# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Mannar R. Maurya' _publ_contact_author_email RKMANFCY@IITR.ERNET.IN _publ_section_title ; Polymer-bound oxidovanadium(IV) and dioxidovanadium(V) complexes: synthesis, characterization and catalytic application for the hydroamination of styrene and vinyl pyridine ; loop_ _publ_author_name 'Mannar R. Maurya' 'Aarti Arya' 'Joao Costa Pessoa' 'Umesh Kumar' 'Amit Kumar' # Attachment 'MRM-Aarti-3.cif' data_ups480mrm _database_code_depnum_ccdc_archive 'CCDC 729960' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C76 H80 N8 O16 V4' _chemical_formula_weight 1565.24 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' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P212121 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 20.070(4) _cell_length_b 10.750(2) _cell_length_c 8.5203(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1838.3(6) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour Brown _exptl_crystal_size_max 0.52 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.19 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.414 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 812 _exptl_absorpt_coefficient_mu 0.566 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.698 _exptl_absorpt_correction_T_max 0.896 _exptl_absorpt_process_details 'North et al., 1968' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _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 40295 _diffrn_reflns_av_R_equivalents 0.0401 _diffrn_reflns_av_sigmaI/netI 0.0241 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.60 _diffrn_reflns_theta_max 26.88 _reflns_number_total 3931 _reflns_number_gt 3602 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker KAPPA X8APEX' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0000P)^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 Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_number_reflns 3931 _refine_ls_number_parameters 238 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0337 _refine_ls_R_factor_gt 0.0281 _refine_ls_wR_factor_ref 0.0477 _refine_ls_wR_factor_gt 0.0469 _refine_ls_goodness_of_fit_ref 2.133 _refine_ls_restrained_S_all 2.133 _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 V4 V 0.444965(14) 0.05673(3) 0.47756(3) 0.02896(9) Uani 1 1 d . . . O1 O 0.53582(5) 0.11834(9) 0.49216(14) 0.0367(3) Uani 1 1 d . . . O2 O 0.46170(6) -0.01837(10) 0.70331(12) 0.0348(3) Uani 1 1 d . . . O3 O 0.41356(6) 0.20622(11) 0.59617(13) 0.0369(3) Uani 1 1 d . . . O4 O 0.41882(6) 0.10515(10) 0.30981(14) 0.0379(3) Uani 1 1 d . . . N1 N 0.48367(7) -0.10834(12) 0.39097(15) 0.0296(3) Uani 1 1 d . . . N2 N 0.35004(7) -0.03693(13) 0.52571(17) 0.0357(3) Uani 1 1 d . . . C6 C 0.59292(9) -0.02557(16) 0.3252(2) 0.0332(4) Uani 1 1 d . . . C1 C 0.58982(9) 0.08272(16) 0.4183(2) 0.0346(5) Uani 1 1 d . . . C2 C 0.64860(10) 0.15360(18) 0.4329(3) 0.0506(6) Uani 1 1 