Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_contact_author_name 'Peter Scott' _publ_contact_author_address ; Department of Chemistry University of Warwick Gibbett Hill Rd COVENTRY CV4 7AL UNITED KINGDOM ; _publ_section_title ; Group 4 catalysts for ethene polymerization containing tetradentate salicylaldiminato ligands ; _publ_contact_author_email PETER.SCOTT@WARWICK.AC.UK loop_ _publ_author_name P.Scott G.Clarkson V.C.Gibson P.K.Y.Goh M.Hammond P.D.Knight T.M.Smit A.J.P.White D.J.Williams # Attachment 'VG00701.cif' data_VG0070 _database_code_depnum_ccdc_archive 'CCDC 615711' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C42 H51 N3 O2 Cl2 Ti' _chemical_formula_weight 748.66 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2191 1.8069 '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 11.989(2) _cell_length_b 13.040(2) _cell_length_c 13.724(2) _cell_angle_alpha 97.867(13) _cell_angle_beta 99.001(11) _cell_angle_gamma 99.407(12) _cell_volume 2061.3(6) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 11.09 _cell_measurement_theta_max 28.03 _exptl_crystal_description needles _exptl_crystal_colour Ruby _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.47 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.206 _exptl_crystal_density_method ? _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 3.233 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; SHELXTL, Bruker AXS Ltd., Version 5.03 (release 1994) Semi-empirical absorption correction using psi-scans implemented in the XPREP program. ; _exptl_absorpt_correction_T_min 0.1853 _exptl_absorpt_correction_T_max 0.3046 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6456 _diffrn_reflns_av_R_equivalents 0.0253 _diffrn_reflns_av_sigmaI/netI 0.0406 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.31 _diffrn_reflns_theta_max 60.00 _reflns_number_total 6113 _reflns_number_observed 4935 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 284 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0678P)^2^+0.6851P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0002(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5829 _refine_ls_number_parameters 452 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0619 _refine_ls_R_factor_obs 0.0474 _refine_ls_wR_factor_all 0.1308 _refine_ls_wR_factor_obs 0.1195 _refine_ls_goodness_of_fit_all 1.031 _refine_ls_goodness_of_fit_obs 1.077 _refine_ls_restrained_S_all 1.050 _refine_ls_restrained_S_obs 1.077 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti Ti 0.26521(4) 0.22752(4) 0.02963(4) 0.0388(2) Uani 1 d . . Cl1 Cl 0.24167(7) 0.26830(6) -0.13163(6) 0.0554(2) Uani 1 d . . Cl2 Cl 0.08532(7) 0.26461(8) 0.04422(8) 0.0669(3) Uani 1 d . . O1 O 0.3672(2) 0.34903(15) 0.0888(2) 0.0435(5) Uani 1 d . . C1 C 0.4688(3) 0.3704(2) 0.1519(2) 0.0414(6) Uani 1 d . . C2 C 0.5063(3) 0.4691(2) 0.2137(2) 0.0455(7) Uani 1 d . . C3 C 0.6090(3) 0.4807(2) 0.2808(3) 0.0515(8) Uani 1 d . . H3A H 0.6347(3) 0.5449(2) 0.3236(3) 0.062 Uiso 1 calc R . C4 C 0.6767(3) 0.4034(2) 0.2892(2) 0.0491(7) Uani 1 d . . C5 C 0.6403(3) 0.3097(2) 0.2227(2) 0.0464(7) Uani 1 d . . H5A H 0.6850(3) 0.2578(2) 0.2242(2) 0.056 Uiso 1 calc R . C6 C 0.5372(3) 0.2914(2) 0.1529(2) 0.0418(6) Uani 1 d . . C7 C 0.5139(3) 0.2006(2) 0.0739(2) 0.0417(7) Uani 1 d . . H7A H 0.5690(3) 0.1579(2) 0.0740(2) 0.050 Uiso 1 calc R . N7 N 0.4242(2) 0.1726(2) 0.0032(2) 0.0388(5) Uani 1 d . . C8 C 0.4332(3) 0.1053(2) -0.0869(2) 0.0407(6) Uani 1 d . . C9 C 0.5384(3) 0.1116(3) -0.1172(3) 0.0494(7) Uani 1 d . . H9A H 0.6037(3) 0.1514(3) -0.0747(3) 0.059 Uiso 1 calc R . C10 C 0.5488(3) 0.0590(3) -0.2112(3) 0.0589(9) Uani 1 d . . H10A H 0.6211(3) 0.0607(3) -0.2283(3) 0.071 Uiso 1 calc R . C11 C 0.4537(3) 0.0060(3) -0.2767(3) 0.0595(9) Uani 1 d . . H11A H 0.4613(3) -0.0260(3) -0.3396(3) 0.071 Uiso 1 calc R . C12 C 0.3434(3) -0.0015(2) -0.2511(2) 0.0490(7) Uani 1 d . . C13 C 0.2430(3) -0.0537(3) -0.3194(3) 0.0604(9) Uani 1 d . . H13A H 0.2494(3) -0.0805(3) -0.3843(3) 0.072 Uiso 1 calc R . C14 C 0.1371(3) -0.0659(3) -0.2936(3) 0.0598(9) Uani 1 d . . H14A H 0.0724(3) -0.0993(3) -0.3407(3) 0.072 Uiso 1 calc R . C15 C 0.1261(3) -0.0277(3) -0.1954(2) 0.0499(7) Uani 1 d . . H15A H 0.0545(3) -0.0385(3) -0.1764(2) 0.060 Uiso 1 calc R . C16 C 0.2210(3) 0.0252(2) -0.1278(2) 0.0407(6) Uani 1 d . . C17 C 0.3329(3) 0.0445(2) -0.1524(2) 0.0400(6) Uani 1 d . . N18 N 0.2119(2) 0.0616(2) -0.0263(2) 0.0391(5) Uani 1 d . . C18 C 0.1752(2) -0.0110(2) 0.0232(2) 0.0402(6) Uani 1 d . . H18A H 0.1478(2) -0.0786(2) -0.0129(2) 0.048 Uiso 1 calc R . C19 C 0.1728(3) 0.0030(2) 0.1283(2) 0.0409(6) Uani 1 d . . C20 C 0.1328(3) -0.0880(2) 0.1669(2) 0.0446(7) Uani 1 d . . H20A H 0.1012(3) -0.1508(2) 0.1233(2) 0.054 Uiso 1 calc R . C21 C 0.1398(3) -0.0853(2) 0.2683(2) 0.0457(7) Uani 1 d . . C22 C 0.1830(3) 0.0137(3) 0.3303(2) 0.0494(7) Uani 1 d . . H22A H 0.1835(3) 0.0173(3) 0.3985(2) 0.059 Uiso 1 calc R . C23 C 0.2248(3) 0.1059(2) 0.2970(2) 0.0458(7) Uani 1 d . . C24 C 0.2238(3) 0.0992(2) 0.1925(2) 0.0420(6) Uani 1 d . . O24 O 0.2725(2) 0.17967(15) 0.1535(2) 0.0439(5) Uani 1 d . . C25 C 0.4395(3) 0.5595(2) 0.2046(3) 0.0526(8) Uani 1 d . . C26 C 0.4346(4) 0.5868(3) 0.0995(3) 0.0673(10) Uani 1 d . . H26A H 0.3930(4) 0.6432(3) 0.0931(3) 0.101 Uiso 1 calc R . H26B H 0.3964(4) 0.5260(3) 0.0511(3) 0.101 Uiso 1 calc R . H26C H 0.5113(4) 0.6083(3) 0.0881(3) 0.101 Uiso 1 calc R . C27 C 0.3175(3) 0.5279(3) 0.2262(4) 0.0711(11) Uani 1 d . . H27A H 0.3223(3) 0.5111(3) 0.2925(4) 0.107 Uiso 1 calc R . H27B H 0.2767(3) 0.4675(3) 0.1785(4) 0.107 Uiso 1 calc R . H27C H 0.2774(3) 0.5855(3) 0.2211(4) 0.107 Uiso 1 calc R . C28 C 0.4993(4) 0.6598(3) 0.2796(3) 0.0719(11) Uani 1 d . . H28A H 0.5037(4) 0.6451(3) 0.3466(3) 0.108 Uiso 1 calc R . H28B H 0.4560(4) 0.7148(3) 0.2715(3) 0.108 Uiso 1 calc R . H28C H 0.5755(4) 0.6820(3) 0.2673(3) 0.108 Uiso 1 calc R . C29 C 0.7850(3) 0.4262(3) 0.3706(3) 