotarion about 'a' axis. After the refinement the BASF parameter shows that the weight of the two components of the twin are 0.624(1)/0.376(1) ; _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^)+(0.0593P)^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_number_reflns 2722 _refine_ls_number_parameters 72 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0521 _refine_ls_R_factor_gt 0.0394 _refine_ls_wR_factor_ref 0.0974 _refine_ls_wR_factor_gt 0.0942 _refine_ls_goodness_of_fit_ref 0.963 _refine_ls_restrained_S_all 0.963 _refine_ls_shift/su_max 0.017 _refine_ls_shift/su_mean 0.003 _refine_diff_density_max 1.03 _refine_diff_density_min -0.589 _refine_diff_density_rms 0.186 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Co Co -0.25 0.25 0 0.01010(13) Uani 1 2 d S . . V V -0.39513(3) 0.52352(5) -0.30898(7) 0.00730(11) Uani 1 1 d . . . O1 O -0.30298(15) 0.4036(2) -0.1979(3) 0.0142(4) Uani 1 1 d . . . O2 O -0.32975(16) 0.3365(2) 0.1779(3) 0.0153(4) Uani 1 1 d . . . O3 O -0.44053(15) 0.4564(2) -0.5794(3) 0.0113(4) Uani 1 1 d . . . N N -0.40011(19) 0.1269(3) -0.1595(4) 0.0168(5) Uani 1 1 d . . . C1 C -0.4017(3) -0.0117(4) -0.1598(5) 0.0249(7) Uani 1 1 d . . . H1 H -0.3354 -0.0589 -0.0982 0.03 Uiso 1 1 calc R . . C2 C -0.5 0.1843(5) -0.25 0.0221(9) Uani 1 2 d S . . H2 H -0.5 0.2787 -0.25 0.026 Uiso 1 2 calc SR . . C3 C -0.5 -0.0840(5) -0.25 0.0287(11) Uani 1 2 d S . . H3 H -0.5 -0.1783 -0.25 0.034 Uiso 1 2 calc SR . . 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 Co 0.0102(2) 0.0116(3) 0.0080(3) 0.00081(19) 0.0028(2) 0.00432(19) V 0.00688(18) 0.0101(2) 0.0052(2) 0.00103(17) 0.00250(17) -0.00048(17) O1 0.0166(9) 0.0158(10) 0.0104(10) 0.0034(8) 0.0051(8) 0.0072(8) O2 0.0194(10) 0.0139(10) 0.0148(10) 0.0010(8) 0.0089(8) 0.0063(8) O3 0.0093(8) 0.0187(11) 0.0069(9) -0.0019(8) 0.0040(7) 0.0009(7) N 0.0146(11) 0.0189(13) 0.0136(12) -0.0024(10) 0.0011(9) 0.0043(10) C1 0.0199(14) 0.0261(17) 0.0274(19) -0.0008(14) 0.0072(13) 0.0030(14) C2 0.022(2) 0.019(2) 0.025(2) 0 0.0079(18) 0 C3 0.030(2) 0.017(2) 0.040(3) 0 0.014(2) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 Co O1 2.003(2) . ? Co O1 2.003(2) 7_455 ? Co O2 2.0742(18) . ? Co O2 2.0742(18) 7_455 ? Co N 2.213(3) . ? Co N 2.213(3) 7_455 ? V O2 1.637(2) 6_565 ? V O1 1.657(2) . ? V O3 1.897(2) . ? V O3 1.9225(18) 6_566 ? V O3 1.983(2) 5_464 ? V V 3.0774(16) 5_464 ? V V 3.1071(13) 2_454 ? O2 V 1.637(2) 6_566 ? O3 V 1.9225(18) 6_565 ? O3 V 1.983(2) 5_464 ? N C2 1.337(3) . ? N C1 1.367(4) . ? C1 C3 1.389(4) . ? C1 H1 0.93 . ? C2 N 1.337(3) 2_454 ? C2 H2 0.93 . ? C3 C1 1.389(4) 2_454 ? C3 H3 0.93 . ? 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 Co O1 180.00(7) . 7_455 ? O1 Co O2 89.54(8) . . ? O1 Co O2 90.46(8) 7_455 . ? O1 Co O2 90.46(8) . 7_455 ? O1 Co O2 89.54(8) 7_455 7_455 ? O2 Co O2 180 . 7_455 ? O1 Co N 92.74(9) . . ? O1 Co N 87.26(9) 7_455 . ? O2 Co N 89.88(8) . . ? O2 Co N 90.12(8) 7_455 . ? O1 Co N 87.26(9) . 7_455 ? O1 Co N 92.74(9) 7_455 7_455 ? O2 Co N 90.12(8) . 7_455 ? O2 Co N 89.88(8) 7_455 7_455 ? N Co N 180 . 7_455 ? O2 V O1 109.43(11) 6_565 . ? O2 V O3 102.32(9) 6_565 . ? O1 V O3 97.54(10) . . ? O2 V O3 106.41(9) 6_565 6_566 ? O1 V O3 93.54(9) . 6_566 ? O3 V O3 143.60(9) . 6_566 ? O2 V O3 113.05(9) 6_565 5_464 ? O1 V O3 137.49(9) . 5_464 ? O3 V O3 75.09(9) . 5_464 ? O3 V O3 73.39(9) 6_566 5_464 ? O2 V V 112.58(7) 6_565 5_464 ? O1 V V 123.78(8) . 5_464 ? O3 V V 38.52(6) . 5_464 ? O3 V V 108.18(6) 6_566 5_464 ? O3 V V 36.57(6) 5_464 5_464 ? O2 V V 122.14(7) 6_565 2_454 ? O1 V V 114.71(7) . 2_454 ? O3 V V 106.82(6) . 2_454 ? O3 V V 37.98(6) 6_566 2_454 ? O3 V V 36.62(6) 5_464 2_454 ? V V V 70.20(3) 5_464 2_454 ? V O1 Co 150.75(11) . . ? V O2 Co 139.49(11) 6_566 . ? V O3 V 137.16(10) . 6_565 ? V O3 V 104.91(9) . 5_464 ? V O3 V 105.39(9) 6_565 5_464 ? C2 N C1 114.3(3) . . ? C2 N Co 121.5(2) . . ? C1 N Co 124.00(19) . . ? N C1 C3 121.6(3) . . ? N C1 H1 119.2 . . ? C3 C1 H1 119.2 . . ? N C2 N 129.9(4) 2_454 . ? N C2 H2 115.1 2_454 . ? N C2 H2 115.1 . . ? C1 C3 C1 118.3(5) . 2_454 ? C1 C3 H3 120.8 . . ? C1 C3 H3 120.8 2_454 . ? # END of CIF