d . . . H2 H 0.6492 0.2216 0.5004 0.061 Uiso 1 1 calc R . . C3 C 0.70432(11) 0.1244(2) 0.3502(3) 0.0653(7) Uani 1 1 d . . . H3 H 0.7421 0.1738 0.3606 0.078 Uiso 1 1 calc R . . C5 C 0.65131(10) -0.0521(2) 0.2412(2) 0.0515(5) Uani 1 1 d . . . H5 H 0.6528 -0.1222 0.1774 0.062 Uiso 1 1 calc R . . C4 C 0.70604(12) 0.0229(2) 0.2509(3) 0.0703(8) Uani 1 1 d . . . H4 H 0.7439 0.0059 0.1917 0.084 Uiso 1 1 calc R . . C7 C 0.54110(9) -0.11631(16) 0.32355(19) 0.0330(4) Uani 1 1 d . . . H7 H 0.5496 -0.1890 0.2679 0.040 Uiso 1 1 calc R . . C9 C 0.40140(9) -0.24203(16) 0.5267(3) 0.0479(5) Uani 1 1 d . . . H9A H 0.3859 -0.3275 0.5241 0.057 Uiso 1 1 calc R . . H9B H 0.4316 -0.2340 0.6149 0.057 Uiso 1 1 calc R . . C10 C 0.34305(10) -0.15869(18) 0.5533(2) 0.0413(5) Uani 1 1 d . . . C11 C 0.28226(11) -0.2066(2) 0.6039(3) 0.0614(7) Uani 1 1 d . . . H11 H 0.2782 -0.2913 0.6240 0.074 Uiso 1 1 calc R . . C12 C 0.22884(12) -0.1304(3) 0.6242(3) 0.0708(7) Uani 1 1 d . . . H12 H 0.1883 -0.1624 0.6581 0.085 Uiso 1 1 calc R . . C13 C 0.23553(11) -0.0063(2) 0.5940(3) 0.0662(7) Uani 1 1 d . . . H13 H 0.1998 0.0478 0.6069 0.079 Uiso 1 1 calc R . . C14 C 0.29667(10) 0.0367(2) 0.5439(2) 0.0485(5) Uani 1 1 d . . . H14 H 0.3011 0.1210 0.5217 0.058 Uiso 1 1 calc R . . C15 C 0.45106(9) 0.02774(16) 0.83653(19) 0.0339(4) Uani 1 1 d . . . C17 C 0.42413(9) 0.14594(17) 0.8600(2) 0.0416(5) Uani 1 1 d . . . H17 H 0.4165 0.1710 0.9629 0.050 Uiso 1 1 calc R . . C18 C 0.40811(8) 0.22785(16) 0.7425(2) 0.0336(4) Uani 1 1 d . . . C19 C 0.38234(9) 0.35568(17) 0.7839(2) 0.0470(6) Uani 1 1 d . . . H19A H 0.4190 0.4082 0.8133 0.071 Uiso 1 1 calc R . . H19B H 0.3517 0.3493 0.8701 0.071 Uiso 1 1 calc R . . H19C H 0.3600 0.3908 0.6948 0.071 Uiso 1 1 calc R . . C16 C 0.47001(9) -0.05037(18) 0.9762(2) 0.0545(5) Uani 1 1 d . . . H16A H 0.4620 -0.1365 0.9531 0.082 Uiso 1 1 calc R . . H16C H 0.4438 -0.0260 1.0652 0.082 Uiso 1 1 calc R . . H16B H 0.5164 -0.0385 0.9994 0.082 Uiso 1 1 calc R . . C8 C 0.43955(10) -0.21579(16) 0.3771(2) 0.0426(5) Uani 1 1 d . . . H8A H 0.4658 -0.2884 0.3499 0.051 Uiso 1 1 calc R . . H8B H 0.4081 -0.2012 0.2926 0.051 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 V4 0.03591(17) 0.02626(15) 0.02469(14) -0.00142(13) -0.00011(14) 0.00127(15) O1 0.0373(7) 0.0334(6) 0.0394(7) -0.0059(6) 0.0011(6) -0.0049(5) O2 0.0463(9) 0.0335(7) 0.0245(6) -0.0016(5) -0.0007(5) 0.0043(6) O3 0.0480(8) 0.0310(7) 0.0315(7) -0.0059(6) 0.0004(6) 0.0066(6) O4 0.0484(8) 0.0360(8) 0.0294(7) 0.0018(6) -0.0029(6) 0.0040(6) N1 0.0348(9) 0.0273(8) 0.0266(7) -0.0036(6) -0.0007(7) -0.0012(7) N2 0.0347(9) 0.0349(9) 0.0376(8) -0.0010(8) 0.0017(7) 0.0005(7) C6 0.0325(11) 0.0341(11) 0.0329(10) 0.0084(8) 0.0006(9) 0.0030(9) C1 0.0343(12) 0.0336(11) 0.0360(10) 0.0102(8) -0.0073(9) -0.0015(10) C2 0.0414(14) 0.0345(12) 0.0760(17) 0.0097(11) -0.0098(12) -0.0044(10) C3 0.0322(14) 0.0569(17) 0.107(2) 0.0115(15) 0.0044(14) -0.0044(12) C5 