# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full CrystEngComm #TrackingRef '- CoBpaV2O6.cif' _journal_coden_Cambridge 1350 _publ_contact_author ; Dra. Miren Karmele Urtiaga Greaves Facultad de Ciencia y Tecnolog\'ia Dpto. de Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco Apartado 644 48080 Bilbao Spain ; _publ_contact_author_phone '34 4 601000 ext 5372' _publ_contact_author_fax '34 4 4648500' _publ_contact_author_email karmele.urtiaga@ehu.es loop_ _publ_author_name _publ_author_address 'Roberto F. de Luis' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; "Jos\'e L. Mesa " ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'M. Karmele Urtiaga' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Edurne S. Larrea' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; "Mar\'ia I. Arriortua" ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; ; T.Rojo ; ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencia y Tecnolog\'ia Uiversidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; _publ_requested_category FM _publ_contact_author_name 'Dra. Miren Karmele Urtiaga Greaves' #\#CIF_1.1 # CIF produced by WinGX routine CIF_UPDATE # Created on 2008-03-12 at 10:03:20 # Using CIFtbx version 2.6.2 16 Jun 1998 # Dictionary name : cif_core.dic # Dictionary vers : 2.3 # Request file : c:\wingx\files\archive.dat # CIF files read : ni567_i ni567_i_exp struct data_CoBpaV2O6_Ni(H2O)2bpe(V4O11) _database_code_depnum_ccdc_archive 'CCDC 871305' #TrackingRef '- CoBpaV2O6.cif' _audit_creation_date 2008-03-12T10:03:20-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.3 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C12 H12 Co N2 O6 V2' _chemical_formula_sum 'C12 H12 Co N2 O6 V2' _chemical_formula_weight 441.05 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.4026(12) _cell_length_b 8.5005(11) _cell_length_c 11.1893(16) _cell_angle_alpha 94.214(11) _cell_angle_beta 93.028(11) _cell_angle_gamma 106.597(18) _cell_volume 761.56(18) _cell_formula_units_Z 2 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 8555 _cell_measurement_theta_min 2.66 _cell_measurement_theta_max 33.69 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description Prism _exptl_crystal_colour Brown _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.12 _exptl_crystal_density_diffrn 1.923 _exptl_crystal_density_meas 1.92(1) _exptl_crystal_density_method flotation' _exptl_crystal_F_000 438 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1 1 -1 0.0380 1 -1 1 0.0260 0 0 1 0.0540 0 1 1 0.1280 0 1 -1 0.0920 1 0 0 0.1250 0 -1 1 0.0500 0 0 -1 0.0850 -1 0 0 0.0700 0 -1 -1 0.1040 _exptl_special_details ; ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 2.308 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.6685 _exptl_absorpt_correction_T_max 0.8724 _exptl_absorpt_process_details ; X-RED (Stoe & Cie, March 2001 Revision 1.22) and X-SHAPE (Stoe & Cie, October 1999, Revision 1.06) 