# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_ml25-mach _database_code_depnum_ccdc_archive 'CCDC 864584' #TrackingRef 'ml25-mach.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C32 H37 N Zr' _chemical_formula_sum 'C32 H37 N Zr' _chemical_formula_weight 526.85 _chemical_compound_source 'synthesized by the authors' 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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.9090(4) _cell_length_b 10.9060(2) _cell_length_c 17.5040(4) _cell_angle_alpha 90.00 _cell_angle_beta 97.8340(13) _cell_angle_gamma 90.00 _cell_volume 2630.43(11) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 6218 _cell_measurement_theta_min 1 _cell_measurement_theta_max 27.5 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.330 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1104 _exptl_absorpt_coefficient_mu 0.438 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector' _diffrn_measurement_method '\f and \w scans to fill the Ewald sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 39109 _diffrn_reflns_av_R_equivalents 0.0381 _diffrn_reflns_av_sigmaI/netI 0.0338 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.48 _diffrn_reflns_theta_max 27.48 _reflns_number_total 6020 _reflns_number_gt 4888 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997)' _computing_cell_refinement 'COLLECT and DENZO' _computing_data_reduction 'COLLECT and DENZO' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0438P)^2^+0.4972P] 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_number_reflns 6020 _refine_ls_number_parameters 314 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0426 _refine_ls_R_factor_gt 0.0303 _refine_ls_wR_factor_ref 0.0803 _refine_ls_wR_factor_gt 0.0750 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _refine_ls_shift/su_max 0.002 _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 Zr1 Zr 0.281763(12) 0.831155(15) 0.316796(9) 0.02063(7) Uani 1 1 d . . . C1 C 0.19722(15) 0.82899(16) 0.17731(9) 0.0260(4) Uani 1 1 d . . . C2 C 0.27738(14) 0.91032(19) 0.18201(10) 0.0302(4) Uani 1 1 d . . . H2 H 0.2737 0.9949 0.1757 0.036 Uiso 1 1 calc R . . C3 C 0.36387(16) 0.8412(2) 0.19781(11) 0.0376(5) Uani 1 1 d . . . H3 H 0.4267 0.8720 0.2026 0.045 Uiso 1 1 calc R . . C4 C 0.33821(16) 0.7186(2) 0.20498(11) 0.0389(5) Uani 1 1 d . . . H4 H 0.3810 0.6534 0.2156 0.047 Uiso 1 1 calc R . . C5 C 0.23597(15) 0.71070(19) 0.19327(10) 0.0312(4) Uani 1 1 d . . . H5 H 0.2000 0.6392 0.1957 0.037 Uiso 1 1 calc R . . C6 C 0.09175(15) 0.86325(18) 0.15440(10) 0.0293(4) Uani 1 1 d . . . C7 C 0.08139(18) 0.9289(2) 0.07634(11) 0.0451(6) Uani 1 1 d . . . H7A H 0.1187 1.0032 0.0811 0.068 Uiso 1 1 calc R . . H7B H 0.0143 0.9481 0.0602 0.068 Uiso 1 1 calc R . . H7C H 0.1046 0.8765 0.0388 0.068 Uiso 1 1 calc R . . C8 C 0.02762(16) 0.7490(2) 0.14623(12) 0.0394(5) Uani 1 1 d . . . H8A H 0.0461 0.6977 0.1061 0.059 Uiso 1 1 calc R . . H8B H -0.0390 0.7730 0.1334 0.059 Uiso 1 1 calc R . . H8C H 0.0355 0.7047 0.1940 0.059 Uiso 1 1 calc R . . C9 C 0.05566(14) 0.95213(17) 0.21398(11) 0.0306(4) Uani 1 1 d . . . H9A H 0.0973 1.0238 0.2204 0.037 Uiso 1 1 calc R . . H9B H -0.0098 0.9791 0.1954 0.037 Uiso 1 1 calc R . . C10 C 0.05707(13) 0.88726(16) 0.29082(10) 0.0254(4) Uani 1 1 d . . . C11 C -0.03691(14) 0.85809(16) 0.32100(11) 0.0265(4) Uani 1 1 d . . . C12 C -0.12807(15) 0.88326(18) 0.28083(12) 0.0333(4) Uani 1 1 d . . . H12 H -0.1331 0.9199 0.2325 0.040 Uiso 1 1 calc R . . C13 C -0.21189(15) 0.8542(2) 0.31226(13) 0.0393(5) Uani 1 1 d . . . H13 H -0.2724 0.8719 0.2848 0.047 Uiso 1 1 calc R . . C14 C -0.20598(16) 0.7996(2) 0.38367(14) 0.0432(5) Uani 1 1 d . . . H14 H -0.2621 0.7799 0.4044 0.052 Uiso 1 1 calc R . . C15 C -0.11600(16) 0.7743(2) 0.42429(13) 0.0411(5) Uani 1 1 d . . . H15 H -0.1117 0.7376 0.4726 0.049 Uiso 1 1 calc R . . C16 C -0.03201(15) 0.80303(19) 0.39367(12) 0.0346(5) Uani 1 1 d . . . H16 H 0.0282 0.7856 0.4217 0.042 Uiso 1 1 calc R . . C17 C 0.31127(14) 0.63809(16) 0.37013(10) 0.0263(4) Uani 1 1 d . . . C18 C 0.23964(15) 0.58068(18) 0.40341(11) 0.0336(4) Uani 1 1 d . . . H18 H 0.1802 0.6199 0.4028 0.040 Uiso 1 1 calc R . . C19 C 0.25274(17) 0.46536(19) 0.43815(13) 0.0441(5) Uani 1 1 d . . . H19 H 0.2022 0.4292 0.4597 0.053 Uiso 1 1 calc R . . C20 C 0.34047(17) 0.40484(19) 0.44058(13) 0.0433(5) Uani 1 1 d . . . H20 H 0.3496 0.3284 0.4640 0.052 Uiso 1 1 calc R . . C21 C 0.41422(16) 0.45993(18) 0.40763(12) 0.0382(5) Uani 1 1 d . . . H21 H 0.4738 0.4207 0.4088 0.046 Uiso 1 1 calc R . . C22 C 0.39949(15) 0.57315(18) 0.37309(11) 0.0331(4) Uani 1 1 d . . . H22 H 0.4498 0.6083 0.3508 0.040 Uiso 1 1 calc R . . C23 C 0.38833(14) 0.88145(17) 0.44392(10) 0.0287(4) Uani 1 1 d . . . C24 C 0.43245(13) 0.93556(16) 0.38344(11) 0.0276(4) Uani 1 1 d . . . C25 C 0.36990(13) 1.03005(16) 0.35007(10) 0.0255(4) Uani 1 1 d . . . C26 C 0.28668(13) 1.03234(16) 0.38906(10) 0.0243(4) Uani 1 1 d . . . C27 C 0.29827(14) 0.93938(16) 0.44660(10) 0.0260(4) Uani 1 1 d . . . C28 C 0.43654(17) 0.7916(2) 0.50270(11) 0.0407(5) Uani 1 1 d . . . H28A H 0.4750 0.8355 0.5435 0.061 Uiso 1 1 calc R . . H28B H 0.4775 0.7373 0.4784 0.061 Uiso 1 1 calc R . . H28C H 0.3878 0.7447 0.5235 0.061 Uiso 1 1 calc R . . C29 C 0.53359(15) 0.9082(2) 0.36645(14) 0.0412(5) Uani 1 1 d . . . H29A H 0.5417 0.9409 0.3168 0.062 Uiso 1 1 calc R . . H29B H 0.5435 0.8211 0.3665 0.062 Uiso 1 1 calc R . . H29C H 0.5800 0.9453 0.4052 0.062 Uiso 1 1 calc R . . C30 C 0.39378(16) 1.12416(18) 0.29272(12) 0.0357(5) Uani 1 1 d . . . H30A H 0.4303 1.1896 0.3194 0.054 Uiso 1 1 calc R . . H30B H 0.3348 1.1563 0.2651 0.054 Uiso 1 1 calc R . . H30C H 0.4315 1.0866 0.2570 0.054 Uiso 1 1 calc R . . C31 C 0.20449(15) 1.12271(17) 0.37687(12) 0.0331(4) Uani 1 1 d . . . H31A H 0.2164 1.1880 0.4137 0.050 Uiso 1 1 calc R . . H31B H 0.1449 1.0822 0.3835 0.050 Uiso 1 1 calc R . . H31C H 0.1996 1.1556 0.3256 0.050 Uiso 1 1 calc R . . C32 C 0.22940(16) 0.91165(19) 0.50350(10) 0.0360(5) Uani 1 1 d . . . H32A H 0.2265 0.8246 0.5111 0.054 Uiso 1 1 calc R . . H32B H 0.1659 0.9418 0.4840 0.054 Uiso 1 1 calc R . . H32C H 0.2518 0.9508 0.5518 0.054 Uiso 1 1 calc R . . N1 N 0.13762(11) 0.85188(13) 0.32610(8) 0.0237(3) Uani 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 Zr1 0.01866(10) 0.02441(10) 0.01876(10) 0.00089(6) 0.00234(7) 0.00113(7) C1 0.0324(11) 0.0308(10) 0.0148(8) 0.0005(7) 0.0031(8) -0.0039(8) C2 0.0306(11) 0.0395(11) 0.0204(9) 0.0039(8) 0.0028(8) -0.0073(9) C3 0.0277(11) 0.0637(15) 0.0230(10) -0.0022(9) 0.0093(9) -0.0040(10) C4 0.0409(13) 0.0535(13) 0.0234(10) -0.0054(9) 0.0080(9) 0.0157(11) C5 0.0414(12) 0.0317(10) 0.0205(9) -0.0040(8) 0.0040(9) 