0.0489(14) 0.0458(13) 0.0597(13) 0.0067(12) 0.0111(11) 0.0107(13) C4 0.0426(15) 0.0632(17) 0.105(2) 0.0145(16) 0.0229(14) 0.0048(13) C7 0.0422(13) 0.0297(10) 0.0272(9) -0.0028(8) -0.0037(9) 0.0082(9) C9 0.0457(12) 0.0282(10) 0.0698(14) 0.0005(11) 0.0053(12) -0.0103(9) C10 0.0371(12) 0.0411(12) 0.0456(12) -0.0004(10) 0.0036(9) -0.0065(10) C11 0.0479(15) 0.0546(15) 0.0818(17) 0.0064(13) 0.0123(13) -0.0141(13) C12 0.0432(16) 0.085(2) 0.0839(19) 0.0051(15) 0.0145(13) -0.0154(15) C13 0.0373(15) 0.0749(18) 0.0863(18) -0.0027(14) 0.0092(13) 0.0063(13) C14 0.0386(12) 0.0511(13) 0.0558(13) -0.0001(12) 0.0015(10) 0.0051(11) C15 0.0334(11) 0.0406(11) 0.0276(9) -0.0010(8) -0.0006(9) -0.0061(10) C17 0.0527(15) 0.0436(12) 0.0286(10) -0.0110(9) -0.0005(9) 0.0069(10) C18 0.0207(10) 0.0351(11) 0.0450(12) -0.0141(9) -0.0010(9) -0.0027(9) C19 0.0424(13) 0.0449(13) 0.0538(13) -0.0206(11) -0.0078(10) 0.0089(10) C16 0.0796(15) 0.0556(12) 0.0283(9) 0.0046(12) -0.0003(10) 0.0066(12) C8 0.0408(12) 0.0339(11) 0.0531(12) -0.0154(9) -0.0008(11) -0.0036(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 V4 O4 1.6091(12) . ? V4 O1 1.9439(11) . ? V4 O3 2.0003(12) . ? V4 N1 2.0729(14) . ? V4 O2 2.1129(11) . ? V4 N2 2.1936(14) . ? O1 C1 1.311(2) . ? O2 C15 1.2569(18) . ? O3 C18 1.273(2) . ? N1 C7 1.291(2) . ? N1 C8 1.460(2) . ? N2 C10 1.337(2) . ? N2 C14 1.341(2) . ? C6 C5 1.402(2) . ? C6 C1 1.410(2) . ? C6 C7 1.426(2) . ? C1 C2 1.410(2) . ? C2 C3 1.359(3) . ? C2 H2 0.9300 . ? C3 C4 1.381(3) . ? C3 H3 0.9300 . ? C5 C4 1.365(3) . ? C5 H5 0.9300 . ? C4 H4 0.9300 . ? C7 H7 0.9300 . ? C9 C10 1.492(2) . ? C9 C8 1.513(3) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C11 1.393(3) . ? C11 C12 1.360(3) . ? C11 H11 0.9300 . ? C12 C13 1.365(3) . ? C12 H12 0.9300 . ? C13 C14 1.379(3) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? C15 C17 1.395(2) . ? C15 C16 1.505(2) . ? C17 C18 1.372(2) . ? C17 H17 0.9300 . ? C18 C19 1.510(2) . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? C16 H16A 0.9600 . ? C16 H16C 0.9600 . ? C16 H16B 0.9600 . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? 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 O4 V4 O1 104.63(6) . . ? O4 V4 O3 94.94(6) . . ? O1 V4 O3 89.40(5) . . ? O4 V4 N1 94.76(6) . . ? O1 V4 N1 87.88(5) . . ? O3 V4 N1 170.30(5) . . ? O4 V4 O2 169.76(6) . . ? O1 V4 O2 85.58(5) . . ? O3 V4 O2 84.10(5) . . ? N1 V4 O2 86.41(5) . . ? O4 V4 N2 91.80(6) . . ? O1 V4 N2 163.56(5) . . ? O3 V4 N2 90.03(5) . . ? N1 V4 N2 89.95(6) . . ? O2 V4 N2 78.02(5) . . ? C1 O1 V4 130.19(11) . . ? C15 O2 V4 130.12(11) . . ? C18 O3 V4 131.96(12) . . ? C7 N1 C8 116.94(15) . . ? C7 N1 V4 123.36(12) . . ? C8 N1 V4 118.60(11) . . ? C10 N2 C14 118.27(16) . . ? C10 N2 V4 124.98(12) . . ? C14 N2 V4 116.40(12) . . ? C5 C6 C1 119.44(18) . . ? C5 C6 C7 117.75(18) . . ? C1 C6 C7 122.56(16) . . ? O1 C1 C6 123.22(16) . . ? O1 C1 C2 119.44(17) . . ? C6 C1 C2 117.33(17) . . ? C3 