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 153(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_detector 'image plate (34 cm diameter)' _diffrn_measurement_device '2-circle goniometer' _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_detector_type STOE _diffrn_detector_area_resol_mean 6.67 _diffrn_source 'sealed X-ray tube, 12 x 0.4 mm long-fine focus' _diffrn_source_voltage 50 _diffrn_source_current 40 _diffrn_source_power 2.00 _diffrn_radiation_polarisn_norm 0 _diffrn_radiation_collimation '0.5 mm diameter, monocapillary' _diffrn_measurement_method 'rotation method' _diffrn_measurement_details ; 222 frames, detector distance = 70 mm ; _diffrn_reflns_av_R_equivalents 0.0492 _diffrn_reflns_av_unetI/netI 0.0713 _diffrn_reflns_number 11512 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 33.34 _diffrn_measured_fraction_theta_max 0.956 _diffrn_reflns_theta_full 27.5 _diffrn_measured_fraction_theta_full 0.971 _reflns_number_total 5642 _reflns_number_gt 3887 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # 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. ; _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^)+(0.0107P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 5642 _refine_ls_number_parameters 208 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0583 _refine_ls_R_factor_gt 0.0293 _refine_ls_wR_factor_ref 0.0603 _refine_ls_wR_factor_gt 0.0545 _refine_ls_goodness_of_fit_ref 0.851 _refine_ls_restrained_S_all 0.851 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.667 _refine_diff_density_min -0.634 _refine_diff_density_rms 0.126 #----------------------------------------------------------------------------# # 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 H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' V V 0.3005 0.5294 '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' 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 0.18638(3) 0.34456(3) 0.05805(2) 0.00949(6) Uani 1 1 d . . . V1 V 0.26294(4) 0.74391(3) -0.01723(3) 0.00970(6) Uani 1 1 d . . . V2 V 0.42318(4) 0.08848(3) 0.17973(2) 0.00894(6) Uani 1 1 d . . . O1 O 0.29515(19) 0.56175(15) 0.00039(11) 0.0155(3) Uani 1 1 d . . . O2 O 0.36418(19) 0.83021(17) -0.14286(12) 0.0173(3) Uani 1 1 d . . . O3 O -0.05998(18) 0.28045(17) 0.04035(12) 0.0162(3) Uani 1 1 d . . . O4 O 0.4206(2) 0.10024(18) 0.32451(11) 0.0191(3) Uani 1 1 d . . . O5 O 0.3415(2) 0.87651(16) 0.11589(12) 0.0180(3) Uani 1 1 d . . . O6 O 0.3089(2) 0.20262(17) 0.12520(12) 0.0181(3) Uani 1 1 d . . . N1 N 0.1894(2) 0.22296(18) -0.11501(13) 0.0126(3) Uani 1 1 d . . . N2 N 0.1819(2) 0.46475(18) 0.23306(13) 0.0131(3) Uani 1 1 d . . . C1 C 0.2049(3) 0.0358(2) -0.33043(15) 0.0130(3) Uani 1 1 d . . . C2 C 0.1760(3) 0.6500(2) 0.45198(15) 0.0136(3) Uani 1 1 d . . . C3 C 0.2145(3) -0.0652(2) -0.44582(16) 0.0185(4) Uani 1 1 d . . . H3A H 0.3288 -0.0275 -0.4722 0.022 Uiso 1 1 calc R . . H3B H 0.1373 -0.0460 -0.5093 0.022 Uiso 1 1 calc R . . C4 C 0.2817(3) 