0.0007(9) C6 0.0300(11) 0.0349(10) 0.0213(9) 0.0042(8) -0.0030(8) -0.0056(8) C7 0.0455(14) 0.0599(14) 0.0273(10) 0.0142(10) -0.0047(10) -0.0021(11) C8 0.0360(12) 0.0456(12) 0.0355(11) -0.0049(9) 0.0003(9) -0.0124(10) C9 0.0246(10) 0.0321(10) 0.0330(10) 0.0079(8) -0.0033(8) 0.0009(8) C10 0.0225(10) 0.0253(9) 0.0277(9) -0.0017(7) 0.0010(8) 0.0002(7) C11 0.0214(9) 0.0261(9) 0.0314(10) -0.0056(7) 0.0017(8) 0.0024(7) C12 0.0268(11) 0.0349(10) 0.0371(11) -0.0054(9) 0.0007(9) 0.0021(9) C13 0.0180(10) 0.0422(12) 0.0564(15) -0.0139(10) 0.0005(10) 0.0027(8) C14 0.0277(12) 0.0432(12) 0.0620(15) -0.0098(11) 0.0183(11) -0.0052(9) C15 0.0351(12) 0.0452(13) 0.0457(12) 0.0034(10) 0.0155(10) -0.0012(10) C16 0.0244(10) 0.0426(11) 0.0376(11) 0.0034(9) 0.0070(9) 0.0029(9) C17 0.0285(10) 0.0269(9) 0.0222(9) -0.0039(7) -0.0013(8) 0.0055(8) C18 0.0309(11) 0.0320(10) 0.0383(11) -0.0012(9) 0.0055(9) 0.0049(9) C19 0.0403(13) 0.0359(11) 0.0586(14) 0.0118(10) 0.0160(11) -0.0019(10) C20 0.0478(14) 0.0288(10) 0.0537(13) 0.0083(10) 0.0079(11) 0.0040(10) C21 0.0376(12) 0.0337(11) 0.0437(12) 0.0026(9) 0.0062(10) 0.0106(9) C22 0.0303(11) 0.0339(10) 0.0361(11) 0.0035(9) 0.0083(9) 0.0010(9) C23 0.0287(11) 0.0279(9) 0.0265(9) -0.0008(8) -0.0073(8) 0.0017(8) C24 0.0193(9) 0.0282(9) 0.0338(10) -0.0035(8) -0.0020(8) -0.0005(7) C25 0.0212(9) 0.0267(9) 0.0280(9) -0.0002(7) 0.0014(8) -0.0021(7) C26 0.0207(9) 0.0251(9) 0.0259(9) -0.0033(7) -0.0009(7) -0.0001(7) C27 0.0311(10) 0.0254(9) 0.0206(8) -0.0032(7) -0.0001(8) -0.0018(8) C28 0.0475(14) 0.0382(11) 0.0309(11) 0.0020(9) -0.0144(10) 0.0047(10) C29 0.0214(11) 0.0420(12) 0.0590(14) -0.0053(10) 0.0011(10) 0.0016(9) C30 0.0322(12) 0.0336(10) 0.0419(12) 0.0061(9) 0.0067(10) -0.0055(9) C31 0.0287(11) 0.0284(9) 0.0418(11) -0.0042(9) 0.0029(9) 0.0032(8) C32 0.0453(13) 0.0392(11) 0.0242(9) -0.0024(8) 0.0078(9) -0.0054(10) N1 0.0214(8) 0.0281(8) 0.0213(7) -0.0003(6) 0.0021(6) 0.0012(6) _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 Zr1 N1 2.0459(15) . ? Zr1 C17 2.3171(18) . ? Zr1 C2 2.5053(17) . ? Zr1 C3 2.5104(19) . ? Zr1 C25 2.5204(18) . ? Zr1 C4 2.5243(18) . ? Zr1 C24 2.5266(19) . ? Zr1 C26 2.5289(17) . ? Zr1 C5 2.5359(18) . ? Zr1 C27 2.5429(17) . ? Zr1 C23 2.5593(18) . ? Zr1 C1 2.5617(18) . ? C1 C5 1.411(3) . ? C1 C2 1.418(3) . ? C1 C6 1.514(3) . ? C2 C3 1.415(3) . ? C2 H2 0.9300 . ? C3 C4 1.393(3) . ? C3 H3 0.9300 . ? C4 C5 1.411(3) . ? C4 H4 0.9300 . ? C5 H5 0.9300 . ? C6 C8 1.527(3) . ? C6 C7 1.532(3) . ? C6 C9 1.556(3) . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 C10 1.517(2) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 N1 1.264(2) . ? C10 C11 1.509(3) . ? C11 C12 1.391(3) . ? C11 C16 1.400(3) . ? C12 C13 1.392(3) . ? C12 H12 0.9300 . ? C13 C14 1.377(3) . ? C13 H13 0.9300 . ? C14 C15 1.380(3) . ? C14 H14 0.9300 . ? C15 C16 1.386(3) . ? C15 H15 0.9300 . ? C16 H16 0.9300 . ? C17 C18 1.372(3) . ? C17 C22 1.412(3) . ? C18 C19 1.398(3) . ? C18 H18 0.9300 . ? C19 C20 1.383(3) . ? C19 H19 0.9300 . ? C20 C21 1.381(3) . ? C20 H20 0.9300 . ? C21 C22 1.378(3) . ? C21 H21 0.9300 . ? C22 H22 0.9300 . ? C23 C27 1.409(3) . ? C23 C24 1.422(3) . ? C23 C28 1.510(3) . ? C24 C25 1.422(3) . ? C24 C29 1.507(3) . ? C25 C26 1.422(2) . ? C25 C30 1.504(3) . ? C26 C27 1.423(2) . ? C26 C31 1.502(3) . ? C27 C32 1.504(3) . ? C28 H28A 0.9600 . ? C28 H28B 0.9600 . ? C28 H28C 0.9600 . ? C29 H29A 0.9600 . ? C29 H29B 0.9600 . ? C29 H29C 0.9600 . ? C30 H30A 0.9600 . ? C30 H30B 0.9600 . ? C30 H30C 0.9600 . ? C31 H31A 0.9600 . ? C31 H31B 0.9600 . ? C31 H31C 0.9600 . ? C32 H32A 0.9600 . ? C32 H32B 0.9600 . ? C32 H32C 0.9600 . ? 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 N1 Zr1 C17 100.95(6) . . ? N1 Zr1 C2 97.96(6) . . ? C17 Zr1 C2 132.29(6) . . ? N1 Zr1 C3 128.52(7) . . ? C17 Zr1 C3 107.35(7) . . ? C2 Zr1 C3 32.77(7) . . ? N1 Zr1 C25 109.73(6) . . ? C17 Zr1 C25 129.43(6) . . ? C2 Zr1 C25 82.51(6) . . ? C3 Zr1 C25 83.82(6) . . ? N1 Zr1 C4 121.81(7) . . ? C17 Zr1 C4 79.28(7) . . ? C2 Zr1 C4 53.67(7) . . ? C3 Zr1 C4 32.13(7) . . ? C25 Zr1 C4 113.87(7) . . ? N1 Zr1 C24 132.35(6) . . ? C17 Zr1 C24 97.66(6) . . ? C2 Zr1 C24 101.05(6) . . ? C3 Zr1 C24 85.46(7) . . ? C25 Zr1 C24 32.73(6) . . ? C4 Zr1 C24 104.54(7) . . ? N1 Zr1 C26 79.88(6) . . ? C17 Zr1 C26 126.56(6) . . ? C2 Zr1 C26 99.65(6) . . ? C3 Zr1 C26 113.14(6) . . ? C25 Zr1 C26 32.71(5) . . ? C4 Zr1 C26 145.04(7) . . ? C24 Zr1 C26 54.12(6) . . ? N1 Zr1 C5 89.43(6) . . ? C17 Zr1 C5 83.28(6) . . ? C2 Zr1 C5 53.45(6) . . ? C3 Zr1 C5 53.48(7) . . ? C25 Zr1 C5 134.47(6) . . ? C4 Zr1 C5 32.39(7) . . ? C24 Zr1 C5 136.32(6) . . ? C26 Zr1 C5 149.59(6) . . ? N1 Zr1 C27 81.24(6) . . ? C17 Zr1 C27 94.15(6) . . ? C2 Zr1 C27 132.00(6) . . ? C3 Zr1 C27 136.49(7) . . ? C25 Zr1 C27 54.00(6) . . ? C4 Zr1 C27 156.74(7) . . ? C24 Zr1 C27 53.85(6) . . ? C26 Zr1 C27 32.58(6) . . ? C5 Zr1 C27 169.70(6) . . ? N1 Zr1 C23 111.40(6) . . ? C17 Zr1 C23 78.15(6) . . ? C2 Zr1 C23 132.98(6) . . ? C3 Zr1 C23 115.91(7) . . ? C25 Zr1 C23 53.76(6) . . ? C4 Zr1 C23 125.02(7) . . ? C24 Zr1 C23 32.47(6) . . ? C26 Zr1 C23 53.57(6) . . ? C5 Zr1 C23 154.25(6) . . ? C27 Zr1 C23 32.07(6) . . ? N1 Zr1 C1 75.48(6) . . ? C17 Zr1 C1 114.13(6) . . ? C2 Zr1 C1 32.49(6) . . ? C3 Zr1 C1 53.93(7) . . ? C25 Zr1 C1 111.95(6) . . ? C4 Zr1 C1 53.66(6) . . ? C24 Zr1 C1 133.50(6) . . ? C26 Zr1 C1 117.54(6) . . ? C5 Zr1 C1 32.14(6) . . ? C27 Zr1 C1 146.07(6) . . ? C23 Zr1 C1 165.21(6) . . ? C5 C1 C2 106.51(18) . . ? C5 C1 C6 127.45(17) . . ? C2 C1 C6 125.93(17) . . ? C5 C1 Zr1 72.93(10) . . ? C2 C1 Zr1 71.57(10) . . ? C6 C1 Zr1 123.54(11) . . ? C3 C2 C1 108.58(18) . . ? C3 C2 Zr1 73.81(11) . . ? C1 C2 Zr1 75.94(10) . . ? C3 C2 H2 125.7 . . ? C1 C2 H2 125.7 . . ? Zr1 C2 H2 116.5 . . ? C4 C3 C2 107.91(19) . . ? C4 C3 Zr1 74.49(11) . . ? C2 C3 Zr1 73.42(10) . . ? C4 C3 H3 126.0 . . ? C2 C3 H3 126.0 . . ? Zr1 C3 H3 118.0 . . ? C3 C4 C5 108.12(19) . . ? C3 C4 Zr1 73.39(11) . . ? C5 C4 Zr1 74.26(10) . . ? C3 C4 H4 125.9 . . ? C5 C4 H4 125.9 . . ? Zr1 C4 H4 118.3 . . ? C1 C5 C4 108.83(19) . . ? C1 C5 Zr1 74.93(10) . . ? C4 C5 Zr1 73.35(11) . . ? C1 C5 H5 125.6 . . ? C4 C5 H5 125.6 . . ? Zr1 C5 H5 118.0 . . ? C1 C6 C8 110.85(17) . . ? C1 C6 C7 108.75(16) . . ? C8 C6 C7 108.35(17) . . ? C1 C6 C9 111.45(15) . . ? C8 C6 C9 109.46(16) . . ? C7 C6 C9 107.87(16) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C10 C9 C6 109.70(15) . . ? C10 C9 H9A 109.7 . . ? C6 C9 H9A 109.7 . . ? C10 C9 H9B 109.7 . . ? C6 C9 H9B 109.7 . . ? H9A C9 H9B 108.2 . . ? N1 C10 C11 121.14(16) . . ? N1 C10 C9 118.62(16) . . ? C11 C10 C9 120.10(16) . . ? C12 C11 C16 118.18(18) . . ? C12 C11 C10 123.70(17) . . ? C16 C11 C10 118.12(17) . . ? C11 