0.0641(10) Uani 1 d . . C30 C 0.8576(4) 0.5331(4) 0.3707(4) 0.098(2) Uani 1 d . . H30A H 0.8109(4) 0.5862(4) 0.3752(4) 0.146 Uiso 1 calc R . H30B H 0.8880(4) 0.5319(4) 0.3099(4) 0.146 Uiso 1 calc R . H30C H 0.9199(4) 0.5489(4) 0.4270(4) 0.146 Uiso 1 calc R . C31 C 0.7449(5) 0.4320(5) 0.4733(3) 0.100(2) Uani 1 d . . H31A H 0.6997(5) 0.4861(5) 0.4802(3) 0.150 Uiso 1 calc R . H31B H 0.8109(5) 0.4482(5) 0.5262(3) 0.150 Uiso 1 calc R . H31C H 0.6993(5) 0.3654(5) 0.4770(3) 0.150 Uiso 1 calc R . C32 C 0.8549(5) 0.3410(4) 0.3635(5) 0.116(2) Uani 1 d . . H32A H 0.8071(5) 0.2743(4) 0.3636(5) 0.173 Uiso 1 calc R . H32B H 0.9172(5) 0.3555(4) 0.4198(5) 0.173 Uiso 1 calc R . H32C H 0.8853(5) 0.3385(4) 0.3027(5) 0.173 Uiso 1 calc R . C33 C 0.1088(3) -0.1829(3) 0.3162(3) 0.0559(8) Uani 1 d . . C34 C 0.0681(4) -0.2828(3) 0.2377(3) 0.0654(10) Uani 1 d . . H34A H 0.0494(4) -0.3423(3) 0.2703(3) 0.098 Uiso 1 calc R . H34B H 0.1281(4) -0.2934(3) 0.2007(3) 0.098 Uiso 1 calc R . H34C H 0.0011(4) -0.2753(3) 0.1927(3) 0.098 Uiso 1 calc R . C35 C 0.2192(4) -0.1965(4) 0.3851(3) 0.0859(14) Uani 1 d . . H35A H 0.2022(4) -0.2573(4) 0.4163(3) 0.129 Uiso 1 calc R . H35B H 0.2460(4) -0.1350(4) 0.4357(3) 0.129 Uiso 1 calc R . H35C H 0.2776(4) -0.2055(4) 0.3459(3) 0.129 Uiso 1 calc R . C36 C 0.0141(5) -0.1688(4) 0.3773(4) 0.090(2) Uani 1 d . . H36A H -0.0046(5) -0.2304(4) 0.4070(4) 0.136 Uiso 1 calc R . H36B H -0.0531(5) -0.1589(4) 0.3342(4) 0.136 Uiso 1 calc R . H36C H 0.0407(5) -0.1083(4) 0.4290(4) 0.136 Uiso 1 calc R . C37 C 0.2670(4) 0.2108(3) 0.3693(3) 0.0613(9) Uani 1 d . . C38 C 0.1935(5) 0.2903(3) 0.3355(4) 0.092(2) Uani 1 d . . H38A H 0.1140(5) 0.2631(3) 0.3351(4) 0.138 Uiso 1 calc R . H38B H 0.2032(5) 0.3016(3) 0.2694(4) 0.138 Uiso 1 calc R . H38C H 0.2174(5) 0.3560(3) 0.3810(4) 0.138 Uiso 1 calc R . C39 C 0.2535(5) 0.1988(4) 0.4774(3) 0.090(2) Uani 1 d . . H39A H 0.1742(5) 0.1730(4) 0.4789(3) 0.135 Uiso 1 calc R . H39B H 0.2787(5) 0.2661(4) 0.5201(3) 0.135 Uiso 1 calc R . H39C H 0.2992(5) 0.1499(4) 0.5004(3) 0.135 Uiso 1 calc R . C40 C 0.3944(4) 0.2519(4) 0.3709(3) 0.091(2) Uani 1 d . . H40A H 0.4193(4) 0.3174(4) 0.4164(3) 0.136 Uiso 1 calc R . H40B H 0.4051(4) 0.2628(4) 0.3049(3) 0.136 Uiso 1 calc R . H40C H 0.4386(4) 0.2013(4) 0.3922(3) 0.136 Uiso 1 calc R . N50 N 0.7897(3) 0.2726(4) 0.0289(4) 0.1033(15) Uani 1 d . . C51 C 0.8237(4) 0.3593(4) 0.0455(4) 0.0806(12) Uani 1 d . . C52 C 0.8653(7) 0.4716(5) 0.0673(6) 0.144(3) Uani 1 d . . H52A H 0.8727(7) 0.4979(5) 0.0062(6) 0.216 Uiso 1 d R . H52B H 0.9389(7) 0.4864(5) 0.1109(6) 0.216 Uiso 1 d R . H52C H 0.8119(7) 0.5052(5) 0.0994(6) 0.216 Uiso 1 d 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 Ti 0.0327(3) 0.0341(3) 0.0471(3) 0.0016(2) 0.0062(2) 0.0041(2) Cl1 0.0555(5) 0.0545(4) 0.0564(4) 0.0135(3) 0.0048(4) 0.0128(4) Cl2 0.0391(4) 0.0809(6) 0.0783(6) -0.0007(5) 0.0096(4) 0.0176(4) O1 0.0358(11) 0.0357(10) 0.0551(12) 0.0031(9) 0.0024(9) 0.0046(8) C1 0.037(2) 0.0357(14) 0.049(2) 0.0036(12) 0.0085(13) 0.0024(12) C2 0.046(2) 0.0347(15) 0.051(2) 0.0029(13) 0.0042(14) 0.0034(13) C3 0.055(2) 0.036(2) 0.056(2) -0.0013(13) 0.000(2) 0.0030(14) C4 0.047(2) 0.042(2) 0.052(2) 0.0048(13) -0.0016(15) 0.0021(14) C5 0.042(2) 0.041(2) 0.053(2) 0.0054(13) 0.0009(14) 0.0072(13) C6 0.039(2) 0.0342(14) 0.048(2) 0.0017(12) 0.0026(13) 0.0036(12) C7 0.038(2) 0.0329(14) 0.052(2) 0.0048(12) 0.0046(13) 0.0041(12) N7 0.0358(13) 0.0341(11) 0.0453(13) 0.0049(10) 0.0078(11) 0.0041(10) C8 0.041(2) 0.0358(14) 0.045(2) 0.0028(12) 0.0105(13) 0.0080(12) C9 0.042(2) 0.051(2) 0.057(2) 0.0064(14) 0.0142(14) 0.0118(14) C10 0.048(2) 0.064(2) 0.068(2) 0.004(2) 0.023(2) 0.014(2) C11 0.060(2) 0.065(2) 0.055(2) -0.001(2) 0.022(2) 0.013(2) C12 0.054(2) 0.048(2) 0.045(2) 0.0014(13) 0.0145(14) 0.0087(14) C13 0.067(2) 0.063(2) 0.044(2) -0.008(2) 0.013(2) 0.003(2) C14 0.060(2) 0.061(2) 0.046(2) -0.009(2) 0.002(2) 0.001(2) C15 0.043(2) 0.050(2) 0.051(2) -0.0031(14) 0.0067(14) 0.0027(14) C16 0.040(2) 0.0357(14) 0.044(2) 0.0016(12) 0.0092(13) 0.0024(12) C17 0.042(2) 0.0352(14) 0.043(2) 0.0021(12) 0.0098(13) 0.0088(12) N18 0.0367(13) 0.0385(12) 0.0394(12) 0.0007(10) 0.0075(10) 0.0031(10) C18 0.0356(15) 0.0366(14) 0.044(2) 0.0001(12) 0.0066(12) 0.0001(12) C19 0.0371(15) 0.0382(15) 0.046(2) 0.0036(12) 0.0099(12) 0.0041(12) C20 0.043(2) 0.039(2) 0.049(2) 0.0043(13) 0.0065(13) 0.0044(13) C21 0.041(2) 0.046(2) 0.050(2) 0.0083(13) 0.0109(13) 0.0067(13) C22 0.049(2) 0.054(2) 0.046(2) 0.0043(14) 0.0156(14) 0.0056(15) C23 0.044(2) 0.047(2) 0.043(2) -0.0001(13) 0.0113(13) 0.0036(14) C24 0.0352(15) 0.042(2) 0.046(2) 0.0021(13) 0.0070(12) 0.0045(12) O24 0.0459(12) 0.0347(10) 0.0482(11) 0.0010(8) 0.0121(9) 0.0007(9) C25 0.053(2) 0.037(2) 0.064(2) 0.0018(14) 0.008(2) 0.0091(14) C26 0.076(3) 0.047(2) 0.077(2) 0.013(2) 0.001(2) 0.015(2) C27 0.062(2) 0.053(2) 0.099(3) -0.001(2) 0.027(2) 0.016(2) C28 0.077(3) 0.039(2) 0.090(3) -0.008(2) 0.000(2) 0.012(2) C29 0.064(2) 0.047(2) 0.066(2) 0.000(2) -0.019(2) 0.006(2) C30 0.064(3) 0.084(3) 0.118(4) 0.021(3) -0.028(3) -0.021(2) C31 0.119(4) 0.107(4) 0.067(3) 0.014(3) -0.010(3) 0.027(3) C32 0.086(4) 0.098(4) 0.132(5) -0.030(3) -0.053(3) 0.039(3) C33 0.064(2) 0.052(2) 0.054(2) 0.016(2) 0.015(2) 0.007(2) C34 0.076(3) 0.048(2) 0.070(2) 0.016(2) 0.011(2) 0.003(2) C35 0.103(4) 0.083(3) 0.070(3) 0.029(2) -0.008(2) 0.020(3) C36 0.109(4) 0.073(3) 0.104(4) 0.026(3) 0.066(3) 0.007(3) C37 0.073(2) 0.054(2) 0.049(2) -0.010(2) 0.021(2) -0.005(2) C38 0.132(4) 0.055(2) 0.089(3) -0.015(2) 0.033(3) 0.024(3) C39 0.124(4) 0.077(3) 0.055(2) -0.015(2) 0.032(3) -0.014(3) C40 0.086(3) 0.096(3) 0.065(3) -0.021(2) 0.016(2) -0.030(3) N50 0.059(2) 0.080(3) 0.161(5) -0.012(3) 0.017(3) 0.015(2) C51 0.065(3) 0.079(3) 0.090(3) -0.007(2) 0.010(2) 0.012(2) C52 0.171(7) 0.082(4) 0.152(6) 0.003(4) -0.004(5) -0.009(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 Ti O1 1.835(2) . ? Ti O24 1.884(2) . ? Ti N18 2.150(2) . ? Ti