0.5507(2) 0.43995(16) 0.0186(4) Uani 1 1 d . . . H4 H 0.3544 0.5447 0.5063 0.022 Uiso 1 1 calc R . . C5 C 0.1702(3) 0.7495(2) 0.56848(15) 0.0169(4) Uani 1 1 d . . . H5A H 0.2493 0.7297 0.6302 0.020 Uiso 1 1 calc R . . H5B H 0.0570 0.7120 0.5968 0.020 Uiso 1 1 calc R . . C6 C 0.3340(3) 0.1763(2) -0.28764(16) 0.0166(4) Uani 1 1 d . . . H6 H 0.4300 0.2104 -0.3313 0.020 Uiso 1 1 calc R . . C7 C 0.0719(3) 0.6515(2) 0.35107(16) 0.0170(4) Uani 1 1 d . . . H7 H -0.0042 0.7153 0.3552 0.020 Uiso 1 1 calc R . . C8 C 0.0672(3) -0.0071(2) -0.26216(15) 0.0143(3) Uani 1 1 d . . . H8 H -0.0243 -0.1008 -0.2880 0.017 Uiso 1 1 calc R . . C9 C 0.0792(3) 0.5600(2) 0.24461(16) 0.0154(4) Uani 1 1 d . . . H9 H 0.0084 0.5648 0.1767 0.019 Uiso 1 1 calc R . . C10 C 0.2810(3) 0.4601(2) 0.33071(16) 0.0181(4) Uani 1 1 d . . . H10 H 0.3532 0.3924 0.3249 0.022 Uiso 1 1 calc R . . C11 C 0.0645(3) 0.0882(2) -0.15595(15) 0.0141(3) Uani 1 1 d . . . H11 H -0.0299 0.0565 -0.1104 0.017 Uiso 1 1 calc R . . C12 C 0.3219(3) 0.2662(2) -0.18098(16) 0.0168(4) Uani 1 1 d . . . H12 H 0.4107 0.3617 -0.1538 0.020 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 Co1 0.00995(14) 0.00818(10) 0.01015(10) -0.00087(8) 0.00023(9) 0.00285(9) V1 0.00875(16) 0.00718(11) 0.01207(12) -0.00033(9) 0.00163(11) 0.00072(10) V2 0.01007(16) 0.00867(12) 0.00807(12) -0.00037(9) 0.00089(10) 0.00293(10) O1 0.0202(8) 0.0086(5) 0.0177(6) 0.0010(4) 0.0051(5) 0.0037(5) O2 0.0122(8) 0.0204(6) 0.0198(6) 0.0086(5) 0.0043(5) 0.0033(5) O3 0.0100(8) 0.0204(6) 0.0163(6) -0.0037(5) 0.0022(5) 0.0024(5) O4 0.0234(9) 0.0246(7) 0.0097(5) 0.0012(5) 0.0026(5) 0.0076(6) O5 0.0201(8) 0.0111(5) 0.0205(6) -0.0043(5) -0.0041(5) 0.0033(5) O6 0.0205(8) 0.0176(6) 0.0191(6) 0.0013(5) -0.0014(5) 0.0105(6) N1 0.0136(9) 0.0109(6) 0.0128(6) -0.0012(5) 0.0001(6) 0.0033(6) N2 0.0159(9) 0.0118(6) 0.0118(6) -0.0018(5) 0.0015(6) 0.0050(6) C1 0.0187(11) 0.0108(7) 0.0102(7) -0.0008(6) 0.0019(7) 0.0057(7) C2 0.0173(10) 0.0116(7) 0.0109(7) -0.0027(6) 0.0018(7) 0.0033(7) C3 0.0288(13) 0.0131(8) 0.0121(8) -0.0041(6) 0.0052(7) 0.0042(7) C4 0.0209(12) 0.0227(9) 0.0133(8) -0.0051(7) -0.0038(7) 0.0105(8) C5 0.0260(12) 0.0133(7) 0.0106(7) -0.0029(6) 0.0034(7) 0.0051(7) C6 0.0180(11) 0.0153(8) 0.0152(8) -0.0028(6) 0.0057(7) 0.0030(7) C7 0.0256(12) 0.0154(8) 0.0130(7) -0.0025(6) 0.0003(7) 0.0118(8) C8 0.0165(10) 0.0111(7) 0.0134(7) -0.0034(6) 0.0020(7) 0.0022(7) C9 0.0213(11) 0.0147(8) 0.0114(7) -0.0020(6) -0.0012(7) 0.0080(7) C10 0.0176(11) 0.0218(9) 0.0165(8) -0.0053(7) -0.0009(7) 0.0102(8) C11 0.0162(10) 0.0123(7) 0.0129(7) -0.0017(6) 0.0036(7) 0.0031(7) C12 0.0152(11) 0.0150(8) 0.0175(8) -0.0049(6) 0.0017(7) 0.0013(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 O6 1.9597(13) . ? Co1 O3 1.9793(15) . ? Co1 O1 1.9833(13) . ? Co1 N1 2.1320(14) . ? Co1 N2 2.1484(14) . ? V1 O3 1.6619(15) 2_565 ? V1 O1 1.6699(12) . ? V1 O5 1.7747(13) . ? V1 O2 1.7775(14) . ? V2 O4 1.6174(13) . ? V2 O6 1.6714(14) . ? V2 O2 1.8040(16) 2_665 ? V2 O5 1.8112(13) 1_545 ? O2 V2 1.8040(15) 2_665 ? O3 V1 1.6619(15) 2_565 ? O5 V2 1.8112(13) 1_565 ? N1 C11 1.345(2) . ? N1 C12 1.346(3) . ? N2 C9 1.347(2) . ? N2 C10 1.348(2) . ? C1 C8 1.396(3) . ? C1 C6 1.397(3) . ? C1 C3 1.516(2) . ? C2 C7 1.395(3) . ? C2 C4 1.394(3) . ? C2 C5 1.512(2) . ? C3 C5 1.534(2) 1_544 ? C4 C10 1.394(2) . ? C5 C3 1.534(2) 1_566 ? C6 C12 1.393(2) . ? C7 C9 1.388(2) . ? C8 C11 1.393(2) . ? 