C12 C13 120.7(2) . . ? C11 C12 H12 119.7 . . ? C13 C12 H12 119.7 . . ? C14 C13 C12 120.5(2) . . ? C14 C13 H13 119.7 . . ? C12 C13 H13 119.7 . . ? C13 C14 C15 119.5(2) . . ? C13 C14 H14 120.3 . . ? C15 C14 H14 120.3 . . ? C14 C15 C16 120.6(2) . . ? C14 C15 H15 119.7 . . ? C16 C15 H15 119.7 . . ? C15 C16 C11 120.6(2) . . ? C15 C16 H16 119.7 . . ? C11 C16 H16 119.7 . . ? C18 C17 C22 115.68(17) . . ? C18 C17 Zr1 119.13(14) . . ? C22 C17 Zr1 125.17(14) . . ? C17 C18 C19 122.4(2) . . ? C17 C18 H18 118.8 . . ? C19 C18 H18 118.8 . . ? C20 C19 C18 120.3(2) . . ? C20 C19 H19 119.8 . . ? C18 C19 H19 119.8 . . ? C21 C20 C19 118.82(19) . . ? C21 C20 H20 120.6 . . ? C19 C20 H20 120.6 . . ? C22 C21 C20 119.9(2) . . ? C22 C21 H21 120.0 . . ? C20 C21 H21 120.0 . . ? C21 C22 C17 122.84(19) . . ? C21 C22 H22 118.6 . . ? C17 C22 H22 118.6 . . ? C27 C23 C24 108.33(16) . . ? C27 C23 C28 125.61(18) . . ? C24 C23 C28 125.44(19) . . ? C27 C23 Zr1 73.32(10) . . ? C24 C23 Zr1 72.50(10) . . ? C28 C23 Zr1 127.15(13) . . ? C25 C24 C23 107.73(16) . . ? C25 C24 C29 126.71(17) . . ? C23 C24 C29 125.04(18) . . ? C25 C24 Zr1 73.40(10) . . ? C23 C24 Zr1 75.03(11) . . ? C29 C24 Zr1 123.91(13) . . ? C26 C25 C24 107.95(15) . . ? C26 C25 C30 125.22(17) . . ? C24 C25 C30 126.17(17) . . ? C26 C25 Zr1 73.97(10) . . ? C24 C25 Zr1 73.88(10) . . ? C30 C25 Zr1 125.29(13) . . ? C25 C26 C27 107.83(16) . . ? C25 C26 C31 126.64(16) . . ? C27 C26 C31 125.36(16) . . ? C25 C26 Zr1 73.32(10) . . ? C27 C26 Zr1 74.25(10) . . ? C31 C26 Zr1 122.00(12) . . ? C23 C27 C26 108.14(16) . . ? C23 C27 C32 125.54(17) . . ? C26 C27 C32 126.25(17) . . ? C23 C27 Zr1 74.61(10) . . ? C26 C27 Zr1 73.17(10) . . ? C32 C27 Zr1 120.69(12) . . ? C23 C28 H28A 109.5 . . ? C23 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C23 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C24 C29 H29A 109.5 . . ? C24 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C24 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C25 C30 H30A 109.5 . . ? C25 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C25 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? C26 C31 H31A 109.5 . . ? C26 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? C26 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? C27 C32 H32A 109.5 . . ? C27 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C27 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C10 N1 Zr1 143.90(13) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.726 _refine_diff_density_min -0.484 _refine_diff_density_rms 0.058 data_ccdc864585 _database_code_depnum_ccdc_archive 'CCDC 864585' #TrackingRef '864585.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H34 Cl2 N Zr, C H4 O, Cl' _chemical_formula_sum 'C27 H38 Cl3 N O Zr' _chemical_formula_weight 590.15 _chemical_compound_source 'synthesized by the authors' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/n' _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 8.3978(3) _cell_length_b 14.4909(5) _cell_length_c 22.8225(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.074(2) _cell_angle_gamma 90.00 _cell_volume 2777.31(16) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 9891 _cell_measurement_theta_min 2.27 _cell_measurement_theta_max 30.59 _exptl_crystal_description bar _exptl_crystal_colour colourless _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.411 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1224 _exptl_absorpt_coefficient_mu 0.704 _exptl_absorpt_correction_type gaussian _exptl_absorpt_correction_T_min 0.7464 _exptl_absorpt_correction_T_max 0.8861 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 35399 _diffrn_reflns_av_R_equivalents 0.0317 _diffrn_reflns_av_sigmaI/netI 0.0240 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 1.66 _diffrn_reflns_theta_max 27.50 _reflns_number_total 6359 _reflns_number_gt 5522 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0253P)^2^+1.7297P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6359 _refine_ls_number_parameters 318 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0324 _refine_ls_R_factor_gt 0.0247 _refine_ls_wR_factor_ref 0.0609 _refine_ls_wR_factor_gt 0.0572 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _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 Zr1 Zr 0.828821(18) 0.291378(10) 0.798096(6) 0.01415(5) Uani 1 1 d . . . N1 N 1.35392(19) 0.09198(11) 0.98011(7) 0.0249(3) Uani 1 1 d . . . H1N H 1.345(3) 0.0361(17) 0.9726(10) 0.037(6) Uiso 1 1 d . . . H2N H 1.441(3) 0.1138(15) 0.9932(10) 0.037(6) Uiso 1 1 d . . . C1 C 0.99412(18) 0.21319(11) 0.88206(7) 0.0150(3) Uani 1 1 d . . . C2 C 1.0926(2) 0.27895(11) 0.85415(7) 0.0197(3) Uani 1 1 d . . . H2 H 1.1877 0.2656 0.8333 0.024 Uiso 1 1 calc R . . C3 C 1.0273(2) 0.36697(12) 0.86220(8) 0.0230(4) Uani 1 1 d . . . H3 H 1.0705 0.4234 0.8482 0.028 Uiso 1 1 calc R . . C4 C 0.8852(2) 0.35693(12) 0.89503(7) 0.0223(4) Uani 1 1 d . . . H4 H 0.8155 0.4052 0.9066 0.027 Uiso 1 1 calc R . . C5 C 0.8660(2) 0.26238(11) 0.90727(7) 0.0180(3) Uani 1 1 d . . . H5 H 0.7809 0.2360 0.9289 0.022 Uiso 1 1 calc R . . C6 C 1.03103(19) 0.11184(11) 0.89223(7) 0.0163(3) Uani 1 1 d . . . C7 C 1.1687(2) 0.07790(12) 0.85405(8) 0.0252(4) Uani 1 1 d . . . H7A H 1.1360 0.0785 0.8128 0.038 Uiso 1 1 calc R . . H7B H 1.1974 0.0149 0.8655 0.038 Uiso 1 1 calc R . . H7C H 1.2608 0.1186 0.8593 0.038 Uiso 1 1 calc R . . C8 C 0.8848(2) 0.05035(12) 0.88168(8) 0.0258(4) Uani 1 1 d . . . H8A H 0.7979 0.0701 0.9074 0.039 Uiso 1 1 calc R . . H8B H 0.9123 -0.0140 0.8902 0.039 Uiso 1 1 calc R . . H8C H 0.8511 0.0557 0.8407 0.039 Uiso 1 1 calc R . . C9 C 1.07699(19) 0.09834(11) 0.95830(7) 0.0171(3) Uani 1 1 d . . . H9A H 0.9904 0.1236 0.9829 0.021 Uiso 1 1 calc R . . H9B H 1.0846 0.0314 0.9665 0.021 Uiso 1 1 calc R . . C10 C 1.22948(19) 0.14300(11) 0.97562(7) 0.0177(3) Uani 1 1 d . . . C11 C 1.24254(19) 0.24315(11) 0.98581(7) 0.0171(3) Uani 1 1 d . . . C12 C 1.3806(2) 0.29030(12) 0.96978(8) 0.0233(4) Uani 1 1 d . . . H12 H 1.4684 0.2575 0.9538 0.028 Uiso 1 1 calc R . . C13 C 1.3894(2) 0.38481(13) 0.97714(9) 0.0288(4) Uani 1 1 d . . . H13 H 1.4828 0.4171 0.9657 0.035 Uiso 1 1 calc R . . C14 C 1.2618(2) 0.43283(13) 1.00125(8) 0.0287(4) Uani 1 1 d . . . H14 H 1.2677 0.4979 1.0059 0.034 Uiso 1 1 calc R . . C15 C 1.1267(2) 0.38586(12) 1.01843(8) 0.0254(4) Uani 1 1 d . . . H15 H 1.0409 0.4186 1.0358 0.031 Uiso 1 1 calc R . . C16 C 1.1155(2) 0.29152(12) 1.01051(7) 0.0200(3) Uani 1 1 d . . . H16 H 1.0216 0.2597 1.0218 0.024 Uiso 1 1 calc R . . C17 C 0.6350(2) 0.41852(11) 0.77543(7) 0.0209(3) Uani 1 1 d . . . C18 C 0.6278(2) 0.35883(12) 0.72631(8) 0.0235(4) Uani 1 1 d . . . C19 C 0.7762(2) 0.36165(13) 0.69786(7) 0.0258(4) Uani 1 1 d . . . C20 C 0.8766(2) 0.42175(12) 0.72949(8) 0.0256(4) Uani 1 1 d . . . C21 C 0.7871(2) 0.46006(12) 0.77662(8) 0.0231(4) Uani 1 1 d . . . C22 C 0.8132(3) 0.31685(17) 0.63993(9) 0.0528(7) Uani 1 1 d . . . H22A H 0.7677 0.2546 0.6391 0.079 Uiso 1 1 calc R . . H22B H 0.9289 0.3131 0.6349 0.079 Uiso 1 1 calc R . . H22C H 0.7671 0.3537 0.6081 0.079 Uiso 1 1 calc R . . C23 C 1.0408(2) 0.44994(17) 0.71059(12) 0.0505(7) Uani 1 1 d . . . H23A H 1.0988 0.3957 0.6964 0.076 Uiso 1 1 calc R . . H23B H 1.0978 0.4769 0.7439 0.076 Uiso 1 1 calc R . . H23C H 1.0329 0.4956 0.6791 0.076 Uiso 1 1 calc R . . C24 C 0.8367(3) 0.54047(13) 0.81356(10) 0.0428(6) Uani 1 1 d . . . H24A H 0.8062 0.5980 0.7940 0.064 Uiso 1 1 calc R . . H24B H 0.9525 0.5392 0.8191 0.064 Uiso 1 1 calc R . . H24C H 0.7841 0.5368 0.8518 0.064 Uiso 1 1 calc R . . C25 C 0.4980(3) 0.44099(15) 0.81515(10) 0.0403(5) Uani 1 1 d . . . H25A H 0.5385 0.4687 0.8514 0.061 Uiso 1 1 calc R . . H25B H 0.4397 0.3843 0.8245 0.061 Uiso 1 1 calc R . . H25C H 0.4265 0.4846 0.7955 0.061 Uiso 1 1 calc R . . C26 C 0.4818(3) 0.30988(15) 0.70400(11) 0.0447(6) Uani 1 1 d . . . H26A H 0.4249 0.3500 0.6765 0.067 Uiso 1 1 calc R . . H26B H 0.4119 0.2948 0.7370 0.067 Uiso 1 1 calc R . . H26C H 0.5134 0.2530 0.6840 0.067 Uiso 1 1 calc R . . C27 C 0.6941(3) 0.36682(17) 0.10040(11) 0.0534(7) Uani 1 1 d . . . H27A H 0.7386 0.3235 0.1290 0.080 Uiso 1 1 calc R . . H27B H 0.5775 0.3650 0.1023 0.080 Uiso 1 1 calc R . . H27C H 0.7313 0.4294 0.1093 0.080 Uiso 1 1 calc R . . Cl1 Cl 0.97580(6) 0.18712(3) 0.734645(18) 0.02768(10) Uani 1 1 d . . . Cl2 Cl 0.59282(5) 0.19913(3) 0.82176(2) 0.02706(10) Uani 1 1 d . . . Cl3 Cl 0.68859(5) 0.12474(3) 0.035476(19) 0.02329(9) Uani 1 1 d . . . O1 O 0.74384(18) 0.34188(10) 0.04408(7) 0.0358(3) Uani 1 1 d . . . H1O H 0.725(3) 0.2906(16) 0.0410(10) 0.036(7) 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 Zr1 0.01516(8) 0.01457(8) 0.01273(8) 0.00056(5) 0.00064(5) -0.00060(6) N1 0.0200(8) 0.0177(8) 0.0369(9) -0.0005(6) -0.0076(7) 0.0023(6) C1 0.0150(7) 0.0165(8) 0.0136(7) 0.0002(6) -0.0019(6) 0.0003(6) C2 0.0157(8) 0.0220(9) 0.0214(8) 0.0026(6) -0.0029(6) -0.0035(7) C3 0.0277(9) 0.0171(8) 0.0241(9) 0.0028(7) -0.0102(7) -0.0062(7) C4 0.0323(10) 0.0181(8) 0.0167(8) -0.0048(6) -0.0065(7) 0.0069(7) C5 0.0208(8) 0.0209(8) 0.0123(7) -0.0005(6) 0.0001(6) 0.0034(7) C6 0.0156(8) 0.0144(8) 0.0189(8) -0.0006(6) 0.0000(6) 0.0011(6) C7 0.0275(9) 0.0249(9) 0.0231(9) -0.0013(7) 0.0041(7) 0.0097(7) C8 0.0250(9) 0.0173(8) 0.0350(10) -0.0026(7) -0.0060(7) -0.0019(7) C9 0.0166(8) 0.0143(8) 0.0204(8) 0.0037(6) 0.0016(6) 0.0004(6) C10 0.0176(8) 0.0196(8) 0.0158(8) 0.0034(6) 0.0011(6) 0.0015(6) C11 0.0180(8) 0.0183(8) 0.0151(8) 0.0014(6) -0.0026(6) 0.0005(6) C12 0.0180(8) 0.0240(9) 0.0279(9) 0.0001(7) 0.0003(7) -0.0005(7) C13 0.0263(9) 0.0244(9) 0.0356(11) 0.0011(8) -0.0032(8) -0.0083(8) C14 0.0355(11) 0.0190(9) 0.0315(10) -0.0037(7) -0.0081(8) -0.0012(8) C15 0.0278(9) 0.0240(9) 0.0245(9) -0.0062(7) -0.0024(7) 0.0052(7) C16 0.0204(8) 0.0232(8) 0.0163(8) 0.0006(6) -0.0008(6) 0.0011(7) C17 0.0223(9) 0.0194(8) 0.0210(9) 0.0052(6) 0.0043(7) 0.0051(7) C18 0.0247(9) 0.0208(9) 0.0251(9) 0.0047(7) -0.0076(7) 0.0034(7) C19 0.0341(10) 0.0279(9) 0.0154(8) 0.0061(7) 0.0018(7) 0.0113(8) C20 0.0208(9) 0.0260(9) 0.0301(10) 0.0156(7) 0.0052(7) 0.0039(7) C21 0.0304(9) 0.0160(8) 0.0229(9) 0.0060(6) -0.0062(7) 0.0003(7) C22 0.088(2) 0.0543(14) 0.0163(10) 0.0024(9) 0.0036(11) 0.0372(14) C23 0.0249(11) 0.0521(14) 0.0745(17) 0.0371(13) 0.0151(11) 0.0014(10) C24 0.0649(15) 0.0162(9) 0.0472(13) 0.0018(8) -0.0261(11) -0.0004(9) C25 0.0417(12) 0.0342(11) 0.0452(13) 0.0115(9) 0.0241(10) 0.0157(10) C26 0.0410(13) 0.0354(12) 0.0577(15) 0.0098(10) -0.0291(11) -0.0050(10) C27 0.0729(18) 0.0454(14) 0.0419(14) -0.0059(11) 0.0172(12) 0.0011(13) Cl1 0.0366(2) 0.0282(2) 0.0183(2) -0.00470(16) 0.00036(17) 0.01147(19) Cl2 0.0217(2) 0.0284(2) 0.0311(2) 0.00754(18) -0.00226(17) -0.00896(17) Cl3 0.0198(2) 0.0190(2) 0.0311(2) 0.00053(16) -0.00061(16) 0.00179(16) O1 0.0400(9) 0.0256(8) 0.0418(9) -0.0050(6) 0.0170(7) -0.0046(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 Zr1 Cl1 2.4306(4) . ? Zr1 Cl2 2.4513(4) . ? Zr1 C4 2.4530(16) . ? Zr1 C3 2.4722(17) . ? Zr1 C20 2.4866(17) . ? Zr1 C17 2.5118(16) . ? Zr1 C21 2.5174(17) . ? Zr1 C19 2.5423(17) . ? Zr1 C5 2.5456(16) . ? Zr1 C18 2.5461(17) . ? Zr1 C2 2.5628(17) . ? Zr1 C1 2.6222(15) . ? N1 C10 1.284(2) . ? N1 H1N 0.83(2) . ? N1 H2N 0.85(2) . ? C1 C5 1.414(2) . ? C1 C2 1.414(2) . ? C1 C6 1.519(2) . ? C2 C3 1.401(2) . ? C2 H2 0.9500 . ? C3 C4 1.417(3) . ? C3 H3 0.9500 . ? C4 C5 1.408(2) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C7 1.530(2) . ? C6 C8 1.536(2) . ? C6 C9 1.568(2) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 C10 1.488(2) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C11 1.474(2) . ? C11 C12 1.395(2) . ? C11 C16 1.396(2) . ? C12 C13 1.382(3) . ? C12 H12 0.9500 . ? C13 C14 1.392(3) . ? C13 H13 0.9500 . ? C14 C15 1.381(3) . ? C14 H14 0.9500 . ? C15 C16 1.382(2) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 C21 1.412(2) . ? C17 C18 1.417(2) . ? C17 C25 1.501(2) . ? C18 C19 1.406(3) . ? C18 C26 1.505(3) . ? C19 C20 1.410(3) . ? C19 C22 1.506(3) . ? C20 C21 1.425(3) . ? C20 C23 1.502(3) . ? C21 C24 1.497(3) . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 H25A 0.9800 . ? C25 H25B 0.9800 . ? C25 H25C 0.9800 . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? C27 O1 1.400(3) . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? O1 H1O 0.76(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 Cl1 Zr1 Cl2 101.750(17) . . ? Cl1 Zr1 C4 132.88(4) . . ? Cl2 Zr1 C4 99.64(5) . . ? Cl1 Zr1 C3 106.59(5) . . ? Cl2 Zr1 C3 130.98(4) . . ? C4 Zr1 C3 33.45(6) . . ? Cl1 Zr1 C20 90.84(4) . . ? Cl2 Zr1 C20 133.16(4) . . ? C4 Zr1 C20 104.04(6) . . ? C3 Zr1 C20 85.81(6) . . ? Cl1 Zr1 C17 131.50(4) . . ? Cl2 Zr1 C17 85.49(4) . . ? C4 Zr1 C17 91.48(6) . . ? C3 Zr1 C17 103.48(6) . . ? C20 Zr1 C17 54.41(5) . . ? Cl1 Zr1 C21 123.93(4) . . ? Cl2 Zr1 C21 117.38(4) . . ? C4 Zr1 C21 79.99(6) . . ? C3 Zr1 C21 77.21(6) . . ? C20 Zr1 C21 33.09(6) . . ? C17 Zr1 C21 32.61(6) . . ? Cl1 Zr1 C19 78.51(4) . . ? Cl2 Zr1 C19 106.07(5) . . ? C4 Zr1 C19 133.59(6) . . ? C3 Zr1 C19 118.13(6) . . ? C20 Zr1 C19 32.55(6) . . ? C17 Zr1 C19 53.77(5) . . ? C21 Zr1 C19 53.98(6) . . ? Cl1 Zr1 C5 114.76(4) . . ? Cl2 Zr1 C5 78.03(4) . . ? C4 Zr1 C5 32.64(5) . . ? C3 Zr1 C5 54.00(6) . . ? C20 Zr1 C5 136.22(6) . . ? C17 Zr1 C5 113.66(5) . . ? C21 Zr1 C5 111.57(5) . . ? C19 Zr1 C5 165.43(6) . . ? Cl1 Zr1 C18 