N7 2.207(2) . ? Ti Cl2 2.3184(11) . ? Ti Cl1 2.3315(10) . ? O1 C1 1.344(4) . ? C1 C2 1.404(4) . ? C1 C6 1.418(4) . ? C2 C3 1.390(5) . ? C2 C25 1.538(4) . ? C3 C4 1.399(5) . ? C4 C5 1.382(4) . ? C4 C29 1.533(5) . ? C5 C6 1.404(4) . ? C6 C7 1.450(4) . ? C7 N7 1.296(4) . ? N7 C8 1.444(4) . ? C8 C9 1.381(4) . ? C8 C17 1.428(4) . ? C9 C10 1.409(5) . ? C10 C11 1.356(5) . ? C11 C12 1.412(5) . ? C12 C13 1.413(5) . ? C12 C17 1.438(4) . ? C13 C14 1.361(5) . ? C14 C15 1.406(5) . ? C15 C16 1.367(4) . ? C16 C17 1.424(4) . ? C16 N18 1.435(4) . ? N18 C18 1.298(4) . ? C18 C19 1.434(4) . ? C19 C20 1.409(4) . ? C19 C24 1.415(4) . ? C20 C21 1.375(4) . ? C21 C22 1.415(4) . ? C21 C33 1.530(4) . ? C22 C23 1.389(5) . ? C23 C24 1.424(4) . ? C23 C37 1.535(4) . ? C24 O24 1.333(4) . ? C25 C26 1.528(5) . ? C25 C27 1.539(5) . ? C25 C28 1.542(5) . ? C29 C32 1.499(6) . ? C29 C30 1.518(6) . ? C29 C31 1.556(7) . ? C33 C34 1.530(5) . ? C33 C36 1.533(6) . ? C33 C35 1.551(6) . ? C37 C40 1.529(6) . ? C37 C38 1.540(6) . ? C37 C39 1.543(5) . ? N50 C51 1.116(6) . ? C51 C52 1.442(7) . ? 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 Ti O24 90.57(9) . . ? O1 Ti N18 155.88(9) . . ? O24 Ti N18 81.86(9) . . ? O1 Ti N7 82.39(9) . . ? O24 Ti N7 92.27(9) . . ? N18 Ti N7 75.11(9) . . ? O1 Ti Cl2 105.08(7) . . ? O24 Ti Cl2 88.71(7) . . ? N18 Ti Cl2 97.65(7) . . ? N7 Ti Cl2 172.46(7) . . ? O1 Ti Cl1 96.08(7) . . ? O24 Ti Cl1 173.35(7) . . ? N18 Ti Cl1 91.95(7) . . ? N7 Ti Cl1 88.45(7) . . ? Cl2 Ti Cl1 89.72(4) . . ? C1 O1 Ti 134.3(2) . . ? O1 C1 C2 120.4(3) . . ? O1 C1 C6 118.2(3) . . ? C2 C1 C6 121.3(3) . . ? C3 C2 C1 115.8(3) . . ? C3 C2 C25 122.5(3) . . ? C1 C2 C25 121.7(3) . . ? C2 C3 C4 125.2(3) . . ? C5 C4 C3 117.0(3) . . ? C5 C4 C29 123.9(3) . . ? C3 C4 C29 119.0(3) . . ? C4 C5 C6 121.3(3) . . ? C5 C6 C1 119.0(3) . . ? C5 C6 C7 118.6(3) . . ? C1 C6 C7 121.6(3) . . ? N7 C7 C6 126.7(3) . . ? C7 N7 C8 118.3(3) . . ? C7 N7 Ti 117.8(2) . . ? C8 N7 Ti 123.9(2) . . ? C9 C8 C17 119.3(3) . . ? C9 C8 N7 119.2(3) . . ? C17 C8 N7 120.9(3) . . ? C8 C9 C10 121.5(3) . . ? C11 C10 C9 120.1(3) . . ? C10 C11 C12 121.1(3) . . ? C11 C12 C13 121.9(3) . . ? C11 C12 C17 119.2(3) . . ? C13 C12 C17 118.9(3) . . ? C14 C13 C12 122.2(3) . . ? C13 C14 C15 119.7(3) . . ? C16 C15 C14 119.8(3) . . ? C15 C16 C17 122.8(3) . . ? C15 C16 N18 120.4(3) . . ? C17 C16 N18 116.8(3) . . ? C16 C17 C8 125.0(3) . . ? C16 C17 C12 116.5(3) . . ? C8 C17 C12 118.5(3) . . ? C18 N18 C16 115.7(2) . . ? C18 N18 Ti 126.8(2) . . ? C16 N18 Ti 117.5(2) . . ? N18 C18 C19 126.3(3) . . ? C20 C19 C24 121.2(3) . . ? C20 C19 C18 116.5(3) . . ? C24 C19 C18 121.7(3) . . ? C21 C20 C19 120.9(3) . . ? C20 C21 C22 116.8(3) . . ? C20 C21 C33 123.8(3) . . ? C22 C21 C33 119.3(3) . . ? C23 C22 C21 125.0(3) . . ? C22 C23 C24 116.9(3) . . ? C22 C23 C37 121.5(3) . . ? C24 C23 C37 121.6(3) . . ? O24 C24 C19 119.0(3) . . ? O24 C24 C23 122.1(3) . . ? C19 C24 C23 118.9(3) . . ? C24 O24 Ti 139.3(2) . . ? C26 C25 C2 108.9(3) . . ? C26 C25 C27 110.7(3) . . ? C2 C25 C27 110.6(3) . . ? C26 C25 C28 107.6(3) . . ? C2 C25 C28 111.5(3) . . ? C27 C25 C28 107.5(3) . . ? C32 C29 C30 111.1(4) . . ? C32 C29 C4 112.8(3) . . ? C30 C29 C4 111.2(3) . . ? C32 C29 C31 107.4(4) . . ? C30 C29 C31 106.6(4) . . ? C4 C29 C31 107.3(4) . . ? C21 C33 C34 111.7(3) . . ? C21 C33 C36 110.2(3) . . ? C34 C33 C36 109.0(3) . . ? C21 C33 C35 107.7(3) . . ? C34 C33 C35 107.9(3) . . ? C36 C33 C35 110.3(4) . . ? C40 C37 C23 110.6(3) . . ? C40 C37 C38 110.8(4) . . ? C23 C37 C38 108.3(3) . . ? C40 C37 C39 107.5(4) . . ? C23 C37 C39 111.8(3) . . ? C38 C37 C39 107.9(4) . . ? N50 C51 C52 178.8(6) . . ? _refine_diff_density_max 0.312 _refine_diff_density_min -0.342 _refine_diff_density_rms 0.046 # Attachment 'VG00771.cif' data_VG0077 _database_code_depnum_ccdc_archive 'CCDC 615712' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C43 H57 N5 O2 Cl2 Ti' _chemical_formula_weight 794.74 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2191 1.8069 '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 12.515(2) _cell_length_b 14.189(2) _cell_length_c 14.437(2) _cell_angle_alpha 88.054(10) _cell_angle_beta 84.511(11) _cell_angle_gamma 64.388(10) _cell_volume 2301.0(6) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 10.95 _cell_measurement_theta_max 25.00 _exptl_crystal_description plates _exptl_crystal_colour Orange/red _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.147 _exptl_crystal_density_method ? _exptl_crystal_F_000 844 _exptl_absorpt_coefficient_mu 2.934 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; SHELXTL, Bruker AXS Ltd., Version 5.03 (release 1994) Semi-empirical absorption correction using psi-scans implemented in the XPREP program. ; _exptl_absorpt_correction_T_min 0.4868 _exptl_absorpt_correction_T_max 0.7081 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7166 _diffrn_reflns_av_R_equivalents 0.0471 _diffrn_reflns_av_sigmaI/netI 0.0771 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.08 _diffrn_reflns_theta_max 60.00 _reflns_number_total 6801 _reflns_number_observed 4430 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 681 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0898P)^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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0025(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 6120 _refine_ls_number_parameters 479 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1078 _refine_ls_R_factor_obs 0.0630 _refine_ls_wR_factor_all 0.1775 _refine_ls_wR_factor_obs 0.1489 _refine_ls_goodness_of_fit_all 1.023 _refine_ls_goodness_of_fit_obs 1.105 _refine_ls_restrained_S_all 1.048 _refine_ls_restrained_S_obs 1.105 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Ti Ti 0.45612(8) 0.32314(6) 0.21577(6) 0.0398(2) Uani 1 d . . Cl1 Cl 0.38480(13) 0.39352(10) 0.36635(8) 0.0603(3) Uani 1 d . . Cl2 Cl 0.51042(13) 0.28760(10) 0.05465(8) 0.0626(4) Uani 1 