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 O6 Co1 O3 122.25(7) . . ? O6 Co1 O1 123.75(7) . . ? O3 Co1 O1 113.99(6) . . ? O6 Co1 N1 88.34(6) . . ? O3 Co1 N1 90.24(6) . . ? O1 Co1 N1 90.96(6) . . ? O6 Co1 N2 91.37(6) . . ? O3 Co1 N2 89.49(6) . . ? O1 Co1 N2 89.61(6) . . ? N1 Co1 N2 179.42(6) . . ? O3 V1 O1 109.69(7) 2_565 . ? O3 V1 O5 109.19(7) 2_565 . ? O1 V1 O5 108.56(6) . . ? O3 V1 O2 108.84(7) 2_565 . ? O1 V1 O2 110.15(7) . . ? O5 V1 O2 110.39(7) . . ? O4 V2 O6 108.70(7) . . ? O4 V2 O2 108.33(7) . 2_665 ? O6 V2 O2 109.41(7) . 2_665 ? O4 V2 O5 110.72(7) . 1_545 ? O6 V2 O5 110.21(7) . 1_545 ? O2 V2 O5 109.44(7) 2_665 1_545 ? V1 O1 Co1 141.10(9) . . ? V1 O2 V2 136.07(9) . 2_665 ? V1 O3 Co1 170.78(9) 2_565 . ? V1 O5 V2 145.60(9) . 1_565 ? V2 O6 Co1 176.75(10) . . ? C11 N1 C12 117.68(15) . . ? C11 N1 Co1 120.09(12) . . ? C12 N1 Co1 121.87(12) . . ? C9 N2 C10 117.27(15) . . ? C9 N2 Co1 117.51(12) . . ? C10 N2 Co1 125.10(12) . . ? C8 C1 C6 117.00(15) . . ? C8 C1 C3 121.66(17) . . ? C6 C1 C3 121.34(17) . . ? C7 C2 C4 116.71(15) . . ? C7 C2 C5 120.81(17) . . ? C4 C2 C5 122.47(17) . . ? C1 C3 C5 112.65(15) . 1_544 ? C10 C4 C2 120.13(18) . . ? C2 C5 C3 112.05(15) . 1_566 ? C12 C6 C1 120.04(18) . . ? C9 C7 C2 120.13(17) . . ? C11 C8 C1 119.73(17) . . ? N2 C9 C7 123.04(17) . . ? N2 C10 C4 122.70(17) . . ? N1 C11 C8 122.98(18) . . ? N1 C12 C6 122.57(18) . . ? # Attachment '- NiBpaV2O6_2H2O.cif' data_NiBpaV2O6_2H2O_Ni(H2O)2bpe(V4O11) _database_code_depnum_ccdc_archive 'CCDC 871306' #TrackingRef '- NiBpaV2O6_2H2O.cif' _audit_creation_date 2008-03-12T10:03:20-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.3 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C12 H14 N2 Ni O7 V2' _chemical_formula_sum 'C12 H18 N2 Ni O9 V2' _chemical_formula_weight 494.86 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'C 2/c' _symmetry_space_group_name_Hall '-C 2yc' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 28.258(5) _cell_length_b 9.612(5) _cell_length_c 14.579(5) _cell_angle_alpha 90.000(5) _cell_angle_beta 110.191(5) _cell_angle_gamma 90.000(5) _cell_volume 3717(2) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7832 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 27.91 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description Prism _exptl_crystal_colour Green _exptl_crystal_size_max 0.150 _exptl_crystal_size_mid 0.086 _exptl_crystal_size_min 0.076 _exptl_crystal_density_diffrn 1.754 _exptl_crystal_density_meas 1.75(1) _exptl_crystal_density_method flotation' _exptl_crystal_F_000 