C2 C1 121.2(2) . . ? C3 C2 H2 119.4 . . ? C1 C2 H2 119.4 . . ? C2 C3 C4 121.4(2) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? C4 C5 C6 121.4(2) . . ? C4 C5 H5 119.3 . . ? C6 C5 H5 119.3 . . ? C5 C4 C3 118.9(2) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? N1 C7 C6 126.98(16) . . ? N1 C7 H7 116.5 . . ? C6 C7 H7 116.5 . . ? C10 C9 C8 114.40(17) . . ? C10 C9 H9A 108.7 . . ? C8 C9 H9A 108.7 . . ? C10 C9 H9B 108.7 . . ? C8 C9 H9B 108.7 . . ? H9A C9 H9B 107.6 . . ? N2 C10 C11 120.55(19) . . ? N2 C10 C9 118.61(16) . . ? C11 C10 C9 120.84(18) . . ? C12 C11 C10 120.5(2) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C11 C12 C13 119.1(2) . . ? C11 C12 H12 120.4 . . ? C13 C12 H12 120.4 . . ? C12 C13 C14 118.3(2) . . ? C12 C13 H13 120.9 . . ? C14 C13 H13 120.9 . . ? N2 C14 C13 123.3(2) . . ? N2 C14 H14 118.4 . . ? C13 C14 H14 118.4 . . ? O2 C15 C17 123.69(16) . . ? O2 C15 C16 116.82(16) . . ? C17 C15 C16 119.49(15) . . ? C18 C17 C15 124.79(16) . . ? C18 C17 H17 117.6 . . ? C15 C17 H17 117.6 . . ? O3 C18 C17 125.28(16) . . ? O3 C18 C19 115.12(16) . . ? C17 C18 C19 119.59(17) . . ? C18 C19 H19A 109.5 . . ? C18 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C18 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? H16C C16 H16B 109.5 . . ? N1 C8 C9 112.72(14) . . ? N1 C8 H8A 109.0 . . ? C9 C8 H8A 109.0 . . ? N1 C8 H8B 109.0 . . ? C9 C8 H8B 109.0 . . ? H8A C8 H8B 107.8 . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 26.88 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.289 _refine_diff_density_min -0.204 _refine_diff_density_rms 0.037 # Attachment 'MRM.Aatri-3_rev.cif.txt' data_ups480 _database_code_depnum_ccdc_archive 'CCDC 745474' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H20 N2 O4 V' _chemical_formula_weight 391.31 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' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) _symmetry_space_group_name_Hall P2ac2ab loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 8.5203(17) _cell_length_b 10.749(2) _cell_length_c 20.070(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1838.2(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour ? _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.414 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 812 _exptl_absorpt_coefficient_mu 0.566 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8266 _exptl_absorpt_correction_T_max 0.9456 _exptl_absorpt_process_details 'North et al., 1968' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _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 40295 _diffrn_reflns_av_R_equivalents 0.0401 _diffrn_reflns_av_sigmaI/netI 0.0241 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.60 _diffrn_reflns_theta_max 26.88 _reflns_number_total 3931 _reflns_number_gt 3602 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Apex2 V.1.0-27 (Bruker Nonius, 2005)' _computing_cell_refinement 