101.08(4) . . ? Cl2 Zr1 C18 79.37(4) . . ? C4 Zr1 C18 123.96(6) . . ? C3 Zr1 C18 131.04(6) . . ? C20 Zr1 C18 53.88(6) . . ? C17 Zr1 C18 32.53(6) . . ? C21 Zr1 C18 53.84(6) . . ? C19 Zr1 C18 32.09(6) . . ? C5 Zr1 C18 140.67(6) . . ? Cl1 Zr1 C2 79.31(4) . . ? Cl2 Zr1 C2 123.38(4) . . ? C4 Zr1 C2 53.95(6) . . ? C3 Zr1 C2 32.24(5) . . ? C20 Zr1 C2 103.16(6) . . ? C17 Zr1 C2 135.54(6) . . ? C21 Zr1 C2 106.58(6) . . ? C19 Zr1 C2 128.79(6) . . ? C5 Zr1 C2 52.77(5) . . ? C18 Zr1 C2 156.94(6) . . ? Cl1 Zr1 C1 84.15(4) . . ? Cl2 Zr1 C1 91.76(4) . . ? C4 Zr1 C1 53.63(5) . . ? C3 Zr1 C1 53.35(5) . . ? C20 Zr1 C1 134.65(6) . . ? C17 Zr1 C1 144.07(5) . . ? C21 Zr1 C1 129.44(5) . . ? C19 Zr1 C1 157.22(5) . . ? C5 Zr1 C1 31.71(5) . . ? C18 Zr1 C1 170.43(5) . . ? C2 Zr1 C1 31.62(5) . . ? C10 N1 H1N 118.3(16) . . ? C10 N1 H2N 120.7(15) . . ? H1N N1 H2N 121(2) . . ? C5 C1 C2 106.82(14) . . ? C5 C1 C6 125.50(14) . . ? C2 C1 C6 126.96(14) . . ? C5 C1 Zr1 71.16(9) . . ? C2 C1 Zr1 71.87(9) . . ? C6 C1 Zr1 129.59(10) . . ? C3 C2 C1 108.98(15) . . ? C3 C2 Zr1 70.32(9) . . ? C1 C2 Zr1 76.51(9) . . ? C3 C2 H2 125.5 . . ? C1 C2 H2 125.5 . . ? Zr1 C2 H2 119.4 . . ? C2 C3 C4 107.82(15) . . ? C2 C3 Zr1 77.44(10) . . ? C4 C3 Zr1 72.53(10) . . ? C2 C3 H3 126.1 . . ? C4 C3 H3 126.1 . . ? Zr1 C3 H3 116.1 . . ? C5 C4 C3 107.54(15) . . ? C5 C4 Zr1 77.30(9) . . ? C3 C4 Zr1 74.02(10) . . ? C5 C4 H4 126.2 . . ? C3 C4 H4 126.2 . . ? Zr1 C4 H4 114.8 . . ? C4 C5 C1 108.83(15) . . ? C4 C5 Zr1 70.06(9) . . ? C1 C5 Zr1 77.14(9) . . ? C4 C5 H5 125.6 . . ? C1 C5 H5 125.6 . . ? Zr1 C5 H5 119.0 . . ? C1 C6 C7 112.21(13) . . ? C1 C6 C8 111.97(13) . . ? C7 C6 C8 109.18(14) . . ? C1 C6 C9 108.51(13) . . ? C7 C6 C9 108.81(13) . . ? C8 C6 C9 105.91(13) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C10 C9 C6 114.33(13) . . ? C10 C9 H9A 108.7 . . ? C6 C9 H9A 108.7 . . ? C10 C9 H9B 108.7 . . ? C6 C9 H9B 108.7 . . ? H9A C9 H9B 107.6 . . ? N1 C10 C11 119.60(16) . . ? N1 C10 C9 118.09(16) . . ? C11 C10 C9 122.28(14) . . ? C12 C11 C16 119.72(16) . . ? C12 C11 C10 120.18(15) . . ? C16 C11 C10 120.09(15) . . ? C13 C12 C11 119.88(17) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C12 C13 C14 120.16(17) . . ? C12 C13 H13 119.9 . . ? C14 C13 H13 119.9 . . ? C15 C14 C13 119.96(17) . . ? C15 C14 H14 120.0 . . ? C13 C14 H14 120.0 . . ? C14 C15 C16 120.41(17) . . ? C14 C15 H15 119.8 . . ? C16 C15 H15 119.8 . . ? C15 C16 C11 119.85(16) . . ? C15 C16 H16 120.1 . . ? C11 C16 H16 120.1 . . ? C21 C17 C18 108.25(15) . . ? C21 C17 C25 126.12(18) . . ? C18 C17 C25 125.32(18) . . ? C21 C17 Zr1 73.91(10) . . ? C18 C17 Zr1 75.06(9) . . ? C25 C17 Zr1 122.11(12) . . ? C19 C18 C17 108.09(16) . . ? C19 C18 C26 125.40(18) . . ? C17 C18 C26 126.12(18) . . ? C19 C18 Zr1 73.81(10) . . ? C17 C18 Zr1 72.40(9) . . ? C26 C18 Zr1 125.18(12) . . ? C18 C19 C20 108.11(16) . . ? C18 C19 C22 125.2(2) . . ? C20 C19 C22 126.28(19) . . ? C18 C19 Zr1 74.10(10) . . ? C20 C19 Zr1 71.55(10) . . ? C22 C19 Zr1 125.56(13) . . ? C19 C20 C21 108.15(15) . . ? C19 C20 C23 124.70(19) . . ? C21 C20 C23 126.6(2) . . ? C19 C20 Zr1 75.90(10) . . ? C21 C20 Zr1 74.64(9) . . ? C23 C20 Zr1 122.43(13) . . ? C17 C21 C20 107.29(16) . . ? C17 C21 C24 126.43(18) . . ? C20 C21 C24 125.54(18) . . ? C17 C21 Zr1 73.48(9) . . ? C20 C21 Zr1 72.27(9) . . ? C24 C21 Zr1 127.41(12) . . ? C19 C22 H22A 109.5 . . ? C19 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C19 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C20 C23 H23A 109.5 . . ? C20 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C20 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C21 C24 H24A 109.5 . . ? C21 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C21 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C17 C25 H25A 109.5 . . ? C17 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C17 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? C18 C26 H26A 109.5 . . ? C18 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C18 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? O1 C27 H27A 109.5 . . ? O1 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? O1 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C27 O1 H1O 105.9(18) . . ? 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 Cl1 Zr1 C1 C5 -165.22(10) . . . . ? Cl2 Zr1 C1 C5 -63.59(9) . . . . ? C4 Zr1 C1 C5 37.10(10) . . . . ? C3 Zr1 C1 C5 79.06(11) . . . . ? C20 Zr1 C1 C5 109.39(11) . . . . ? C17 Zr1 C1 C5 21.17(14) . . . . ? C21 Zr1 C1 C5 64.81(12) . . . . ? C19 Zr1 C1 C5 154.35(14) . . . . ? C18 Zr1 C1 C5 -41.6(4) . . . . ? C2 Zr1 C1 C5 115.69(14) . . . . ? Cl1 Zr1 C1 C2 79.09(9) . . . . ? Cl2 Zr1 C1 C2 -179.28(9) . . . . ? C4 Zr1 C1 C2 -78.59(11) . . . . ? C3 Zr1 C1 C2 -36.63(10) . . . . ? C20 Zr1 C1 C2 -6.30(13) . . . . ? C17 Zr1 C1 C2 -94.52(12) . . . . ? C21 Zr1 C1 C2 -50.88(12) . . . . ? C19 Zr1 C1 C2 38.66(19) . . . . ? C5 Zr1 C1 C2 -115.69(14) . . . . ? C18 Zr1 C1 C2 -157.3(3) . . . . ? Cl1 Zr1 C1 C6 -44.29(13) . . . . ? Cl2 Zr1 C1 C6 57.34(13) . . . . ? C4 Zr1 C1 C6 158.03(16) . . . . ? C3 Zr1 C1 C6 -160.02(16) . . . . ? C20 Zr1 C1 C6 -129.68(13) . . . . ? C17 Zr1 C1 C6 142.09(12) . . . . ? C21 Zr1 C1 C6 -174.26(12) . . . . ? C19 Zr1 C1 C6 -84.7(2) . . . . ? C5 Zr1 C1 C6 120.93(18) . . . . ? C18 Zr1 C1 C6 79.3(4) . . . . ? C2 Zr1 C1 C6 -123.38(18) . . . . ? C5 C1 C2 C3 0.34(19) . . . . ? C6 C1 C2 C3 -170.31(15) . . . . ? Zr1 C1 C2 C3 63.34(12) . . . . ? C5 C1 C2 Zr1 -63.00(11) . . . . ? C6 C1 C2 Zr1 126.35(16) . . . . ? Cl1 Zr1 C2 C3 147.58(10) . . . . ? Cl2 Zr1 C2 C3 -115.31(10) . . . . ? C4 Zr1 C2 C3 -38.70(10) . . . . ? C20 Zr1 C2 C3 59.23(11) . . . . ? C17 Zr1 C2 C3 7.19(13) . . . . ? C21 Zr1 C2 C3 25.13(11) . . . . ? C19 Zr1 C2 C3 81.91(12) . . . . ? C5 Zr1 C2 C3 -79.67(11) . . . . ? C18 Zr1 C2 C3 54.39(19) . . . . ? C1 Zr1 C2 C3 -116.17(15) . . . . ? Cl1 Zr1 C2 C1 -96.25(9) . . . . ? Cl2 Zr1 C2 C1 0.86(11) . . . . ? C4 Zr1 C2 C1 77.48(10) . . . . ? C3 Zr1 C2 C1 116.17(15) . . . . ? C20 Zr1 C2 C1 175.40(10) . . . . ? C17 Zr1 C2 C1 123.36(10) . . . . ? C21 Zr1 C2 C1 141.31(9) . . . . ? C19 Zr1 C2 C1 -161.92(9) . . . . ? C5 Zr1 C2 C1 36.50(9) . . . . ? C18 Zr1 C2 C1 170.57(13) . . . . ? C1 C2 C3 C4 -0.59(19) . . . . ? Zr1 C2 C3 C4 66.76(12) . . . . ? C1 C2 C3 Zr1 -67.35(12) . . . . ? Cl1 Zr1 C3 C2 -33.35(10) . . . . ? Cl2 Zr1 C3 C2 89.36(11) . . . . ? C4 Zr1 C3 C2 113.50(14) . . . . ? C20 Zr1 C3 C2 -122.98(11) . . . . ? C17 Zr1 C3 C2 -174.83(10) . . . . ? C21 Zr1 C3 C2 -155.33(11) . . . . ? C19 Zr1 C3 C2 -118.96(10) . . . . ? C5 Zr1 C3 C2 75.54(10) . . . . ? C18 Zr1 C3 C2 -155.03(10) . . . . ? C1 Zr1 C3 C2 35.91(9) . . . . ? Cl1 Zr1 C3 C4 -146.85(9) . . . . ? Cl2 