1968 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1 -1 1 0.0470 1 1 -1 0.0720 1 -1 -1 0.0430 -1 1 1 0.0430 1 0 0 0.0380 -1 0 0 0.0380 _exptl_special_details ; ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 2.034 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.8170 _exptl_absorpt_correction_T_max 0.8759 _exptl_absorpt_process_details ; X-RED (Stoe & Cie, March 2001 Revision 1.22) and X-SHAPE (Stoe & Cie, October 1999, Revision 1.06) 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 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_detector 'image plate (34 cm diameter)' _diffrn_measurement_device '2-circle goniometer' _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_detector_type STOE _diffrn_detector_area_resol_mean 6.67 _diffrn_source 'sealed X-ray tube, 12 x 0.4 mm long-fine focus' _diffrn_source_voltage 50 _diffrn_source_current 40 _diffrn_source_power 2.00 _diffrn_radiation_polarisn_norm 0 _diffrn_radiation_collimation '0.5 mm diameter, monocapillary' _diffrn_measurement_method 'rotation method' _diffrn_measurement_details ; 222 frames, detector distance = 90 mm ; _diffrn_reflns_av_R_equivalents 0.0662 _diffrn_reflns_av_unetI/netI 0.1150 _diffrn_reflns_number 10579 _diffrn_reflns_limit_h_min -35 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.25 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.996 _diffrn_measured_fraction_theta_max 0.996 _reflns_number_total 3778 _reflns_number_gt 2327 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # 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. ; _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^)+(0.0107P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_number_reflns 3778 _refine_ls_number_parameters 244 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0824 _refine_ls_R_factor_gt 0.0389 _refine_ls_wR_factor_ref 0.0768 _refine_ls_wR_factor_gt 0.0678 _refine_ls_goodness_of_fit_ref 0.709 _refine_ls_restrained_S_all 0.709 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.725 _refine_diff_density_min -0.416 _refine_diff_density_rms 0.093 #----------------------------------------------------------------------------# # 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 0.0000 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' V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 '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 N1 N -0.14537(13) 0.7049(4) 0.4253(2) 0.0159(7) Uani 1 1 d . . . N2 N 0.20044(13) 0.7859(4) 0.7698(2) 0.0176(7) Uani 1 1 d . . . C10 C 0.18141(17) 0.8018(4) 0.6722(3) 0.0215(9) Uani 1 1 d . C . H10A H 0.2038 0.8082 0.6384 0.026 Uiso 1 1 calc R A 1 C5 C -0.12339(18) 0.5924(5) 0.4760(3) 0.0256(10) Uani 1 1 d . C . H5A H -0.1429 0.5131 0.4719 0.031 Uiso 1 1 calc R B 1 C1A C -0.11707(19) 0.8161(5) 0.4320(4) 0.0333(12) Uani 1 1 d . C 1 H1A H -0.1316 0.8950 0.3965 0.040 Uiso 1 1 calc R C 1 C2A C -0.0668(2) 0.8198(6) 0.4896(5) 0.0577(18) Uani 1 1 d . C 