'Bruker SAINT V7.12A' _computing_data_reduction 'Bruker SAINT 6.14' _computing_structure_solution '6.12 Bruker AXS' _computing_structure_refinement '6.12 Bruker AXS' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0378P)^2^+0.0880P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.012(15) _refine_ls_number_reflns 3931 _refine_ls_number_parameters 315 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0307 _refine_ls_R_factor_gt 0.0253 _refine_ls_wR_factor_ref 0.0630 _refine_ls_wR_factor_gt 0.0599 _refine_ls_goodness_of_fit_ref 1.034 _refine_ls_restrained_S_all 1.034 _refine_ls_shift/su_max 0.001 _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 V1 V 0.27233(3) 0.80670(2) 0.194991(14) 0.02808(8) Uani 1 1 d . . . O1 O 0.25800(15) 0.86835(10) 0.28602(6) 0.0375(3) Uani 1 1 d . . . N1 N 0.35919(15) 0.64140(13) 0.23365(7) 0.0306(3) Uani 1 1 d . . . C1 C 0.3314(2) 0.83266(16) 0.33976(9) 0.0351(4) Uani 1 1 d . . . O2 O 0.04639(13) 0.73174(11) 0.21194(6) 0.0356(3) Uani 1 1 d . . . N2 N 0.22394(18) 0.71313(13) 0.09991(7) 0.0375(3) Uani 1 1 d . . . C2 C 0.3166(3) 0.9040(2) 0.39867(10) 0.0516(5) Uani 1 1 d . . . H2 H 0.238(3) 0.977(2) 0.3957(12) 0.077(8) Uiso 1 1 d . . . O3 O 0.15384(14) 0.95656(11) 0.16359(6) 0.0381(3) Uani 1 1 d . . . C3 C 0.4003(4) 0.8744(3) 0.45454(12) 0.0672(7) Uani 1 1 d . . . H3 H 0.379(4) 0.926(3) 0.4899(15) 0.094(10) Uiso 1 1 d . . . O4 O 0.44043(14) 0.85527(11) 0.16886(6) 0.0386(3) Uani 1 1 d . . . C4 C 0.4991(4) 0.7728(2) 0.45628(12) 0.0707(8) Uani 1 1 d . . . H4 H 0.547(4) 0.752(3) 0.4954(16) 0.087(9) Uiso 1 1 d . . . C5 C 0.5095(3) 0.6981(2) 0.40162(11) 0.0526(5) Uani 1 1 d . . . H5 H 0.566(3) 0.627(2) 0.3990(10) 0.042(6) Uiso 1 1 d . . . C6 C 0.4248(2) 0.72448(16) 0.34295(9) 0.0351(4) Uani 1 1 d . . . C7 C 0.42676(19) 0.63321(16) 0.29100(9) 0.0334(4) Uani 1 1 d . . . H7 H 0.482(2) 0.5632(18) 0.3020(10) 0.041(5) Uiso 1 1 d . . . C8 C 0.3732(2) 0.53421(19) 0.18968(12) 0.0437(4) Uani 1 1 d . . . H8A H 0.399(2) 0.462(2) 0.2141(10) 0.046(6) Uiso 1 1 d . . . H8B H 0.446(3) 0.5512(18) 0.1621(10) 0.035(5) Uiso 1 1 d . . . C9 C 0.2222(3) 0.50775(17) 0.15174(11) 0.0489(5) Uani 1 1 d . . . H9A H 0.243(3) 0.420(2) 0.1347(11) 0.059(6) Uiso 1 1 d . . . H9B H 0.130(3) 0.509(2) 0.1838(13) 0.066(7) Uiso 1 1 d . . . C10 C 0.1966(2) 0.59109(18) 0.09303(10) 0.0425(4) Uani 1 1 d . . . C11 C 0.1460(3) 0.5435(3) 0.03194(12) 0.0631(6) Uani 1 1 d . . . H11 H 0.121(3) 0.459(3) 0.0296(14) 0.084(9) Uiso 1 1 d . . . C12 C 0.1250(4) 0.6198(3) -0.02130(14) 0.0712(7) Uani 1 1 d . . . H12 H 0.100(4) 0.589(3) -0.0629(16) 0.103(11) Uiso 1 1 d . . . C13 C 0.1557(3) 0.7434(3) -0.01479(12) 0.0678(7) Uani 1 1 d . . . H13 H 0.144(3) 0.795(3) -0.0533(15) 0.081(8) Uiso 1 1 d . . . C14 C 0.2064(3) 0.7872(2) 0.04656(10) 0.0495(5) Uani 1 1 d . . . H14 H 0.226(3) 0.880(2) 0.0574(10) 0.052(6) Uiso 1 1 d . . . C15 C -0.2260(2) 0.6998(2) 0.22002(15) 0.0563(5) Uani 1 1 d . . . H15A H -0.316(3) 0.722(2) 0.1991(12) 0.063(7) Uiso 1 1 d . . . H15B H -0.200(3) 0.609(3) 0.2115(13) 0.077(8) Uiso 1 1 d . . . H15C H -0.249(4) 0.711(3) 0.2602(18) 0.125(14) Uiso 1 1 d . . . C16 C -0.08641(18) 0.77790(15) 0.20107(9) 0.0341(4) Uani 1 1 d . . . C17 C -0.1101(2) 0.89595(19) 0.17408(10) 0.0439(5) Uani 1 1 d . . . H17 H -0.200(3) 0.915(2) 0.1683(10) 0.050(6) Uiso 1 1 d . . . C18 C 0.0072(2) 0.97815(16) 0.15798(8) 0.0347(4) Uani 1 1 d . . . C19 C -0.0344(3) 1.1053(2) 0.13274(12) 0.0474(5) Uani 1 1 d . . . H19A H -0.112(3) 1.097(2) 0.0999(12) 0.053(6) Uiso 1 1 d . . . H19B H -0.048(4) 1.168(3) 0.1683(14) 0.090(9) Uiso 1 1 d . . . H19C H 0.046(4) 1.141(3) 0.1106(15) 0.089(10) 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 V1 0.02398(12) 0.02555(13) 0.03473(15) 0.00123(12) 0.00013(11) 0.00143(10) O1 0.0399(6) 0.0333(6) 0.0394(6) -0.0054(5) -0.0005(5) 0.0061(5) N1 0.0271(6) 0.0287(7) 0.0359(8) -0.0005(6) 0.0012(6) 0.0037(5) C1 0.0369(8) 0.0332(9) 0.0353(10) -0.0002(8) 0.0058(7) -0.0097(7) O2 0.0262(5) 0.0336(6) 0.0470(8) 0.0044(5) 0.0004(5) 0.0011(5) N2 0.0377(7) 0.0392(8) 0.0355(8) -0.0004(6) -0.0013(6) 0.0001(7) C2 0.0749(15) 0.0398(11) 0.0399(12) -0.0035(9) 0.0102(10) -0.0102(11) O3 0.0344(6) 0.0318(6) 0.0480(7) 0.0061(6) 0.0000(6) 0.0054(5) C3 0.108(2) 0.0582(15) 0.0355(12) -0.0020(11) -0.0055(13) -0.0139(15) O4 0.0312(6) 0.0361(7) 0.0483(7) 0.0037(6) 0.0034(5) -0.0016(5) C4 0.108(2) 0.0636(16) 0.0405(13) 0.0044(11) -0.0230(14) -0.0134(15) C5 0.0620(13) 0.0475(13) 0.0484(12) 0.0107(11) -0.0123(10) -0.0050(12) C6 0.0344(8) 0.0372(10) 0.0337(9) 0.0037(8) 0.0001(7) -0.0090(7) C7 0.0286(8) 0.0305(9) 0.0413(11) 0.0080(8) 0.0026(7) 0.0016(7) C8 0.0536(11) 0.0343(10) 0.0431(11) -0.0039(9) 0.0015(11) 0.0146(8) C9 0.0691(13) 0.0303(9) 0.0472(11) -0.0084(8) -0.0062(12) -0.0009(10) C10 0.0467(11) 0.0408(10) 0.0401(10) -0.0060(8) -0.0047(8) 0.0012(9) C11 0.0820(16) 0.0575(15) 0.0498(14) -0.0149(12) -0.0108(13) -0.0076(13) C12 0.0843(18) 0.085(2) 0.0442(14) -0.0140(14) -0.0162(13) -0.0026(15) C13 0.0875(18) 0.0772(17) 0.0386(13) 0.0063(13) -0.0082(12) 0.0037(14) C14 0.0576(12) 0.0533(13) 0.0377(11) 0.0067(9) -0.0025(9) 0.0022(10) C15 0.0270(8) 0.0571(13) 0.0846(17) 0.0073(13) 0.0002(10) -0.0035(11) C16 0.0276(7) 0.0396(10) 0.0351(9) -0.0042(8) 0.0013(7) 0.0016(6) C17 0.0299(9) 0.0469(11) 0.0549(13) 0.0053(9) 0.0003(8) 0.0131(8) C18 0.0424(10) 0.0365(9) 0.0252(8) -0.0020(7) 0.0011(8) 0.0137(7) C19 0.0564(12) 0.0451(12) 0.0407(12) 0.0092(10) 0.0046(11) 0.0197(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 V1 O4 1.6121(13) . ? V1 O1 1.9472(12) . ? V1 O3 2.0029(12) . ? V1 N1 2.0754(14) . ? V1 O2 2.1145(12) . ? V1 N2 2.1961(15) . ? O1 C1 1.305(2) . ? N1 C7 1.290(2) . ? N1 C8 1.456(2) . ? C1 C6 1.410(2) . ? C1 C2 1.415(3) . ? O2 C16 1.255(2) . ? N2 C10 1.339(2) . ? N2 C14 1.342(2) . ? C2 C3 1.367(3) . ? C2 H2 1.03(3) . ? O3 C18 1.276(2) . ? C3 C4 