d . . O1 O 0.3876(3) 0.2330(2) 0.2179(2) 0.0460(7) Uani 1 d . . O2 O 0.6042(3) 0.2482(2) 0.2549(2) 0.0481(7) Uani 1 d . . N1 N 0.2811(3) 0.4426(3) 0.1808(2) 0.0414(8) Uani 1 d . . N2 N 0.5132(3) 0.4453(3) 0.1858(3) 0.0446(8) Uani 1 d . . C1 C 0.3038(4) 0.2216(3) 0.1727(3) 0.0421(10) Uani 1 d . . C2 C 0.3067(4) 0.1219(3) 0.1617(3) 0.0476(11) Uani 1 d . . C3 C 0.2144(5) 0.1198(4) 0.1166(4) 0.0544(12) Uani 1 d . . H3A H 0.2151(5) 0.0549(4) 0.1077(4) 0.065 Uiso 1 calc R . C4 C 0.1207(4) 0.2073(4) 0.0835(3) 0.0492(11) Uani 1 d . . C5 C 0.1209(4) 0.3039(4) 0.0951(3) 0.0472(10) Uani 1 d . . H5A H 0.0597(4) 0.3638(4) 0.0742(3) 0.057 Uiso 1 calc R . C6 C 0.2130(4) 0.3120(3) 0.1381(3) 0.0431(10) Uani 1 d . . C7 C 0.2030(4) 0.4160(3) 0.1501(3) 0.0445(10) Uani 1 d . . H7A H 0.1328(4) 0.4706(3) 0.1340(3) 0.053 Uiso 1 calc R . C8 C 0.2411(4) 0.5535(3) 0.1977(3) 0.0431(10) Uani 1 d . . C9 C 0.1300(5) 0.6129(4) 0.2401(3) 0.0522(11) Uani 1 d . . H9A H 0.0790(5) 0.5823(4) 0.2583(3) 0.063 Uiso 1 calc R . C10 C 0.0932(5) 0.7200(4) 0.2561(4) 0.0631(14) Uani 1 d . . H10A H 0.0175(5) 0.7608(4) 0.2841(4) 0.076 Uiso 1 calc R . C11 C 0.1708(6) 0.7644(4) 0.2297(4) 0.0664(15) Uani 1 d . . H11A H 0.1471(6) 0.8352(4) 0.2400(4) 0.080 Uiso 1 calc R . C12 C 0.2823(5) 0.7040(4) 0.1886(4) 0.0577(13) Uani 1 d . . H12A H 0.3331(5) 0.7350(4) 0.1710(4) 0.069 Uiso 1 calc R . C13 C 0.3220(4) 0.5971(3) 0.1724(3) 0.0462(10) Uani 1 d . . C14 C 0.4435(5) 0.5331(4) 0.1251(4) 0.0517(11) Uani 1 d . . H14A H 0.4362(5) 0.5056(4) 0.0667(4) 0.062 Uiso 1 calc R . H14B H 0.4847(5) 0.5770(4) 0.1117(4) 0.062 Uiso 1 calc R . C15 C 0.6080(4) 0.4442(4) 0.2148(3) 0.0499(11) Uani 1 d . . H15A H 0.6254(4) 0.4999(4) 0.1969(3) 0.060 Uiso 1 calc R . C16 C 0.6906(4) 0.3655(4) 0.2724(3) 0.0468(10) Uani 1 d . . C17 C 0.7784(5) 0.3873(4) 0.3074(4) 0.0575(12) Uani 1 d . . H17A H 0.7798(5) 0.4515(4) 0.2944(4) 0.069 Uiso 1 calc R . C18 C 0.8624(4) 0.3163(4) 0.3604(3) 0.0519(11) Uani 1 d . . C19 C 0.8559(5) 0.2204(4) 0.3781(4) 0.0545(12) Uani 1 d . . H19A H 0.9114(5) 0.1722(4) 0.4147(4) 0.065 Uiso 1 calc R . C20 C 0.7731(4) 0.1925(3) 0.3450(3) 0.0475(11) Uani 1 d . . C21 C 0.6877(4) 0.2683(4) 0.2909(3) 0.0454(10) Uani 1 d . . C22 C 0.4045(5) 0.0233(4) 0.1995(5) 0.0653(15) Uani 1 d . . C23 C 0.4019(7) 0.0331(5) 0.3045(5) 0.089(2) Uani 1 d . . H23A H 0.3250(7) 0.0438(5) 0.3332(5) 0.134 Uiso 1 calc R . H23B H 0.4173(7) 0.0915(5) 0.3186(5) 0.134 Uiso 1 calc R . H23C H 0.4617(7) -0.0297(5) 0.3281(5) 0.134 Uiso 1 calc R . C24 C 0.5257(6) 0.0065(5) 0.1539(6) 0.089(2) Uani 1 d . . H24A H 0.5269(6) 0.0003(5) 0.0877(6) 0.134 Uiso 1 calc R . H24B H 0.5856(6) -0.0564(5) 0.1772(6) 0.134 Uiso 1 calc R . H24C H 0.5413(6) 0.0648(5) 0.1677(6) 0.134 Uiso 1 calc R . C25 C 0.3862(7) -0.0750(4) 0.1802(6) 0.094(2) Uani 1 d . . H25A H 0.3098(7) -0.0664(4) 0.2084(6) 0.141 Uiso 1 calc R . H25B H 0.4475(7) -0.1351(4) 0.2059(6) 0.141 Uiso 1 calc R . H25C H 0.3898(7) -0.0845(4) 0.1142(6) 0.141 Uiso 1 calc R . C26 C 0.0214(5) 0.1947(4) 0.0373(4) 0.0595(13) Uani 1 d . . C27 C -0.0356(7) 0.1414(7) 0.1063(6) 0.096(2) Uani 1 d . . H27A H 0.0241(7) 0.0748(7) 0.1234(6) 0.144 Uiso 1 calc R . H27B H -0.0963(7) 0.1316(7) 0.0778(6) 0.144 Uiso 1 calc R . H27C H -0.0702(7) 0.1846(7) 0.1609(6) 0.144 Uiso 1 calc R . C28 C 0.0754(7) 0.1280(6) -0.0511(5) 0.096(2) Uani 1 d . . H28A H 0.1376(7) 0.0620(6) -0.0356(5) 0.144 Uiso 1 calc R . H28B H 0.1078(7) 0.1636(6) -0.0947(5) 0.144 Uiso 1 calc R . H28C H 0.0148(7) 0.1167(6) -0.0783(5) 0.144 Uiso 1 calc R . C29 C -0.0775(7) 0.2999(6) 0.0127(6) 0.094(2) Uani 1 d . . H29A H -0.1114(7) 0.3417(6) 0.0681(6) 0.142 Uiso 1 calc R . H29B H -0.1381(7) 0.2886(6) -0.0145(6) 0.142 Uiso 1 calc R . H29C H -0.0452(7) 0.3355(6) -0.0309(6) 0.142 Uiso 1 calc R . C30 C 0.9588(5) 0.3393(5) 0.4007(4) 0.0642(14) Uani 1 d . . C31 C 0.9640(9) 0.4371(8) 0.3621(7) 0.123(4) Uani 1 d . . H31A H 0.9746(9) 0.4328(8) 0.2954(7) 0.185 Uiso 1 calc R . H31B H 1.0296(9) 0.4444(8) 0.3850(7) 0.185 Uiso 1 calc R . H31C H 0.8912(9) 0.4965(8) 0.3813(7) 0.185 Uiso 1 calc R . C32 C 0.9421(9) 0.3388(9) 0.5061(5) 0.116(3) Uani 1 d . . H32A H 0.9395(9) 0.2746(9) 0.5264(5) 0.175 Uiso 1 calc R . H32B H 0.8690(9) 0.3967(9) 0.5274(5) 0.175 Uiso 1 calc R . H32C H 1.0074(9) 0.3446(9) 0.5312(5) 0.175 Uiso 1 calc R . C33 C 1.0826(6) 0.2478(8) 0.3702(6) 0.104(3) Uani 1 d . . H33A H 1.0843(6) 0.1829(8) 0.3931(6) 0.156 Uiso 1 calc R . H33B H 1.1443(6) 0.2595(8) 0.3952(6) 0.156 Uiso 1 calc R . H33C H 1.0953(6) 0.2448(8) 0.3035(6) 0.156 Uiso 1 calc R . C34 C 0.7731(5) 0.0846(4) 0.3635(4) 0.0600(13) Uani 1 d . . C35 C 0.6568(6) 0.0972(5) 0.4156(5) 0.077(2) Uani 1 d . . H35A H 0.5920(6) 0.1402(5) 0.3802(5) 0.115 Uiso 1 calc R . H35B H 0.6477(6) 0.1297(5) 0.4749(5) 0.115 Uiso 1 calc R . H35C H 0.6570(6) 0.0298(5) 0.4247(5) 0.115 Uiso 1 calc R . C36 C 0.8741(7) 0.0152(5) 0.4230(6) 0.096(3) Uani 1 d . . H36A H 0.9494(7) 0.0057(5) 0.3917(6) 0.144 Uiso 1 calc R . H36B H 0.8726(7) -0.0515(5) 0.4321(6) 0.144 Uiso 1 calc R . H36C H 0.8633(7) 0.0483(5) 0.4823(6) 0.144 Uiso 1 calc R . C37 C 0.7931(6) 0.0270(4) 0.2701(5) 0.077(2) Uani 1 d . . H37A H 0.8670(6) 0.0195(4) 0.2379(5) 0.115 Uiso 1 calc R . H37B H 0.7291(6) 0.0665(4) 0.2327(5) 0.115 Uiso 1 calc R . H37C H 0.7954(6) -0.0409(4) 0.2817(5) 0.115 Uiso 1 calc R . N40 N 0.1134(9) 0.4541(6) 0.8791(7) 0.157(4) Uani 1 d . . C41 C 0.1977(7) 0.3807(5) 0.8792(5) 0.086(2) Uani 1 d . . C42 C 0.3044(7) 0.2854(7) 0.8819(6) 0.105(3) Uani 1 d . . H42A H 0.3439(7) 0.2860(7) 0.9355(6) 0.157 Uiso 1 d R . H42B H 0.3562(7) 0.2793(7) 0.8266(6) 0.157 Uiso 1 d R . H42C H 0.2847(7) 0.2270(7) 0.8853(6) 0.157 Uiso 1 d R . N43 N 0.5364(9) 0.6708(8) 0.3272(7) 0.139(3) Uani 1 d . . C44 C 0.4694(9) 0.6572(7) 0.3777(7) 0.097(2) Uani 1 d . . C45 C 0.3868(11) 0.6379(8) 0.4387(7) 0.130(4) Uani 1 d . . H45A H 0.4089(11) 0.6328(8) 0.5012(7) 0.194 Uiso 1 d R . H45B H 0.3859(11) 0.5735(8) 0.4213(7) 0.194 Uiso 1 d R . H45C H 0.3090(11) 0.6941(8) 0.4352(7) 0.194 Uiso 1 d R . N46 N 0.1996(11) 0.2401(11) 0.6785(9) 0.176(5) Uani 1 d . . C47 C 0.2647(9) 0.2297(8) 0.6136(7) 0.103(3) Uani 1 d . . C48 C 0.3436(10) 0.2109(11) 0.5330(7) 0.144(4) Uani 1 d . . H48A H 0.4237(10) 0.1840(11) 0.5502(7) 0.216 Uiso 1 d R . H48B H 0.3248(10) 0.2749(11) 0.4996(7) 0.216 Uiso 1 d R . H48C H 0.3363(10) 0.1607(11) 0.4942(7) 0.216 Uiso 1 d 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 Ti 0.0459(5) 0.0358(4) 0.0440(4) 0.0052(3) -0.0137(3) -0.0220(3) Cl1 0.0816(9) 0.0601(7) 0.0438(6) 0.0008(5) -0.0104(6) -0.0338(6) Cl2 0.0808(9) 0.0616(7) 0.0482(6) -0.0054(5) -0.0041(6) -0.0333(6) O1 0.049(2) 0.0379(15) 0.057(2) 0.0055(12) -0.0201(14) -0.0218(13) O2 0.052(2) 0.044(2) 0.056(2) 0.0061(13) -0.0201(15) -0.0251(14) N1 0.048(2) 0.035(2) 0.045(2) 0.0031(14) -0.013(2) -0.021(2) N2 0.049(2) 0.043(2) 0.047(2) 0.006(2) -0.013(2) -0.023(2) C1 0.048(3) 0.041(2) 0.045(2) -0.001(2) -0.013(2) -0.024(2) C2 0.053(3) 0.037(2) 0.059(3) -0.001(2) -0.011(2) -0.024(2) C3 0.065(3) 0.047(2) 0.063(3) -0.001(2) -0.015(2) -0.034(2) C4 0.056(3) 0.052(3) 0.050(2) -0.002(2) -0.014(2) -0.030(2) C5 0.054(3) 0.047(2) 0.047(2) 0.004(2) -0.014(2) -0.026(2) C6 0.050(3) 0.042(2) 0.045(2) 0.003(2) -0.014(2) -0.026(2) C7 0.050(3) 0.039(2) 0.049(2) 0.005(2) -0.014(2) -0.021(2) C8 0.057(3) 0.034(2) 0.044(2) 0.004(2) -0.014(2) -0.024(2) C9 0.058(3) 0.041(2) 0.059(3) 0.002(2) -0.009(2) -0.022(2) C10 0.062(3) 0.043(2) 0.074(3) -0.007(2) -0.012(3) -0.012(2) C11 0.079(4) 0.037(2) 0.082(4) 0.000(2) -0.023(3) -0.021(3) C12 0.073(4) 0.042(2) 0.071(3) 0.009(2) -0.025(3) -0.034(3) C13 0.057(3) 0.039(2) 0.048(2) 0.010(2) -0.020(2) -0.024(2) C14 0.058(3) 0.044(2) 0.056(3) 0.014(2) -0.012(2) -0.025(2) C15 0.052(3) 0.043(2) 0.060(3) 0.008(2) -0.011(2) -0.025(2) C16 0.049(3) 0.048(2) 0.052(3) 0.002(2) -0.012(2) -0.027(2) C17 0.060(3) 0.060(3) 0.066(3) 0.002(2) -0.015(3) -0.037(3) C18 0.047(3) 0.062(3) 0.054(3) 0.001(2) -0.013(2) -0.028(2) C19 0.049(3) 0.058(3) 0.058(3) 0.006(2) -0.017(2) -0.023(2) C20 0.047(3) 0.043(2) 0.055(3) 0.006(2) -0.016(2) -0.021(2) C21 0.043(2) 0.047(2) 0.051(2) -0.002(2) -0.010(2) -0.023(2) C22 0.071(4) 0.036(2) 0.095(4) 0.006(2) -0.028(3) -0.025(2) C23 0.113(6) 0.066(4) 0.099(5) 0.031(3) -0.049(4) -0.043(4) C24 0.067(4) 0.054(3) 0.143(7) -0.005(4) -0.023(4) -0.020(3) C25 0.091(5) 0.038(3) 0.164(7) 0.009(3) -0.043(5) -0.033(3) C26 0.067(3) 0.065(3) 0.063(3) -0.002(2) -0.026(3) -0.039(3) C27 0.093(5) 0.119(6) 0.115(6) 0.018(5) -0.034(4) -0.077(5) C28 0.109(6) 0.106(5) 0.084(5) -0.031(4) -0.026(4) -0.051(5) C29 0.088(5) 0.091(5) 0.123(6) -0.002(4) -0.057(4) -0.046(4) C30 0.062(3) 0.091(4) 0.060(3) 0.008(3) -0.027(3) -0.049(3) C31 0.137(8) 0.143(8) 0.152(8) 0.050(6) -0.076(7) -0.109(7) C32 0.132(7) 0.201(10) 0.069(4) -0.011(5) -0.030(4) -0.116(8) C33 0.067(4) 0.150(8) 0.112(6) -0.018(5) -0.011(4) -0.061(5) C34 0.060(3) 0.047(3) 0.077(3) 0.014(2) -0.026(3) -0.024(2) C35 0.083(4) 0.072(4) 0.087(4) 0.033(3) -0.023(3) -0.043(3) C36 0.088(5) 0.073(4) 0.141(7) 0.046(4) -0.066(5) -0.040(4) C37 0.083(4) 0.050(3) 0.094(4) -0.006(3) -0.020(3) -0.022(3) N40 0.146(8) 0.086(5) 0.170(9) 0.023(5) -0.008(6) 0.012(5) C41 0.083(5) 0.065(4) 0.094(5) 0.000(3) 0.003(4) -0.020(4) C42 0.084(5) 0.106(6) 0.096(5) 0.003(4) -0.010(4) -0.015(4) N43 0.145(8) 0.164(9) 0.126(7) -0.024(6) 0.008(6) -0.085(7) C44 0.102(6) 0.091(5) 0.102(6) -0.019(4) -0.012(5) -0.043(5) C45 0.165(10) 0.137(8) 0.114(7) -0.036(6) 0.029(7) -0.096(8) N46 0.162(10) 0.213(12) 0.182(11) -0.004(9) 0.023(8) -0.115(10) C47 0.100(6) 0.120(7) 0.114(6) 0.018(5) -0.024(5) -0.068(5) C48 0.150(10) 0.226(14) 0.104(7) 0.025(8) -0.017(7) -0.126(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 Ti O1 1.821(3) . ? Ti O2 1.828(3) . ? Ti N2 2.160(4) . ? Ti N1 2.207(4) . ? Ti Cl1 2.351(2) . ? Ti Cl2 2.368(2) . ? O1 C1 1.354(5) . ? O2 C21 1.346(5) . ? N1 C7 1.307(6) . ? N1 C8 1.451(5) . ? N2 C15 1.289(6) . ? N2 C14 1.487(6) . ? C1 C6 1.411(6) . ? C1 C2 1.414(6) . ? C2 C3 1.390(7) . ? C2 C22 1.532(7) . ? C3 C4 1.397(7) . ? C4 C5 1.388(6) . ? C4 C26 1.543(7) . ? C5 C6 1.409(6) . ? C6 C7 1.441(6) . ? C8 C9 1.370(7) . ? C8 C13 1.412(7) . ? C9 C10 1.405(7) . ? C10 C11 1.387(9) . ? C11 C12 1.370(9) . ? C12 C13 1.398(7) . ? C13 C14 1.501(7) . ? C15 C16 1.452(7) . ? C16 C17 1.403(7) . ? C16 C21 1.412(6) . ? C17 C18 1.376(7) . ? C18 C19 1.411(7) . ? C18 C30 1.545(7) . ? C19 C20 1.386(7) . ? C20 C21 1.420(6) . ? C20 C34 1.545(7) . ? C22 C24 1.516(10) . ? C22 C23 1.523(9) . ? C22 C25 1.546(7) . ? C26 C29 1.528(9) . ? C26 C28 1.531(9) . ? C26 C27 1.533(9) . ? C30 C31 1.503(10) . ? C30 C32 1.516(9) . ? C30 C33 1.565(10) . ? C34 C35 1.513(9) . ? C34 C36 1.543(7) . ? C34 C37 1.544(8) . ? N40 C41 1.117(10) . ? C41 C42 1.435(10) . ? N43 C44 1.133(12) . ? C44 C45 1.405(13) . ? N46 C47 1.150(13) . ? C47 C48 1.405(14) . ? 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 Ti O2 105.87(13) . . ? O1 Ti N2 166.52(14) . . ? O2 Ti N2 85.54(14) . . ? O1 Ti N1 85.20(13) . . ? O2 Ti N1 167.61(13) . . ? N2 Ti N1 84.25(14) . . ? O1 Ti Cl1 98.02(11) . . ? O2 Ti Cl1 89.99(11) . . ? N2 Ti Cl1 88.96(11) . . ? N1 Ti Cl1 82.83(10) . . ? O1 Ti Cl2 88.72(11) . . ? O2 Ti Cl2 97.12(12) . . ? N2 Ti Cl2 82.65(11) . . ? N1 Ti Cl2 88.52(11) . . ? Cl1 Ti Cl2 168.52(5) . . ? C1 O1 Ti 137.0(3) . . ? C21 O2 Ti 137.3(3) . . ? C7 N1 C8 115.8(4) . . ? C7 N1 Ti 121.0(3) . . ? C8 N1 Ti 123.0(3) . . ? C15 N2 C14 117.8(4) . . ? C15 N2 Ti 123.3(3) . . ? C14 N2 Ti 118.9(3) . . ? O1 C1 C6 118.2(4) . . ? O1 C1 C2 120.7(4) . . ? C6 C1 C2 121.1(4) . . ? C3 C2 C1 115.8(4) . . ? C3 C2 C22 122.7(4) . . ? C1 C2 C22 121.5(4) . . ? C2 C3 C4 125.4(4) . . ? C5 C4 C3 117.3(4) . . ? C5 C4 C26 122.4(4) . . ? C3 C4 C26 120.2(4) . . ? C4 C5 C6 120.6(4) . . ? C5 C6 C1 119.8(4) . . ? C5 C6 C7 116.5(4) . . ? C1 C6 C7 123.6(4) . . ? N1 C7 C6 127.6(4) . . ? C9 C8 C13 121.2(4) . . ? C9 C8 N1 120.9(4) . . ? C13 