Zr1 C3 C4 -24.14(12) . . . . ? C20 Zr1 C3 C4 123.52(10) . . . . ? C17 Zr1 C3 C4 71.67(10) . . . . ? C21 Zr1 C3 C4 91.17(10) . . . . ? C19 Zr1 C3 C4 127.54(10) . . . . ? C5 Zr1 C3 C4 -37.96(9) . . . . ? C18 Zr1 C3 C4 91.47(11) . . . . ? C2 Zr1 C3 C4 -113.50(14) . . . . ? C1 Zr1 C3 C4 -77.59(10) . . . . ? C2 C3 C4 C5 0.62(19) . . . . ? Zr1 C3 C4 C5 70.71(12) . . . . ? C2 C3 C4 Zr1 -70.09(12) . . . . ? Cl1 Zr1 C4 C5 -67.04(12) . . . . ? Cl2 Zr1 C4 C5 49.05(10) . . . . ? C3 Zr1 C4 C5 -112.70(14) . . . . ? C20 Zr1 C4 C5 -171.69(10) . . . . ? C17 Zr1 C4 C5 134.73(10) . . . . ? C21 Zr1 C4 C5 165.39(11) . . . . ? C19 Zr1 C4 C5 172.39(10) . . . . ? C18 Zr1 C4 C5 132.66(10) . . . . ? C2 Zr1 C4 C5 -75.47(10) . . . . ? C1 Zr1 C4 C5 -36.00(9) . . . . ? Cl1 Zr1 C4 C3 45.67(12) . . . . ? Cl2 Zr1 C4 C3 161.75(9) . . . . ? C20 Zr1 C4 C3 -58.99(11) . . . . ? C17 Zr1 C4 C3 -112.57(10) . . . . ? C21 Zr1 C4 C3 -81.90(10) . . . . ? C19 Zr1 C4 C3 -74.91(12) . . . . ? C5 Zr1 C4 C3 112.70(14) . . . . ? C18 Zr1 C4 C3 -114.64(10) . . . . ? C2 Zr1 C4 C3 37.23(9) . . . . ? C1 Zr1 C4 C3 76.71(10) . . . . ? C3 C4 C5 C1 -0.41(19) . . . . ? Zr1 C4 C5 C1 68.04(12) . . . . ? C3 C4 C5 Zr1 -68.45(12) . . . . ? C2 C1 C5 C4 0.05(18) . . . . ? C6 C1 C5 C4 170.87(15) . . . . ? Zr1 C1 C5 C4 -63.42(11) . . . . ? C2 C1 C5 Zr1 63.47(11) . . . . ? C6 C1 C5 Zr1 -125.71(15) . . . . ? Cl1 Zr1 C5 C4 132.01(9) . . . . ? Cl2 Zr1 C5 C4 -130.43(10) . . . . ? C3 Zr1 C5 C4 38.94(10) . . . . ? C20 Zr1 C5 C4 11.69(14) . . . . ? C17 Zr1 C5 C4 -50.84(12) . . . . ? C21 Zr1 C5 C4 -15.49(12) . . . . ? C19 Zr1 C5 C4 -22.4(3) . . . . ? C18 Zr1 C5 C4 -74.25(13) . . . . ? C2 Zr1 C5 C4 79.39(11) . . . . ? C1 Zr1 C5 C4 115.79(15) . . . . ? Cl1 Zr1 C5 C1 16.23(10) . . . . ? Cl2 Zr1 C5 C1 113.78(9) . . . . ? C4 Zr1 C5 C1 -115.79(15) . . . . ? C3 Zr1 C5 C1 -76.84(10) . . . . ? C20 Zr1 C5 C1 -104.09(11) . . . . ? C17 Zr1 C5 C1 -166.62(9) . . . . ? C21 Zr1 C5 C1 -131.28(10) . . . . ? C19 Zr1 C5 C1 -138.2(2) . . . . ? C18 Zr1 C5 C1 169.96(9) . . . . ? C2 Zr1 C5 C1 -36.40(9) . . . . ? C5 C1 C6 C7 174.73(15) . . . . ? C2 C1 C6 C7 -16.3(2) . . . . ? Zr1 C1 C6 C7 80.43(17) . . . . ? C5 C1 C6 C8 51.5(2) . . . . ? C2 C1 C6 C8 -139.48(17) . . . . ? Zr1 C1 C6 C8 -42.76(19) . . . . ? C5 C1 C6 C9 -65.00(19) . . . . ? C2 C1 C6 C9 103.98(18) . . . . ? Zr1 C1 C6 C9 -159.30(10) . . . . ? C1 C6 C9 C10 -67.17(17) . . . . ? C7 C6 C9 C10 55.19(18) . . . . ? C8 C6 C9 C10 172.45(13) . . . . ? C6 C9 C10 N1 -101.02(18) . . . . ? C6 C9 C10 C11 77.03(19) . . . . ? N1 C10 C11 C12 34.2(2) . . . . ? C9 C10 C11 C12 -143.86(16) . . . . ? N1 C10 C11 C16 -147.08(17) . . . . ? C9 C10 C11 C16 34.9(2) . . . . ? C16 C11 C12 C13 -1.5(3) . . . . ? C10 C11 C12 C13 177.22(16) . . . . ? C11 C12 C13 C14 0.9(3) . . . . ? C12 C13 C14 C15 0.7(3) . . . . ? C13 C14 C15 C16 -1.6(3) . . . . ? C14 C15 C16 C11 1.0(3) . . . . ? C12 C11 C16 C15 0.6(2) . . . . ? C10 C11 C16 C15 -178.17(15) . . . . ? Cl1 Zr1 C17 C21 -90.01(11) . . . . ? Cl2 Zr1 C17 C21 168.28(10) . . . . ? C4 Zr1 C17 C21 68.72(11) . . . . ? C3 Zr1 C17 C21 37.16(11) . . . . ? C20 Zr1 C17 C21 -37.53(10) . . . . ? C19 Zr1 C17 C21 -78.02(11) . . . . ? C5 Zr1 C17 C21 93.45(11) . . . . ? C18 Zr1 C17 C21 -114.47(14) . . . . ? C2 Zr1 C17 C21 33.22(13) . . . . ? C1 Zr1 C17 C21 81.49(13) . . . . ? Cl1 Zr1 C17 C18 24.46(12) . . . . ? Cl2 Zr1 C17 C18 -77.25(10) . . . . ? C4 Zr1 C17 C18 -176.81(11) . . . . ? C3 Zr1 C17 C18 151.63(10) . . . . ? C20 Zr1 C17 C18 76.94(11) . . . . ? C21 Zr1 C17 C18 114.47(14) . . . . ? C19 Zr1 C17 C18 36.46(10) . . . . ? C5 Zr1 C17 C18 -152.08(10) . . . . ? C2 Zr1 C17 C18 147.70(10) . . . . ? C1 Zr1 C17 C18 -164.03(10) . . . . ? Cl1 Zr1 C17 C25 147.08(14) . . . . ? Cl2 Zr1 C17 C25 45.36(16) . . . . ? C4 Zr1 C17 C25 -54.20(17) . . . . ? C3 Zr1 C17 C25 -85.76(17) . . . . ? C20 Zr1 C17 C25 -160.45(19) . . . . ? C21 Zr1 C17 C25 -122.9(2) . . . . ? C19 Zr1 C17 C25 159.07(19) . . . . ? C5 Zr1 C17 C25 -29.46(18) . . . . ? C18 Zr1 C17 C25 122.6(2) . . . . ? C2 Zr1 C17 C25 -89.69(17) . . . . ? C1 Zr1 C17 C25 -41.4(2) . . . . ? C21 C17 C18 C19 1.34(19) . . . . ? C25 C17 C18 C19 175.26(17) . . . . ? Zr1 C17 C18 C19 -65.71(12) . . . . ? C21 C17 C18 C26 -171.83(17) . . . . ? C25 C17 C18 C26 2.1(3) . . . . ? Zr1 C17 C18 C26 121.12(18) . . . . ? C21 C17 C18 Zr1 67.05(12) . . . . ? C25 C17 C18 Zr1 -119.03(17) . . . . ? Cl1 Zr1 C18 C19 -46.03(11) . . . . ? Cl2 Zr1 C18 C19 -146.07(11) . . . . ? C4 Zr1 C18 C19 119.40(11) . . . . ? C3 Zr1 C18 C19 77.77(13) . . . . ? C20 Zr1 C18 C19 36.84(11) . . . . ? C17 Zr1 C18 C19 115.55(15) . . . . ? C21 Zr1 C18 C19 78.13(12) . . . . ? C5 Zr1 C18 C19 158.15(11) . . . . ? C2 Zr1 C18 C19 42.7(2) . . . . ? C1 Zr1 C18 C19 -168.4(3) . . . . ? Cl1 Zr1 C18 C17 -161.58(9) . . . . ? Cl2 Zr1 C18 C17 98.38(10) . . . . ? C4 Zr1 C18 C17 3.85(13) . . . . ? C3 Zr1 C18 C17 -37.78(13) . . . . ? C20 Zr1 C18 C17 -78.72(11) . . . . ? C21 Zr1 C18 C17 -37.42(10) . . . . ? C19 Zr1 C18 C17 -115.55(15) . . . . ? C5 Zr1 C18 C17 42.59(14) . . . . ? C2 Zr1 C18 C17 -72.88(18) . . . . ? C1 Zr1 C18 C17 76.0(3) . . . . ? Cl1 Zr1 C18 C26 76.21(18) . . . . ? Cl2 Zr1 C18 C26 -23.83(17) . . . . ? C4 Zr1 C18 C26 -118.37(17) . . . . ? C3 Zr1 C18 C26 -160.00(16) . . . . ? C20 Zr1 C18 C26 159.1(2) . . . . ? C17 Zr1 C18 C26 -122.2(2) . . . . ? C21 Zr1 C18 C26 -159.6(2) . . . . ? C19 Zr1 C18 C26 122.2(2) . . . . ? C5 Zr1 C18 C26 -79.6(2) . . . . ? C2 Zr1 C18 C26 164.90(17) . . . . ? C1 Zr1 C18 C26 -46.2(4) . . . . ? C17 C18 C19 C20 0.85(19) . . . . ? C26 C18 C19 C20 174.08(17) . . . . ? Zr1 C18 C19 C20 -63.94(12) . . . . ? C17 C18 C19 C22 -172.59(17) . . . . ? C26 C18 C19 C22 0.6(3) . . . . ? Zr1 C18 C19 C22 122.63(18) . . . . ? C17 C18 C19 Zr1 64.78(12) . . . . ? C26 C18 C19 Zr1 -121.98(18) . . . . ? Cl1 Zr1 C19 C18 133.89(11) . . . . ? Cl2 Zr1 C19 C18 34.82(11) . . . . ? C4 Zr1 C19 C18 -86.19(13) . . . . ? C3 Zr1 C19 C18 -123.30(11) . . . . ? C20 Zr1 C19 C18 -115.84(15) . . . . ? C17 Zr1 C19 C18 -36.98(10) . . . . ? C21 Zr1 C19 C18 -77.66(11) . . . . ? C5 Zr1 C19 C18 -69.7(3) . . . . ? C2 Zr1 C19 C18 -160.09(10) . . . . ? C1 Zr1 C19 C18 175.06(12) . . . . ? Cl1 Zr1 C19 C20 -110.28(10) . . . . ? Cl2 Zr1 C19 C20 150.65(9) . . . . ? C4 Zr1 C19 C20 29.65(14) . . . . ? C3 Zr1 C19 C20 -7.47(12) . . . . ? C17 Zr1 C19 C20 78.86(11) . . . . ? C21 Zr1 C19 C20 38.18(10) . . . . ? C5 Zr1 C19 C20 46.2(3) . . . . ? C18 Zr1 C19 C20 115.84(15) . . . . ? C2 Zr1 C19 C20 -44.25(13) . . . . ? C1 Zr1 C19 C20 -69.10(18) . . . . ? Cl1 Zr1 C19 C22 11.61(19) . . . . ? Cl2 Zr1 C19 C22 -87.5(2) . . . . ? C4 Zr1 C19 C22 151.54(19) . . . . ? C3 Zr1 C19 C22 114.4(2) . . . . ? C20 Zr1 C19 