1.379(4) . ? C3 H3 0.92(3) . ? C4 C5 1.362(4) . ? C4 H4 0.91(3) . ? C5 C6 1.410(3) . ? C5 H5 0.90(2) . ? C6 C7 1.432(3) . ? C7 H7 0.915(19) . ? C8 C9 1.522(3) . ? C8 H8A 0.95(2) . ? C8 H8B 0.85(2) . ? C9 C10 1.496(3) . ? C9 H9A 1.02(2) . ? C9 H9B 1.02(2) . ? C10 C11 1.397(3) . ? C11 C12 1.359(4) . ? C11 H11 0.93(3) . ? C12 C13 1.361(4) . ? C12 H12 0.92(3) . ? C13 C14 1.387(3) . ? C13 H13 0.96(3) . ? C14 H14 1.03(2) . ? C15 C16 1.505(3) . ? C15 H15A 0.91(3) . ? C15 H15B 1.02(3) . ? C15 H15C 0.84(4) . ? C16 C17 1.394(3) . ? C17 C18 1.373(3) . ? C17 H17 0.81(2) . ? C18 C19 1.500(3) . ? C19 H19A 0.94(3) . ? C19 H19B 0.99(3) . ? C19 H19C 0.90(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 O4 V1 O1 104.52(6) . . ? O4 V1 O3 94.88(6) . . ? O1 V1 O3 89.42(5) . . ? O4 V1 N1 94.71(6) . . ? O1 V1 N1 87.88(5) . . ? O3 V1 N1 170.41(5) . . ? O4 V1 O2 169.94(6) . . ? O1 V1 O2 85.50(5) . . ? O3 V1 O2 84.16(5) . . ? N1 V1 O2 86.46(5) . . ? O4 V1 N2 91.86(6) . . ? O1 V1 N2 163.60(6) . . ? O3 V1 N2 90.02(6) . . ? N1 V1 N2 89.98(6) . . ? O2 V1 N2 78.13(5) . . ? C1 O1 V1 130.21(11) . . ? C7 N1 C8 116.74(15) . . ? C7 N1 V1 123.45(12) . . ? C8 N1 V1 118.69(12) . . ? O1 C1 C6 123.39(16) . . ? O1 C1 C2 119.25(17) . . ? C6 C1 C2 117.35(18) . . ? C16 O2 V1 129.97(11) . . ? C10 N2 C14 118.62(17) . . ? C10 N2 V1 124.80(13) . . ? C14 N2 V1 116.26(13) . . ? C3 C2 C1 120.8(2) . . ? C3 C2 H2 124.2(14) . . ? C1 C2 H2 115.0(14) . . ? C18 O3 V1 131.89(12) . . ? C2 C3 C4 121.6(2) . . ? C2 C3 H3 112.7(19) . . ? C4 C3 H3 125.7(19) . . ? C5 C4 C3 119.1(2) . . ? C5 C4 H4 121(2) . . ? C3 C4 H4 119(2) . . ? C4 C5 C6 121.4(2) . . ? C4 C5 H5 125.3(14) . . ? C6 C5 H5 113.3(14) . . ? C5 C6 C1 119.48(19) . . ? C5 C6 C7 117.69(18) . . ? C1 C6 C7 122.58(16) . . ? N1 C7 C6 126.71(16) . . ? N1 C7 H7 120.1(13) . . ? C6 C7 H7 113.2(13) . . ? N1 C8 C9 112.43(15) . . ? N1 C8 H8A 110.8(12) . . ? C9 C8 H8A 107.5(12) . . ? N1 C8 H8B 106.5(14) . . ? C9 C8 H8B 109.3(14) . . ? H8A C8 H8B 110.4(18) . . ? C10 C9 C8 113.92(19) . . ? C10 C9 H9A 108.4(12) . . ? C8 C9 H9A 101.3(13) . . ? C10 C9 H9B 112.1(14) . . ? C8 C9 H9B 109.6(14) . . ? H9A C9 H9B 111.1(19) . . ? N2 C10 C11 120.2(2) . . ? N2 C10 C9 118.68(17) . . ? C11 C10 C9 121.12(19) . . ? C12 C11 C10 120.6(2) . . ? C12 C11 H11 121.3(18) . . ? C10 C11 H11 118.0(18) . . ? C11 C12 C13 119.3(2) . . ? C11 C12 H12 122(2) . . ? C13 C12 H12 119(2) . . ? C12 C13 C14 118.4(2) . . ? C12 C13 H13 118.0(17) . . ? C14 C13 H13 123.5(17) . . ? N2 C14 C13 122.8(2) . . ? N2 C14 H14 112.7(11) . . ? C13 C14 H14 124.3(11) . . ? C16 C15 H15A 113.9(15) . . ? C16 C15 H15B 108.7(15) . . ? H15A C15 H15B 111(2) . . ? C16 C15 H15C 110(3) . . ? H15A C15 H15C 102(3) . . ? H15B C15 H15C 110(3) . . ? O2 C16 C17 123.93(16) . . ? O2 C16 C15 116.64(16) . . ? C17 C16 C15 119.42(17) . . ? C18 C17 C16 124.87(17) . . ? C18 C17 H17 119.7(16) . . ? C16 C17 H17 115.4(16) . . ? O3 C18 C17 125.11(16) . . ? O3 C18 