C8 N1 117.9(4) . . ? C8 C9 C10 120.0(5) . . ? C11 C10 C9 119.4(5) . . ? C12 C11 C10 120.1(5) . . ? C11 C12 C13 121.8(5) . . ? C12 C13 C8 117.4(5) . . ? C12 C13 C14 120.8(4) . . ? C8 C13 C14 121.7(4) . . ? N2 C14 C13 110.2(4) . . ? N2 C15 C16 127.2(4) . . ? C17 C16 C21 119.9(4) . . ? C17 C16 C15 117.6(4) . . ? C21 C16 C15 122.4(4) . . ? C18 C17 C16 121.7(5) . . ? C17 C18 C19 116.7(4) . . ? C17 C18 C30 122.5(5) . . ? C19 C18 C30 120.8(4) . . ? C20 C19 C18 125.0(4) . . ? C19 C20 C21 116.4(4) . . ? C19 C20 C34 122.7(4) . . ? C21 C20 C34 120.9(4) . . ? O2 C21 C16 118.8(4) . . ? O2 C21 C20 120.9(4) . . ? C16 C21 C20 120.3(4) . . ? C24 C22 C23 109.8(6) . . ? C24 C22 C2 110.6(5) . . ? C23 C22 C2 109.8(5) . . ? C24 C22 C25 107.7(5) . . ? C23 C22 C25 107.5(5) . . ? C2 C22 C25 111.3(5) . . ? C29 C26 C28 109.5(6) . . ? C29 C26 C27 107.1(6) . . ? C28 C26 C27 110.3(6) . . ? C29 C26 C4 112.2(4) . . ? C28 C26 C4 109.1(5) . . ? C27 C26 C4 108.6(5) . . ? C31 C30 C32 113.4(7) . . ? C31 C30 C18 112.8(5) . . ? C32 C30 C18 109.4(5) . . ? C31 C30 C33 105.9(7) . . ? C32 C30 C33 107.3(6) . . ? C18 C30 C33 107.7(5) . . ? C35 C34 C36 107.5(5) . . ? C35 C34 C37 110.4(5) . . ? C36 C34 C37 107.4(5) . . ? C35 C34 C20 110.4(5) . . ? C36 C34 C20 111.7(4) . . ? C37 C34 C20 109.5(5) . . ? N40 C41 C42 178.2(10) . . ? N43 C44 C45 178.3(10) . . ? N46 C47 C48 176.2(12) . . ? _refine_diff_density_max 0.352 _refine_diff_density_min -0.337 _refine_diff_density_rms 0.057 # Attachment 'VG01061.cif' data_VG0106 _database_code_depnum_ccdc_archive 'CCDC 615713' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C46 H57 N3 O2 Cl2 Zr' _chemical_formula_weight 846.07 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbca 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' '-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 25.981(4) _cell_length_b 13.1764(4) _cell_length_c 26.4518(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 9055.6(15) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 23 _cell_measurement_theta_min 10.80 _cell_measurement_theta_max 28.00 _exptl_crystal_description prisms _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.23 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.241 _exptl_crystal_density_method ? _exptl_crystal_F_000 3552 _exptl_absorpt_coefficient_mu 3.364 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_process_details ; SHELXTL, Bruker AXS Ltd., Version 5.03 (release 1994) Semi-empirical absorption correction using psi-scans implemented in the XPREP program. ; _exptl_absorpt_correction_T_min 0.2918 _exptl_absorpt_correction_T_max 0.3817 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6721 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0458 _diffrn_reflns_limit_h_min -29 _diffrn_reflns_limit_h_max 0 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 3.34 _diffrn_reflns_theta_max 60.00 _reflns_number_total 6721 _reflns_number_observed 5185 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 439 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+1.5059P] 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 ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00030(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 6282 _refine_ls_number_parameters 488 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0599 _refine_ls_R_factor_obs 0.0414 _refine_ls_wR_factor_all 0.1056 _refine_ls_wR_factor_obs 0.0946 _refine_ls_goodness_of_fit_all 1.032 _refine_ls_goodness_of_fit_obs 1.080 _refine_ls_restrained_S_all 1.048 _refine_ls_restrained_S_obs 1.080 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Zr Zr 0.047931(11) 0.01821(2) 0.152955(10) 0.03772(11) Uani 1 d . . Cl1 Cl -0.02658(4) -0.09174(8) 0.13975(4) 0.0544(2) Uani 1 d . . Cl2 Cl 0.01893(5) 0.16472(8) 0.10453(4) 0.0596(3) Uani 1 d . . O1 O 0.10370(10) 0.0954(2) 0.18494(9) 0.0447(6) Uani 1 d . . C1 C 0.12140(14) 0.1389(3) 0.22712(13) 0.0393(8) Uani 1 d . . C2 C 0.17133(14) 0.1798(3) 0.22921(14) 0.0432(8) Uani 1 d . . C3 C 0.18784(15) 0.2158(3) 0.2756(2) 0.0500(9) Uani 1 d . . H3A H 0.22100(15) 0.2420(3) 0.2777(2) 0.060 Uiso 1 calc R . C4 C 0.1578(2) 0.2152(3) 0.3197(2) 0.0473(9) Uani 1 d . . C5 C 0.10753(15) 0.1815(3) 0.31546(14) 0.0449(8) Uani 1 d . . H5A H 0.08590(15) 0.1844(3) 0.34344(14) 0.054 Uiso 1 calc R . C6 C 0.08857(14) 0.1426(3) 0.26915(13) 0.0392(8) Uani 1 d . . C7 C 0.03509(14) 0.1132(3) 0.26747(13) 0.0398(8) Uani 1 d . . H7A H 0.01584(14) 0.1263(3) 0.29638(13) 0.048 Uiso 1 calc R . N7 N 0.01064(11) 0.0702(2) 0.23004(11) 0.0381(6) Uani 1 d . . C8 C -0.04483(14) 0.0601(3) 0.23654(14) 0.0411(8) Uani 1 d . . C9 C -0.0757(2) 0.1175(3) 0.2049(2) 0.0480(9) Uani 1 d . . H9A H -0.0604(2) 0.1614(3) 0.1819(2) 0.058 Uiso 1 calc R . C10 C -0.1281(2) 0.1110(4) 0.2067(2) 0.0625(11) Uani 1 d . . H10A H -0.1484(2) 0.1513(4) 0.1858(2) 0.075 Uiso 1 calc R . C11 C -0.1506(2) 0.0434(4) 0.2401(2) 0.0696(13) Uani 1 d . . H11A H -0.1862(2) 0.0373(4) 0.2414(2) 0.083 Uiso 1 calc R . C12 C -0.1202(2) -0.0149(4) 0.2716(2) 0.0633(12) Uani 1 d . . H12A H -0.1358(2) -0.0600(4) 0.2938(2) 0.076 Uiso 1 calc R . C13 C -0.0664(2) -0.0081(3) 0.27089(15) 0.0487(9) Uani 1 d . . C14 C -0.0350(2) -0.0754(3) 0.3055(2) 0.0558(10) Uani 1 d . . H14A H -0.0584(2) -0.1167(3) 0.3253(2) 0.067 Uiso 1 calc R . H14B H -0.0160(2) -0.0327(3) 0.3287(2) 0.067 Uiso 1 calc R . C15 C 0.0035(2) -0.1464(3) 0.27783(15) 0.0513(9) Uani 1 d . . H15A H -0.0032(2) -0.2158(3) 0.28799(15) 0.062 Uiso 1 calc R . H15B H -0.0025(2) -0.1418(3) 0.24171(15) 0.062 Uiso 1 calc R . C16 C 0.0593(2) -0.1224(3) 0.28821(14) 0.0465(9) Uani 1 d . . C17 C 0.0763(2) -0.1134(3) 0.33789(14) 0.0579(11) Uani 1 d . . H17A H 0.0528(2) -0.1213(3) 0.36409(14) 0.069 Uiso 1 calc R . C18 C 0.1271(2) -0.0932(4) 0.3495(2) 0.0698(13) Uani 1 d . . H18A H 0.1371(2) -0.0865(4) 0.3831(2) 0.084 Uiso 1 calc R . C19 C 0.1633(2) -0.0829(4) 0.3115(2) 0.0663(13) Uani 1 d . . H19A H 0.1974(2) -0.0682(4) 