C22 121.9(2) . . . . ? C17 Zr1 C19 C22 -159.2(2) . . . . ? C21 Zr1 C19 C22 160.1(2) . . . . ? C5 Zr1 C19 C22 168.0(2) . . . . ? C18 Zr1 C19 C22 -122.3(2) . . . . ? C2 Zr1 C19 C22 77.6(2) . . . . ? C1 Zr1 C19 C22 52.8(3) . . . . ? C18 C19 C20 C21 -2.69(19) . . . . ? C22 C19 C20 C21 170.66(17) . . . . ? Zr1 C19 C20 C21 -68.30(12) . . . . ? C18 C19 C20 C23 -174.49(17) . . . . ? C22 C19 C20 C23 -1.1(3) . . . . ? Zr1 C19 C20 C23 119.90(18) . . . . ? C18 C19 C20 Zr1 65.61(12) . . . . ? C22 C19 C20 Zr1 -121.04(18) . . . . ? Cl1 Zr1 C20 C19 66.83(10) . . . . ? Cl2 Zr1 C20 C19 -40.21(13) . . . . ? C4 Zr1 C20 C19 -158.33(10) . . . . ? C3 Zr1 C20 C19 173.40(11) . . . . ? C17 Zr1 C20 C19 -76.73(11) . . . . ? C21 Zr1 C20 C19 -113.70(15) . . . . ? C5 Zr1 C20 C19 -164.80(10) . . . . ? C18 Zr1 C20 C19 -36.30(10) . . . . ? C2 Zr1 C20 C19 146.04(10) . . . . ? C1 Zr1 C20 C19 149.43(10) . . . . ? Cl1 Zr1 C20 C21 -179.47(10) . . . . ? Cl2 Zr1 C20 C21 73.49(12) . . . . ? C4 Zr1 C20 C21 -44.62(12) . . . . ? C3 Zr1 C20 C21 -72.89(11) . . . . ? C17 Zr1 C20 C21 36.97(10) . . . . ? C19 Zr1 C20 C21 113.70(15) . . . . ? C5 Zr1 C20 C21 -51.09(14) . . . . ? C18 Zr1 C20 C21 77.40(11) . . . . ? C2 Zr1 C20 C21 -100.25(11) . . . . ? C1 Zr1 C20 C21 -96.87(11) . . . . ? Cl1 Zr1 C20 C23 -55.58(18) . . . . ? Cl2 Zr1 C20 C23 -162.62(16) . . . . ? C4 Zr1 C20 C23 79.27(19) . . . . ? C3 Zr1 C20 C23 51.00(19) . . . . ? C17 Zr1 C20 C23 160.9(2) . . . . ? C21 Zr1 C20 C23 123.9(2) . . . . ? C19 Zr1 C20 C23 -122.4(2) . . . . ? C5 Zr1 C20 C23 72.8(2) . . . . ? C18 Zr1 C20 C23 -158.7(2) . . . . ? C2 Zr1 C20 C23 23.64(19) . . . . ? C1 Zr1 C20 C23 27.0(2) . . . . ? C18 C17 C21 C20 -2.97(19) . . . . ? C25 C17 C21 C20 -176.83(17) . . . . ? Zr1 C17 C21 C20 64.85(12) . . . . ? C18 C17 C21 C24 167.53(17) . . . . ? C25 C17 C21 C24 -6.3(3) . . . . ? Zr1 C17 C21 C24 -124.65(18) . . . . ? C18 C17 C21 Zr1 -67.82(12) . . . . ? C25 C17 C21 Zr1 118.32(18) . . . . ? C19 C20 C21 C17 3.50(19) . . . . ? C23 C20 C21 C17 175.09(17) . . . . ? Zr1 C20 C21 C17 -65.65(12) . . . . ? C19 C20 C21 C24 -167.11(17) . . . . ? C23 C20 C21 C24 4.5(3) . . . . ? Zr1 C20 C21 C24 123.74(17) . . . . ? C19 C20 C21 Zr1 69.15(12) . . . . ? C23 C20 C21 Zr1 -119.25(19) . . . . ? Cl1 Zr1 C21 C17 115.49(9) . . . . ? Cl2 Zr1 C21 C17 -13.19(11) . . . . ? C4 Zr1 C21 C17 -108.94(11) . . . . ? C3 Zr1 C21 C17 -142.96(11) . . . . ? C20 Zr1 C21 C17 114.85(15) . . . . ? C19 Zr1 C21 C17 77.32(11) . . . . ? C5 Zr1 C21 C17 -100.52(10) . . . . ? C18 Zr1 C21 C17 37.32(10) . . . . ? C2 Zr1 C21 C17 -156.40(10) . . . . ? C1 Zr1 C21 C17 -131.28(10) . . . . ? Cl1 Zr1 C21 C20 0.64(12) . . . . ? Cl2 Zr1 C21 C20 -128.04(10) . . . . ? C4 Zr1 C21 C20 136.21(12) . . . . ? C3 Zr1 C21 C20 102.19(11) . . . . ? C17 Zr1 C21 C20 -114.85(15) . . . . ? C19 Zr1 C21 C20 -37.53(11) . . . . ? C5 Zr1 C21 C20 144.62(11) . . . . ? C18 Zr1 C21 C20 -77.53(12) . . . . ? C2 Zr1 C21 C20 88.75(11) . . . . ? C1 Zr1 C21 C20 113.87(11) . . . . ? Cl1 Zr1 C21 C24 -120.94(17) . . . . ? Cl2 Zr1 C21 C24 110.38(17) . . . . ? C4 Zr1 C21 C24 14.63(18) . . . . ? C3 Zr1 C21 C24 -19.39(18) . . . . ? C20 Zr1 C21 C24 -121.6(2) . . . . ? C17 Zr1 C21 C24 123.6(2) . . . . ? C19 Zr1 C21 C24 -159.1(2) . . . . ? C5 Zr1 C21 C24 23.05(19) . . . . ? C18 Zr1 C21 C24 160.9(2) . . . . ? C2 Zr1 C21 C24 -32.83(19) . . . . ? C1 Zr1 C21 C24 -7.7(2) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1N Cl3 0.83(2) 2.36(2) 3.1805(17) 172(2) 3_756 N1 H2N Cl3 0.85(2) 2.30(2) 3.1164(17) 162(2) 1_656 O1 H1O Cl3 0.76(2) 2.43(2) 3.1867(16) 175(2) . _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.362 _refine_diff_density_min -0.270 _refine_diff_density_rms 0.057 #===END data_ml39_lamac _database_code_depnum_ccdc_archive 'CCDC 864586' #TrackingRef 'ml39_lamac.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C20 H27 Cl2 N Ti' _chemical_formula_sum 'C20 H27 Cl2 N Ti' _chemical_formula_weight 400.23 _chemical_compound_source 'synthesized by the authors' 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.1970(2) _cell_length_b 11.4753(3) _cell_length_c 21.1072(6) _cell_angle_alpha 90.00 _cell_angle_beta 98.6580(10) _cell_angle_gamma 90.00 _cell_volume 1962.78(9) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 9956 _cell_measurement_theta_min 2.64 _cell_measurement_theta_max 27.51 _exptl_crystal_description plate _exptl_crystal_colour res _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.354 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 840 _exptl_absorpt_coefficient_mu 0.710 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.6555 _exptl_absorpt_correction_T_max 0.9222 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 26027 _diffrn_reflns_av_R_equivalents 0.0247 _diffrn_reflns_av_sigmaI/netI 0.0185 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.95 _diffrn_reflns_theta_max 27.50 _reflns_number_total 4511 _reflns_number_gt 3941 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0299P)^2^+0.9853P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4511 _refine_ls_number_parameters 224 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0333 _refine_ls_R_factor_gt 0.0267 _refine_ls_wR_factor_ref 0.0679 _refine_ls_wR_factor_gt 0.0647 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _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 Ti1 Ti 0.20570(3) 0.32759(2) 0.172783(11) 0.01481(7) Uani 1 1 d . . . C1 C 0.28567(17) 0.27858(12) 0.28975(6) 0.0178(3) Uani 1 1 d . . . C2 C 0.28369(18) 0.17618(12) 0.25289(7) 0.0202(3) Uani 1 1 d . . . H2 H 0.3758 0.1269 0.2508 0.024 Uiso 1 1 calc R . . C3 C 0.12309(19) 0.15855(12) 0.21960(7) 0.0241(3) Uani 1 1 d . . . H3 H 0.0888 0.0967 0.1907 0.029 Uiso 1 1 calc R . . C4 C 0.02265(18) 0.24948(13) 0.23702(7) 0.0248(3) Uani 1 1 d . . . H4 H -0.0923 0.2584 0.2230 0.030 Uiso 1 1 calc R . . C5 C 0.12233(17) 0.32420(13) 0.27868(7) 0.0219(3) Uani 1 1 d . . . H5 H 0.0868 0.3940 0.2966 0.026 Uiso 1 1 calc R . . C6 C 0.42847(17) 0.32012(11) 0.33920(6) 0.0189(3) Uani 1 1 d . . . C7 C 0.4571(2) 0.22537(13) 0.39141(7) 0.0255(3) Uani 1 1 d . . . H7A H 0.3559 0.2142 0.4101 0.038 Uiso 1 1 calc R . . H7B H 0.5466 0.2496 0.4249 0.038 Uiso 1 1 calc R . . H7C H 0.4871 0.1520 0.3724 0.038 Uiso 1 1 calc R . . C8 C 0.3895(2) 0.43516(13) 0.37051(7) 0.0270(3) Uani 1 1 d . . . H8A H 0.3712 0.4963 0.3378 0.041 Uiso 1 1 calc R . . H8B H 0.4824 0.4570 0.4032 0.041 Uiso 1 1 calc R . . H8C H 0.2899 0.4258 0.3906 0.041 Uiso 1 1 calc R . . C9 C 0.58612(17) 0.33200(12) 0.30725(7) 0.0208(3) Uani 1 1 d . . . H9A H 0.6110 0.2556 0.2891 0.025 Uiso 1 1 calc R . . H9B H 0.5643 0.3881 0.2713 0.025 Uiso 1 1 calc R . . C10 C 0.73115(19) 0.37122(13) 