C19 115.29(18) . . ? C17 C18 C19 119.59(17) . . ? C18 C19 H19A 108.4(15) . . ? C18 C19 H19B 114.1(16) . . ? H19A C19 H19B 119(2) . . ? C18 C19 H19C 111.8(19) . . ? H19A C19 H19C 103(2) . . ? H19B C19 H19C 99(3) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O4 V1 O1 C1 -72.39(15) . . . . ? O3 V1 O1 C1 -167.27(14) . . . . ? N1 V1 O1 C1 21.93(14) . . . . ? O2 V1 O1 C1 108.54(14) . . . . ? N2 V1 O1 C1 104.6(2) . . . . ? O4 V1 N1 C7 81.04(14) . . . . ? O1 V1 N1 C7 -23.36(13) . . . . ? O3 V1 N1 C7 -97.1(3) . . . . ? O2 V1 N1 C7 -108.98(13) . . . . ? N2 V1 N1 C7 172.91(13) . . . . ? O4 V1 N1 C8 -86.50(14) . . . . ? O1 V1 N1 C8 169.10(13) . . . . ? O3 V1 N1 C8 95.4(4) . . . . ? O2 V1 N1 C8 83.48(13) . . . . ? N2 V1 N1 C8 5.37(13) . . . . ? V1 O1 C1 C6 -9.6(2) . . . . ? V1 O1 C1 C2 171.26(13) . . . . ? O4 V1 O2 C16 -83.2(4) . . . . ? O1 V1 O2 C16 91.68(15) . . . . ? O3 V1 O2 C16 1.80(15) . . . . ? N1 V1 O2 C16 179.82(16) . . . . ? N2 V1 O2 C16 -89.45(16) . . . . ? O4 V1 N2 C10 120.73(16) . . . . ? O1 V1 N2 C10 -56.4(3) . . . . ? O3 V1 N2 C10 -144.39(15) . . . . ? N1 V1 N2 C10 26.02(15) . . . . ? O2 V1 N2 C10 -60.37(15) . . . . ? O4 V1 N2 C14 -65.84(15) . . . . ? O1 V1 N2 C14 117.0(2) . . . . ? O3 V1 N2 C14 29.04(15) . . . . ? N1 V1 N2 C14 -160.55(14) . . . . ? O2 V1 N2 C14 113.06(14) . . . . ? O1 C1 C2 C3 -175.4(2) . . . . ? C6 C1 C2 C3 5.4(3) . . . . ? O4 V1 O3 C18 168.08(16) . . . . ? O1 V1 O3 C18 -87.40(16) . . . . ? N1 V1 O3 C18 -13.8(4) . . . . ? O2 V1 O3 C18 -1.86(16) . . . . ? N2 V1 O3 C18 76.21(16) . . . . ? C1 C2 C3 C4 -1.6(4) . . . . ? C2 C3 C4 C5 -2.1(4) . . . . ? C3 C4 C5 C6 1.7(4) . . . . ? C4 C5 C6 C1 2.2(3) . . . . ? C4 C5 C6 C7 -172.3(2) . . . . ? O1 C1 C6 C5 175.18(17) . . . . ? C2 C1 C6 C5 -5.6(3) . . . . ? O1 C1 C6 C7 -10.6(3) . . . . ? C2 C1 C6 C7 168.56(17) . . . . ? C8 N1 C7 C6 -177.90(17) . . . . ? V1 N1 C7 C6 14.3(2) . . . . ? C5 C6 C7 N1 -178.70(17) . . . . ? C1 C6 C7 N1 7.0(3) . . . . ? C7 N1 C8 C9 140.76(18) . . . . ? V1 N1 C8 C9 -50.9(2) . . . . ? N1 C8 C9 C10 78.9(2) . . . . ? C14 N2 C10 C11 -2.1(3) . . . . ? V1 N2 C10 C11 171.22(17) . . . . ? C14 N2 C10 C9 177.63(19) . . . . ? V1 N2 C10 C9 -9.1(3) . . . . ? C8 C9 C10 N2 -44.1(3) . . . . ? C8 C9 C10 C11 135.6(2) . . . . ? N2 C10 C11 C12 0.5(4) . . . . ? C9 C10 C11 C12 -179.2(2) . . . . ? C10 C11 C12 C13 0.9(4) . . . . ? C11 C12 C13 C14 -0.6(5) . . . . ? C10 N2 C14 C13 2.4(3) . . . . ? V1 N2 C14 C13 -171.5(2) . . . . ? C12 C13 C14 N2 -1.0(4) . . . . ? V1 O2 C16 C17 -0.3(3) . . . . ? V1 O2 C16 C15 -179.11(16) . . . . ? O2 C16 C17 C18 -2.2(3) . . . . ? C15 C16 C17 C18 176.6(2) . . . . ? V1 O3 C18 C17 0.4(3) . . . . ? V1 O3 C18 C19 179.29(13) . . . . ? C16 C17 C18 O3 2.2(3) . . . . ? C16 C17 C18 C19 -176.63(19) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 26.88 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.143 _refine_diff_density_min -0.169 _refine_diff_density_rms 0.034