1 H2A H -0.0485 0.9017 0.4952 0.069 Uiso 1 1 calc R C 1 C3A C -0.0433(2) 0.7001(6) 0.5399(4) 0.0465(14) Uani 1 1 d . C 1 C4A C -0.0733(2) 0.5882(5) 0.5340(4) 0.0357(12) Uani 1 1 d . C 1 H4A H -0.0600 0.5081 0.5693 0.043 Uiso 1 1 calc R C 1 C6 C 0.16735(17) 0.7750(5) 0.8167(3) 0.0267(10) Uani 1 1 d . C 1 H6 H 0.1796 0.7606 0.8839 0.032 Uiso 1 1 calc R C 1 C7A C 0.11607(19) 0.7841(7) 0.7700(4) 0.0482(15) Uani 1 1 d . C 1 H7A H 0.0945 0.7767 0.8057 0.058 Uiso 1 1 calc R C 1 C8A C 0.0963(2) 0.8043(6) 0.6691(4) 0.0471(14) Uani 1 1 d . C 1 C9A C 0.13076(19) 0.8090(5) 0.6197(4) 0.0325(11) Uani 1 1 d . C 1 H9A H 0.1195 0.8168 0.5520 0.039 Uiso 1 1 calc R C 1 C11A C 0.0136(3) 0.6937(8) 0.5981(6) 0.082(2) Uani 1 1 d . C 1 H11A H 0.0181 0.6503 0.6606 0.099 Uiso 1 1 calc R C 1 H11B H 0.0291 0.6333 0.5633 0.099 Uiso 1 1 calc R C 1 C12A C 0.0401(2) 0.8213(8) 0.6160(6) 0.069(2) Uani 1 1 d . C 1 H12A H 0.0263 0.8805 0.6546 0.083 Uiso 1 1 calc R C 1 H12B H 0.0347 0.8677 0.5541 0.083 Uiso 1 1 calc R C 1 O1 O -0.11964(11) 0.7660(3) 0.2035(2) 0.0234(7) Uani 1 1 d . . . O2 O -0.22553(11) 0.9033(3) 0.4035(2) 0.0160(6) Uani 1 1 d . . . O3 O -0.21590(12) 0.5177(3) 0.2891(2) 0.0171(6) Uani 1 1 d D . . O4 O -0.19611(12) 0.8918(3) 0.0495(2) 0.0241(7) Uani 1 1 d . . . O5 O -0.23447(11) 0.6043(3) 0.45374(19) 0.0180(6) Uani 1 1 d . . . O6 O -0.20202(13) 0.6002(3) 0.0991(2) 0.0260(7) Uani 1 1 d . . . O7 O -0.20902(11) 0.8091(3) 0.22809(19) 0.0171(6) Uani 1 1 d . . . V1 V -0.18039(3) 0.76988(7) 0.14830(5) 0.01281(16) Uani 1 1 d . C . V2 V -0.25407(3) 0.50203(7) 0.52314(5) 0.01364(16) Uani 1 1 d . . . Ni1 Ni -0.22168(2) 0.71215(5) 0.34523(4) 0.01156(12) Uani 1 1 d . . . OW1 O -0.0367(2) 1.1085(8) 0.6526(6) 0.147(3) Uani 1 1 d . . . OW2 O 0.0212(2) 0.3522(7) 0.6769(5) 0.122(3) Uani 1 1 d . . . H3B H -0.2077(18) 0.509(5) 0.237(3) 0.028(13) Uiso 1 1 d D . . H3A H -0.2425(17) 0.468(5) 0.282(4) 0.056(19) Uiso 1 1 d 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 N1 0.0162(18) 0.0183(18) 0.0112(17) -0.0009(15) 0.0023(15) 0.0019(16) N2 0.0188(18) 0.0126(17) 0.0191(19) 0.0009(16) 0.0037(16) 0.0005(16) C10 0.024(2) 0.017(2) 0.020(2) 0.0025(18) 0.0023(19) -0.0020(19) C5 0.021(3) 0.026(2) 0.028(3) 0.007(2) 0.006(2) 0.001(2) C1A 0.021(3) 0.029(3) 0.040(3) 0.010(2) -0.002(2) -0.003(2) C2A 0.025(3) 0.040(3) 0.084(5) 0.016(3) -0.010(3) -0.014(3) C3A 0.022(3) 0.048(3) 0.053(3) 0.011(3) -0.007(3) -0.001(3) C4A 0.029(3) 0.037(3) 0.035(3) 0.015(2) 0.003(2) 0.004(2) C6 0.022(2) 0.035(2) 0.023(2) 0.004(2) 0.007(2) 0.001(2) C7A 0.019(3) 0.073(4) 0.054(4) 0.012(3) 0.015(3) -0.005(3) C8A 0.027(3) 0.048(3) 0.054(4) 0.006(3) -0.002(3) -0.002(3) C9A 0.028(3) 0.031(3) 0.030(3) 0.009(2) -0.001(2) -0.006(2) C11A 0.044(4) 0.059(4) 0.101(6) 0.019(4) -0.029(4) -0.006(4) C12A 0.020(3) 0.071(5) 0.093(6) -0.006(4) -0.008(3) 0.004(3) O1 0.0181(16) 0.0281(17) 0.0203(15) 0.0008(13) 0.0019(13) 0.0009(13) O2 0.0159(15) 0.0170(14) 0.0130(13) -0.0038(12) 0.0021(12) 0.0021(13) O3 