0.3191(2) 0.080 Uiso 1 calc R . C20 C 0.1475(2) -0.0950(3) 0.26186(15) 0.0518(9) Uani 1 d . . H20A H 0.1715(2) -0.0901(3) 0.23590(15) 0.062 Uiso 1 calc R . C21 C 0.0965(2) -0.1143(3) 0.25033(13) 0.0440(9) Uani 1 d . . N22 N 0.08346(12) -0.1214(2) 0.19719(11) 0.0407(7) Uani 1 d . . C22 C 0.10005(15) -0.2019(3) 0.17495(14) 0.0435(8) Uani 1 d . . H22A H 0.11028(15) -0.2545(3) 0.19609(14) 0.052 Uiso 1 calc R . C23 C 0.10486(15) -0.2210(3) 0.12113(13) 0.0417(8) Uani 1 d . . C24 C 0.1176(2) -0.3191(3) 0.10584(14) 0.0488(9) Uani 1 d . . H24A H 0.1189(2) -0.3708(3) 0.12977(14) 0.059 Uiso 1 calc R . C25 C 0.1285(2) -0.3413(3) 0.05568(15) 0.0510(9) Uani 1 d . . C26 C 0.1282(2) -0.2592(3) 0.02199(14) 0.0491(9) Uani 1 d . . H26A H 0.1360(2) -0.2727(3) -0.01166(14) 0.059 Uiso 1 calc R . C27 C 0.11732(14) -0.1605(3) 0.03477(13) 0.0433(8) Uani 1 d . . C28 C 0.10366(14) -0.1418(3) 0.08548(13) 0.0403(8) Uani 1 d . . O28 O 0.09022(10) -0.0487(2) 0.10095(9) 0.0441(6) Uani 1 d . . C29 C 0.2060(2) 0.1830(3) 0.1817(2) 0.0526(10) Uani 1 d . . C30 C 0.1782(2) 0.2378(4) 0.1384(2) 0.0698(13) Uani 1 d . . H30A H 0.1464(2) 0.2035(4) 0.1311(2) 0.105 Uiso 1 calc R . H30B H 0.1996(2) 0.2375(4) 0.1088(2) 0.105 Uiso 1 calc R . H30C H 0.1711(2) 0.3066(4) 0.1481(2) 0.105 Uiso 1 calc R . C31 C 0.2192(2) 0.0748(4) 0.1649(2) 0.0700(13) Uani 1 d . . H31A H 0.1879(2) 0.0380(4) 0.1584(2) 0.105 Uiso 1 calc R . H31B H 0.2383(2) 0.0413(4) 0.1911(2) 0.105 Uiso 1 calc R . H31C H 0.2395(2) 0.0772(4) 0.1346(2) 0.105 Uiso 1 calc R . C32 C 0.2561(2) 0.2401(5) 0.1917(2) 0.0758(15) Uani 1 d . . H32A H 0.2484(2) 0.3081(5) 0.2023(2) 0.114 Uiso 1 calc R . H32B H 0.2763(2) 0.2420(5) 0.1613(2) 0.114 Uiso 1 calc R . H32C H 0.2751(2) 0.2061(5) 0.2178(2) 0.114 Uiso 1 calc R . C33 C 0.1807(2) 0.2526(4) 0.3696(2) 0.0593(11) Uani 1 d . . C34 C 0.1436(2) 0.2410(5) 0.4134(2) 0.0766(15) Uani 1 d . . H34A H 0.1126(2) 0.2779(5) 0.4063(2) 0.115 Uiso 1 calc R . H34B H 0.1591(2) 0.2674(5) 0.4436(2) 0.115 Uiso 1 calc R . H34C H 0.1356(2) 0.1705(5) 0.4181(2) 0.115 Uiso 1 calc R . C35 C 0.1918(3) 0.3674(5) 0.3648(2) 0.088(2) Uani 1 d . . H35A H 0.2153(3) 0.3787(5) 0.3374(2) 0.132 Uiso 1 calc R . H35B H 0.2068(3) 0.3918(5) 0.3957(2) 0.132 Uiso 1 calc R . H35C H 0.1603(3) 0.4030(5) 0.3584(2) 0.132 Uiso 1 calc R . C36 C 0.2300(3) 0.1946(7) 0.3804(2) 0.124(3) Uani 1 d . . H36A H 0.2533(3) 0.2024(7) 0.3525(2) 0.186 Uiso 1 calc R . H36B H 0.2222(3) 0.1240(7) 0.3850(2) 0.186 Uiso 1 calc R . H36C H 0.2457(3) 0.2209(7) 0.4106(2) 0.186 Uiso 1 calc R . C37 C 0.1401(2) -0.4483(4) 0.0365(2) 0.0638(12) Uani 1 d . . C38 C 0.0992(3) -0.4766(5) -0.0029(2) 0.088(2) Uani 1 d . . H38A H 0.0994(3) -0.4276(5) -0.0297(2) 0.132 Uiso 1 calc R . H38B H 0.0659(3) -0.4775(5) 0.0128(2) 0.132 Uiso 1 calc R . H38C H 0.1067(3) -0.5426(5) -0.0164(2) 0.132 Uiso 1 calc R . C39 C 0.1392(4) -0.5255(5) 0.0779(2) 0.135(4) Uani 1 d . . H39A H 0.1467(4) -0.5913(5) 0.0641(2) 0.202 Uiso 1 calc R . H39B H 0.1057(4) -0.5264(5) 0.0933(2) 0.202 Uiso 1 calc R . H39C H 0.1646(4) -0.5085(5) 0.1029(2) 0.202 Uiso 1 calc R . C40 C 0.1924(3) -0.4483(6) 0.0098(3) 0.113(3) Uani 1 d . . H40A H 0.1924(3) -0.3983(6) -0.0166(3) 0.169 Uiso 1 calc R . H40B H 0.1988(3) -0.5141(6) -0.0044(3) 0.169 Uiso 1 calc R . H40C H 0.2190(3) -0.4324(6) 0.0338(3) 0.169 Uiso 1 calc R . C41 C 0.1206(2) -0.0738(4) -0.00417(15) 0.0546(10) Uani 1 d . . C42 C 0.0693(2) -0.0177(4) -0.0088(2) 0.0686(13) Uani 1 d . . H42A H 0.0431(2) -0.0644(4) -0.0195(2) 0.103 Uiso 1 calc R . H42B H 0.0726(2) 0.0357(4) -0.0333(2) 0.103 Uiso 1 calc R . H42C H 0.0601(2) 0.0106(4) 0.0233(2) 0.103 Uiso 1 calc R . C43 C 0.1340(3) -0.1133(5) -0.0574(2) 0.090(2) Uani 1 d . . H43A H 0.1661(3) -0.1492(5) -0.0563(2) 0.135 Uiso 1 calc R . H43B H 0.1368(3) -0.0571(5) -0.0803(2) 0.135 Uiso 1 calc R . H43C H 0.1073(3) -0.1582(5) -0.0689(2) 0.135 Uiso 1 calc R . C44 C 0.1627(2) -0.0003(5) 0.0128(2) 0.088(2) Uani 1 d . . H44A H 0.1948(2) -0.0360(5) 0.0157(2) 0.133 Uiso 1 calc R . H44B H 0.1536(2) 0.0281(5) 0.0451(2) 0.133 Uiso 1 calc R . H44C H 0.1661(2) 0.0533(5) -0.0116(2) 0.133 Uiso 1 calc R . N50 N 0.0118(2) 0.0971(5) 0.4057(2) 0.111(2) Uani 1 d . . C51 C 0.0129(2) 0.1535(5) 0.4370(2) 0.0751(14) Uani 1 d . . C52 C 0.0142(3) 0.2272(5) 0.4775(3) 0.096(2) Uani 1 d . . H52A H 0.0117(3) 0.2943(5) 0.4636(3) 0.143 Uiso 1 d R . H52B H 0.0460(3) 0.2207(5) 0.4958(3) 0.143 Uiso 1 d R . H52C H -0.0141(3) 0.2155(5) 0.5000(3) 0.143 Uiso 1 d 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 Zr 0.0399(2) 0.0391(2) 0.0341(2) -0.00249(12) -0.00428(12) 0.00262(12) Cl1 0.0523(5) 0.0580(5) 0.0529(5) -0.0058(4) -0.0087(4) -0.0096(4) Cl2 0.0737(7) 0.0523(5) 0.0529(5) 0.0098(4) -0.0060(5) 0.0124(5) O1 0.0429(14) 0.0497(14) 0.0415(13) -0.0052(11) -0.0011(11) -0.0017(11) C1 0.036(2) 0.041(2) 0.040(2) -0.0014(15) -0.0071(15) 0.0014(15) C2 0.036(2) 0.046(2) 0.048(2) -0.001(2) -0.004(2) 0.001(2) C3 0.035(2) 0.061(2) 0.054(2) -0.004(2) -0.004(2) -0.003(2) C4 0.043(2) 0.052(2) 0.047(2) -0.007(2) -0.011(2) 0.000(2) C5 0.041(2) 0.052(2) 0.041(2) -0.004(2) 0.001(2) 0.000(2) C6 0.035(2) 0.042(2) 0.040(2) -0.0029(15) -0.0030(14) 0.0014(14) C7 0.038(2) 0.043(2) 0.039(2) -0.0015(14) 0.0019(14) 0.0002(15) N7 0.033(2) 0.0374(15) 0.044(2) -0.0024(12) 0.0007(12) -0.0010(12) C8 0.033(2) 0.042(2) 0.048(2) -0.0101(15) 0.0022(15) -0.0022(15) C9 0.042(2) 0.051(2) 0.051(2) -0.004(2) -0.003(2) 0.001(2) C10 0.043(2) 0.072(3) 0.072(3) -0.013(2) -0.004(2) 0.008(2) C11 0.037(2) 0.090(4) 0.081(3) -0.020(3) 0.004(2) -0.006(2) C12 0.049(2) 0.073(3) 0.068(3) -0.009(2) 0.017(2) -0.016(2) C13 0.044(2) 0.051(2) 0.050(2) -0.010(2) 0.009(2) -0.004(2) C14 0.062(3) 0.058(2) 0.047(2) 0.004(2) 0.017(2) -0.003(2) C15 0.067(3) 0.043(2) 0.044(2) -0.002(2) 0.001(2) 0.001(2) C16 0.059(2) 0.044(2) 0.036(2) -0.0039(15) -0.001(2) 0.005(2) C17 0.075(3) 0.066(3) 0.032(2) 0.001(2) -0.001(2) 0.004(2) C18 0.081(3) 0.088(3) 0.041(2) -0.006(2) -0.017(2) 