0.0238(17) 0.0122(14) 0.0159(15) -0.0039(12) 0.0074(14) -0.0011(13) O4 0.0310(19) 0.0237(16) 0.0204(16) 0.0075(13) 0.0125(15) 0.0062(14) O5 0.0238(17) 0.0200(14) 0.0118(15) 0.0001(12) 0.0083(14) -0.0025(13) O6 0.039(2) 0.0164(15) 0.0250(17) -0.0062(13) 0.0143(16) -0.0079(14) O7 0.0243(17) 0.0136(15) 0.0130(14) 0.0030(11) 0.0058(13) 0.0016(12) V1 0.0172(4) 0.0100(3) 0.0113(3) 0.0005(3) 0.0051(3) -0.0003(3) V2 0.0221(4) 0.0100(3) 0.0103(3) -0.0002(3) 0.0075(3) 0.0001(3) Ni1 0.0152(3) 0.0100(2) 0.0092(3) 0.0000(2) 0.0039(2) 0.0002(2) OW1 0.063(4) 0.177(7) 0.196(7) -0.128(6) 0.039(5) -0.002(4) OW2 0.073(4) 0.164(6) 0.138(6) 0.095(5) 0.049(4) 0.045(4) _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 N1 C1A 1.318(6) . ? N1 C5 1.336(6) . ? N1 Ni1 2.069(3) . ? N2 C6 1.340(5) . ? N2 C10 1.344(5) . ? N2 Ni1 2.093(4) 8_566 ? C10 C9A 1.372(6) . ? C5 C4A 1.376(7) . ? C1A C2A 1.379(7) . ? C2A C3A 1.403(8) . ? C3A C4A 1.354(7) . ? C3A C11A 1.537(8) . ? C6 C7A 1.375(7) . ? C7A C8A 1.394(8) . ? C8A C9A 1.398(7) . ? C8A C12A 1.517(8) . ? C11A C12A 1.413(9) . ? O1 V1 1.625(3) . ? O2 V2 1.652(3) 7_466 ? O2 Ni1 2.043(3) . ? O3 Ni1 2.069(3) . ? O4 V2 1.788(3) 4_455 ? O4 V1 1.789(3) . ? O5 V2 1.638(3) . ? O5 Ni1 2.026(3) . ? O6 V2 1.797(3) 6_565 ? O6 V1 1.802(3) . ? O7 V1 1.673(3) . ? O7 Ni1 2.082(3) . ? V2 O2 1.652(3) 7_466 ? V2 O4 1.788(3) 4_445 ? V2 O6 1.797(3) 6_566 ? Ni1 N2 2.093(4) 8_465 ? 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 C1A N1 C5 117.5(4) . . ? C1A N1 Ni1 120.1(3) . . ? C5 N1 Ni1 122.3(3) . . ? C6 N2 C10 117.0(4) . . ? C6 N2 Ni1 121.6(3) . 8_566 ? C10 N2 Ni1 121.3(3) . 8_566 ? N2 C10 C9A 123.7(4) . . ? N1 C5 C4A 123.2(4) . . ? N1 C1A C2A 122.5(5) . . ? C1A C2A C3A 120.0(5) . . ? C4A C3A C2A 116.3(5) . . ? C4A C3A C11A 121.1(5) . . ? C2A C3A C11A 122.5(5) . . ? C3A C4A C5 120.4(5) . . ? N2 C6 C7A 122.9(4) . . ? C6 C7A C8A 120.2(5) . . ? C7A C8A C9A 116.7(5) . . ? C7A C8A C12A 121.5(6) . . ? C9A C8A C12A 121.8(6) . . ? C10 C9A C8A 119.3(5) . . ? C12A C11A C3A 116.9(6) . . ? C11A C12A C8A 113.3(6) . . ? V2 O2 Ni1 147.67(16) 7_466 . ? V2 O4 V1 142.27(17) 4_455 . ? V2 O5 Ni1 168.25(18) . . ? V2 O6 V1 146.4(2) 6_565 . ? V1 O7 Ni1 136.92(16) . . ? O1 V1 O7 110.04(15) . . ? O1 V1 O4 109.88(15) . . ? O7 V1 O4 111.49(13) . . ? O1 V1 O6 109.34(15) . . ? O7 V1 O6 107.56(13) . . ? O4 V1 O6 108.46(14) . . ? O5 V2 O2 109.72(14) . 7_466 ? O5 V2 O4 110.76(14) . 4_445 ? O2 V2 O4 109.30(14) 7_466 4_445 ? O5 V2 O6 109.23(14) . 6_566 ? O2 V2 O6 107.23(14) 7_466 6_566 ? O4 V2 O6 110.53(15) 4_445 6_566 ? O5 Ni1 O2 94.94(11) . . ? O5 Ni1 N1 88.53(12) . . ? O2 Ni1 N1 89.45(13) . . ? O5 Ni1 O3 84.60(11) . . ? O2 Ni1 O3 178.44(13) . . ? N1 Ni1 O3 89.04(13) . . ? O5 Ni1 O7 175.74(11) . . ? O2 Ni1 O7 89.27(11) . . ? N1 Ni1 O7 92.12(12) . . ? O3 Ni1 O7 91.20(11) . . ? O5 Ni1 N2 88.65(12) . 8_465 ? O2 Ni1 N2 90.78(13) . 8_465 ? N1 Ni1 N2 177.19(13) . 8_465 ? O3 Ni1 N2 90.71(13) . 8_465 ? O7 Ni1 N2 90.68(12) . 8_465 ?