0.014(3) C19 0.060(3) 0.087(3) 0.052(2) -0.008(2) -0.018(2) 0.014(2) C20 0.050(2) 0.061(2) 0.045(2) 0.000(2) -0.004(2) 0.013(2) C21 0.056(2) 0.042(2) 0.034(2) -0.0021(15) -0.007(2) 0.012(2) N22 0.048(2) 0.045(2) 0.0299(14) 0.0002(12) -0.0027(12) 0.0047(13) C22 0.047(2) 0.048(2) 0.035(2) 0.000(2) -0.0017(15) 0.006(2) C23 0.044(2) 0.048(2) 0.033(2) -0.0048(15) -0.0018(15) 0.007(2) C24 0.055(2) 0.053(2) 0.038(2) 0.002(2) -0.003(2) 0.009(2) C25 0.055(2) 0.054(2) 0.044(2) -0.010(2) -0.002(2) 0.009(2) C26 0.046(2) 0.069(3) 0.033(2) -0.008(2) 0.001(2) 0.010(2) C27 0.038(2) 0.057(2) 0.035(2) -0.001(2) -0.0003(14) 0.003(2) C28 0.036(2) 0.047(2) 0.038(2) -0.0011(15) -0.0034(14) 0.0023(15) O28 0.0533(15) 0.0428(13) 0.0362(12) 0.0006(10) -0.0013(11) 0.0053(11) C29 0.045(2) 0.060(3) 0.052(2) -0.001(2) 0.004(2) -0.001(2) C30 0.065(3) 0.087(4) 0.057(3) 0.017(2) 0.010(2) -0.004(3) C31 0.057(3) 0.083(3) 0.071(3) -0.011(2) 0.012(2) 0.011(2) C32 0.046(3) 0.107(4) 0.074(3) -0.005(3) 0.009(2) -0.023(3) C33 0.047(2) 0.077(3) 0.054(2) -0.008(2) -0.010(2) -0.001(2) C34 0.083(3) 0.103(4) 0.043(2) -0.008(2) -0.009(2) -0.020(3) C35 0.097(4) 0.096(4) 0.071(3) -0.028(3) 0.003(3) -0.036(3) C36 0.084(4) 0.201(9) 0.086(4) -0.047(5) -0.043(4) 0.060(5) C37 0.077(3) 0.062(3) 0.052(2) -0.016(2) 0.001(2) 0.019(2) C38 0.105(5) 0.080(4) 0.078(3) -0.034(3) -0.007(3) 0.004(3) C39 0.273(12) 0.057(3) 0.075(4) -0.009(3) -0.004(5) 0.055(5) C40 0.095(5) 0.107(5) 0.136(6) -0.041(5) 0.025(4) 0.034(4) C41 0.058(3) 0.065(3) 0.041(2) 0.006(2) 0.009(2) 0.002(2) C42 0.083(3) 0.077(3) 0.046(2) 0.009(2) -0.007(2) 0.021(3) C43 0.129(5) 0.096(4) 0.044(2) 0.011(3) 0.032(3) 0.017(4) C44 0.079(3) 0.098(4) 0.088(4) 0.026(3) 0.002(3) -0.038(3) N50 0.094(4) 0.146(5) 0.093(4) -0.041(4) 0.010(3) -0.016(4) C51 0.057(3) 0.096(4) 0.073(3) -0.007(3) 0.004(2) 0.000(3) C52 0.080(4) 0.106(5) 0.102(5) -0.032(4) 0.005(3) 0.008(3) _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 Zr O1 1.962(3) . ? Zr O28 1.969(3) . ? Zr N7 2.359(3) . ? Zr N22 2.367(3) . ? Zr Cl2 2.4362(10) . ? Zr Cl1 2.4430(10) . ? O1 C1 1.336(4) . ? C1 C6 1.402(5) . ? C1 C2 1.406(5) . ? C2 C3 1.384(5) . ? C2 C29 1.548(5) . ? C3 C4 1.403(6) . ? C4 C5 1.384(6) . ? C4 C33 1.531(5) . ? C5 C6 1.416(5) . ? C6 C7 1.443(5) . ? C7 N7 1.306(5) . ? N7 C8 1.457(5) . ? C8 C9 1.384(6) . ? C8 C13 1.395(6) . ? C9 C10 1.367(6) . ? C10 C11 1.383(7) . ? C11 C12 1.381(7) . ? C12 C13 1.400(6) . ? C13 C14 1.512(6) . ? C14 C15 1.553(6) . ? C15 C16 1.508(6) . ? C16 C17 1.392(5) . ? C16 C21 1.396(6) . ? C17 C18 1.382(7) . ? C18 C19 1.382(7) . ? C19 C20 1.385(6) . ? C20 C21 1.384(6) . ? C21 N22 1.449(4) . ? N22 C22 1.287(5) . ? C22 C23 1.451(5) . ? C23 C24 1.395(6) . ? C23 C28 1.407(5) . ? C24 C25 1.388(5) . ? C25 C26 1.401(6) . ? C25 C37 1.528(6) . ? C26 C27 1.374(6) . ? C27 C28 1.409(5) . ? C27 C41 1.540(5) . ? C28 O28 1.339(4) . ? C29 C32 1.525(6) . ? C29 C31 1.532(6) . ? C29 C30 1.535(6) . ? C33 C34 1.514(7) . ? C33 C36 1.519(7) . ? C33 C35 1.545(8) . ? C37 C39 1.496(8) . ? C37 C40 1.532(8) . ? C37 C38 1.534(7) . ? C41 C42 1.528(6) . ? C41 C44 1.528(7) . ? C41 C43 1.542(6) . ? N50 C51 1.113(8) . ? C51 C52 1.446(8) . ? 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 Zr O28 96.96(11) . . ? O1 Zr N7 77.29(10) . . ? O28 Zr N7 164.39(10) . . ? O1 Zr N22 84.37(11) . . ? O28 Zr N22 77.29(10) . . ? N7 Zr N22 87.63(10) . . ? O1 Zr Cl2 92.53(8) . . ? O28 Zr Cl2 99.19(8) . . ? N7 Zr Cl2 95.58(8) . . ? N22 Zr Cl2 174.96(8) . . ? O1 Zr Cl1 162.60(8) . . ? O28 Zr Cl1 94.42(8) . . ? N7 Zr Cl1 88.30(7) . . ? N22 Zr Cl1 85.35(8) . . ? Cl2 Zr Cl1 98.61(4) . . ? C1 O1 Zr 146.8(2) . . ? O1 C1 C6 117.9(3) . . ? O1 C1 C2 121.0(3) . . ? C6 C1 C2 121.1(3) . . ? C3 C2 C1 116.9(4) . . ? C3 C2 C29 122.0(3) . . ? C1 C2 C29 121.1(3) . . ? C2 C3 C4 124.2(4) . . ? C5 C4 C3 117.4(4) . . ? C5 C4 C33 122.6(4) . . ? C3 C4 C33 120.0(4) . . ? C4 C5 C6 120.9(4) . . ? C1 C6 C5 119.1(3) . . ? C1 C6 C7 123.5(3) . . ? C5 C6 C7 117.3(3) . . ? N7 C7 C6 127.5(3) . . ? C7 N7 C8 115.6(3) . . ? C7 N7 Zr 125.6(2) . . ? C8 N7 Zr 118.8(2) . . ? C9 C8 C13 120.9(4) . . ? C9 C8 N7 116.8(3) . . ? C13 C8 N7 122.2(3) . . ? C10 C9 C8 121.5(4) . . ? C9 C10 C11 118.9(5) . . ? C12 C11 C10 120.1(4) . . ? C11 C12 C13 121.9(4) . . ? C8 C13 C12 116.7(4) . . ? C8 C13 C14 123.7(4) . . ? C12 C13 C14 119.5(4) . . ? C13 C14 C15 114.6(3) . . ? C16 C15 C14 114.0(3) . . ? C17 C16 C21 116.8(4) . . ? C17 C16 C15 119.7(4) . . ? C21 C16 C15 123.4(3) . . ? C18 C17 C16 122.0(4) . . ? C17 C18 C19 120.5(4) . . ? C18 C19 C20 118.4(5) . . ? C21 C20 C19 121.0(4) . . ? C20 C21 C16 121.3(3) . . ? C20 C21 N22 116.7(4) . . ? C16 C21 N22 122.0(4) . . ? C22 N22 C21 114.7(3) . . ? C22 N22 Zr 123.0(2) . . ? C21 N22 Zr 121.4(2) . . ? N22 C22 C23 128.4(3) . . ? C24 C23 C28 119.9(3) . . ? C24 C23 C22 117.8(3) . . ? C28 C23 C22 121.8(3) . . ? C25 C24 C23 121.4(4) . . ? C24 C25 C26 116.4(4) . . ? C24 C25 C37 123.5(4) . . ? C26 C25 C37 120.1(4) . . ? C27 C26 C25 125.2(4) . . ? C26 C27 C28 116.8(4) . . ? C26 C27 C41 121.8(3) . . ? C28 C27 C41 121.4(4) . . ? O28 C28 C23 118.7(3) . . ? O28 C28 C27 121.1(3) . . ? C23 C28 C27 120.2(3) . . ? C28 O28 Zr 140.2(2) . . ? C32 C29 C31 108.7(4) . . ? C32 C29 C30 107.4(4) . . ? C31 C29 C30 109.0(4) . . ? C32 C29 C2 111.6(4) . . ? C31 C29 C2 109.9(4) . . ? C30 C29 C2 110.2(3) . . ? C34 C33 C36 110.0(5) . . ? C34 C33 C4 112.4(4) . . ? C36 C33 C4 109.2(4) . . ? C34 C33 C35 106.3(4) . . ? C36 C33 C35 110.5(5) . . ? C4 C33 C35 108.4(4) . . ? C39 C37 C25 112.4(4) . . ? C39 C37 C40 110.6(6) . . ? C25 C37 C40 109.2(5) . . ? C39 C37 C38 108.7(6) . . ? C25 C37 C38 108.3(4) . . ? C40 C37 C38 107.6(5) . . ? C42 C41 C44 110.0(5) . . ? C42 C41 C27 111.4(4) . . ? C44 C41 C27 108.2(4) . . ? C42 C41 C43 106.6(4) . . ? C44 C41 C43 108.8(5) . . ? C27 C41 C43 111.9(4) . . ? N50 C51 C52 179.7(7) . . ? _refine_diff_density_max 0.325 _refine_diff_density_min -0.462 _refine_diff_density_rms 0.057