0.35152(7) 0.0241(3) Uani 1 1 d . . . C11 C 0.17478(17) 0.39657(12) 0.06362(6) 0.0194(3) Uani 1 1 d . . . C12 C 0.11497(17) 0.27943(12) 0.06213(6) 0.0186(3) Uani 1 1 d . . . C13 C -0.02561(17) 0.27721(12) 0.09343(7) 0.0190(3) Uani 1 1 d . . . C14 C -0.05210(17) 0.39265(12) 0.11538(7) 0.0200(3) Uani 1 1 d . . . C15 C 0.06826(17) 0.46606(12) 0.09453(7) 0.0198(3) Uani 1 1 d . . . C16 C 0.31672(19) 0.44164(14) 0.03363(7) 0.0268(3) Uani 1 1 d . . . H16A H 0.2747 0.4831 -0.0061 0.040 Uiso 1 1 calc R . . H16B H 0.3858 0.3762 0.0240 0.040 Uiso 1 1 calc R . . H16C H 0.3826 0.4951 0.0634 0.040 Uiso 1 1 calc R . . C17 C 0.17629(19) 0.17853(13) 0.02715(7) 0.0253(3) Uani 1 1 d . . . H17A H 0.1692 0.1069 0.0519 0.038 Uiso 1 1 calc R . . H17B H 0.2914 0.1923 0.0217 0.038 Uiso 1 1 calc R . . H17C H 0.1084 0.1705 -0.0150 0.038 Uiso 1 1 calc R . . C18 C -0.14240(18) 0.17622(13) 0.09214(8) 0.0266(3) Uani 1 1 d . . . H18A H -0.2256 0.1811 0.0537 0.040 Uiso 1 1 calc R . . H18B H -0.1969 0.1785 0.1304 0.040 Uiso 1 1 calc R . . H18C H -0.0809 0.1031 0.0915 0.040 Uiso 1 1 calc R . . C19 C -0.19572(18) 0.43590(14) 0.14533(8) 0.0287(3) Uani 1 1 d . . . H19A H -0.1549 0.4768 0.1853 0.043 Uiso 1 1 calc R . . H19B H -0.2640 0.3697 0.1544 0.043 Uiso 1 1 calc R . . H19C H -0.2620 0.4895 0.1158 0.043 Uiso 1 1 calc R . . C20 C 0.0683(2) 0.59638(12) 0.09777(8) 0.0280(3) Uani 1 1 d . . . H20A H 0.1803 0.6255 0.0967 0.042 Uiso 1 1 calc R . . H20B H 0.0312 0.6214 0.1377 0.042 Uiso 1 1 calc R . . H20C H -0.0064 0.6276 0.0611 0.042 Uiso 1 1 calc R . . Cl1 Cl 0.45212(4) 0.25061(4) 0.146118(18) 0.02880(9) Uani 1 1 d . . . Cl2 Cl 0.31840(5) 0.50837(3) 0.209281(17) 0.02902(10) Uani 1 1 d . . . N1 N 0.84536(17) 0.40294(13) 0.38460(7) 0.0350(3) Uani 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 Ti1 0.01368(12) 0.01362(12) 0.01759(12) 0.00259(9) 0.00382(9) -0.00205(8) C1 0.0218(7) 0.0164(6) 0.0169(6) 0.0054(5) 0.0079(5) 0.0009(5) C2 0.0247(7) 0.0140(6) 0.0225(7) 0.0057(5) 0.0052(6) 0.0005(5) C3 0.0279(8) 0.0187(7) 0.0258(7) 0.0065(6) 0.0045(6) -0.0071(6) C4 0.0192(7) 0.0300(8) 0.0268(8) 0.0104(6) 0.0088(6) -0.0041(6) C5 0.0213(7) 0.0245(7) 0.0224(7) 0.0056(6) 0.0114(6) 0.0029(6) C6 0.0236(7) 0.0161(6) 0.0177(6) 0.0011(5) 0.0056(5) 0.0035(5) C7 0.0324(8) 0.0244(7) 0.0200(7) 0.0055(6) 0.0042(6) 0.0025(6) C8 0.0338(8) 0.0228(7) 0.0246(7) -0.0044(6) 0.0049(6) 0.0066(6) C9 0.0222(7) 0.0195(7) 0.0207(7) 0.0007(5) 0.0036(5) -0.0003(5) C10 0.0267(8) 0.0185(7) 0.0275(8) 0.0009(6) 0.0051(6) 0.0031(6) C11 0.0227(7) 0.0197(7) 0.0147(6) 0.0019(5) -0.0005(5) -0.0051(5) C12 0.0192(7) 0.0181(6) 0.0180(6) 0.0000(5) 0.0011(5) -0.0037(5) C13 0.0170(7) 0.0180(6) 0.0211(7) -0.0001(5) 0.0002(5) -0.0023(5) C14 0.0178(7) 0.0187(7) 0.0222(7) 0.0002(5) -0.0009(5) 0.0006(5) C15 0.0227(7) 0.0160(6) 0.0183(6) 0.0019(5) -0.0042(5) -0.0018(5) C16 0.0316(8) 0.0289(8) 0.0206(7) 0.0021(6) 0.0058(6) -0.0116(6) C17 0.0283(8) 0.0222(7) 0.0262(8) -0.0048(6) 0.0068(6) -0.0020(6) C18 0.0208(7) 0.0230(7) 0.0358(8) -0.0024(6) 0.0040(6) -0.0081(6) C19 0.0220(7) 0.0271(8) 0.0367(9) -0.0029(6) 0.0036(6) 0.0056(6) C20 0.0355(9) 0.0160(7) 0.0289(8) 0.0022(6) -0.0072(7) -0.0012(6) Cl1 0.01692(17) 0.0429(2) 0.02806(19) 0.00405(16) 0.00828(14) 0.00478(15) Cl2 0.0385(2) 0.01868(17) 0.02557(18) 0.00671(13) -0.00934(15) -0.01190(15) N1 0.0300(7) 0.0322(8) 0.0406(8) -0.0059(6) -0.0018(6) -0.0001(6) _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 Ti1 C3 2.3237(14) . ? Ti1 C4 2.3465(14) . ? Ti1 Cl1 2.3493(4) . ? Ti1 Cl2 2.3529(4) . ? Ti1 C14 2.3917(14) . ? Ti1 C13 2.4039(13) . ? Ti1 C12 2.4064(13) . ? Ti1 C11 2.4133(13) . ? Ti1 C5 2.4340(14) . ? Ti1 C2 2.4416(13) . ? Ti1 C15 2.4417(13) . ? Ti1 C1 2.5208(13) . ? C1 C2 1.4081(19) . ? C1 C5 1.4237(19) . ? C1 C6 1.523(2) . ? C2 C3 1.410(2) . ? C2 H2 0.9500 . ? C3 C4 1.412(2) . ? C3 H3 0.9500 . ? C4 C5 1.400(2) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C8 1.5314(19) . ? C6 C7 1.5407(19) . ? C6 C9 1.551(2) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 C10 1.468(2) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 N1 1.140(2) . ? C11 C15 1.413(2) . ? C11 C12 1.4295(19) . ? C11 C16 1.498(2) . ? C12 C13 1.412(2) . ? C12 C17 1.500(2) . ? C13 C14 1.4307(19) . ? C13 C18 1.5009(19) . ? C14 C15 1.417(2) . ? C14 C19 1.502(2) . ? C15 C20 1.4970(19) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C19 H19C 0.9800 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? 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 C3 Ti1 C4 35.19(5) . . ? C3 Ti1 Cl1 95.98(4) . . ? C4 Ti1 Cl1 129.98(4) . . ? C3 Ti1 Cl2 136.22(4) . . ? C4 Ti1 Cl2 113.66(4) . . ? Cl1 Ti1 Cl2 95.774(17) . . ? C3 Ti1 C14 100.62(5) . . ? C4 Ti1 C14 79.57(5) . . ? Cl1 Ti1 C14 136.22(4) . . ? Cl2 Ti1 C14 99.44(4) . . ? C3 Ti1 C13 81.13(5) . . ? C4 Ti1 C13 78.75(5) . . ? Cl1 Ti1 C13 111.04(4) . . ? Cl2 Ti1 C13 132.05(4) . . ? C14 Ti1 C13 34.71(5) . . ? C3 Ti1 C12 98.85(5) . . ? C4 Ti1 C12 110.00(5) . . ? Cl1 Ti1 C12 80.35(4) . . ? Cl2 Ti1 C12 124.68(3) . . ? C14 Ti1 C12 57.29(5) . . ? C13 Ti1 C12 34.15(5) . . ? C3 Ti1 C11 133.19(5) . . ? C4 Ti1 C11 133.84(5) . . ? Cl1 Ti1 C11 82.25(4) . . ? Cl2 Ti1 C11 90.17(3) . . ? C14 Ti1 C11 57.05(5) . . ? C13 Ti1 C11 56.99(5) . . ? C12 Ti1 C11 34.51(4) . . ? C3 Ti1 C5 57.05(5) . . ? C4 Ti1 C5 33.99(5) . . ? Cl1 Ti1 C5 125.76(4) . . ? Cl2 Ti1 C5 82.19(4) . . ? C14 Ti1 C5 96.97(5) . . ? C13 Ti1 C5 109.57(5) . . ? C12 Ti1 C5 143.05(5) . . ? C11 Ti1 C5 151.44(5) . . ? C3 Ti1 C2 34.32(5) . . ? C4 Ti1 C2 56.74(5) . . ? Cl1 Ti1 C2 75.72(4) . . ? Cl2 Ti1 C2 110.59(4) . . ? C14 Ti1 C2 133.81(5) . . ? C13 Ti1 C2 114.10(5) . . ? C12 Ti1 C2 121.28(5) . . ? C11 Ti1 C2 150.87(5) . . ? C5 Ti1 C2 55.47(5) . . ? C3 Ti1 C15 134.16(5) . . ? C4 Ti1 C15 111.68(5) . . ? Cl1 Ti1 C15 114.11(4) . . ? Cl2 Ti1 C15 76.48(3) . . ? C14 Ti1 C15 34.07(5) . . ? C13 Ti1 C15 56.63(5) . . ? C12 Ti1 C15 56.58(5) . . ? C11 Ti1 C15 33.82(5) . . ? C5 Ti1 C15 117.83(5) . . ? C2 Ti1 C15 167.86(5) . . ? C3 Ti1 C1 56.41(5) . . ? C4 Ti1 C1 56.18(5) . . ? Cl1 Ti1 C1 92.56(3) . . ? Cl2 Ti1 C1 81.06(3) . . ? C14 Ti1 C1 130.20(5) . . ? C13 Ti1 C1 133.66(5) . . ? C12 Ti1 C1 153.66(5) . . ? C11 Ti1 C1 169.34(5) . . ? C5 Ti1 C1 33.34(4) . . ? C2 Ti1 C1 32.92(4) . . ? C15 Ti1 C1 146.43(5) . . ? C2 C1 C5 106.49(13) . . ? C2 C1 C6 125.70(12) . . ? C5 C1 C6 127.18(12) . . ? C2 C1 Ti1 70.45(8) . . ? C5 C1 Ti1 69.99(8) . . ? C6 C1 Ti1 131.39(9) . . ? C1 C2 C3 109.10(13) . . ? C1 C2 Ti1 76.63(8) . . ? C3 C2 Ti1 68.26(8) . . ? C1 C2 H2 125.5 . . ? C3 C2 H2 125.5 . . ? Ti1 C2 H2 121.2 . . ? C2 C3 C4 107.54(13) . . ? C2 C3 Ti1 77.42(8) . . ? C4 C3 Ti1 73.29(8) . . ? C2 C3 H3 126.2 . . ? C4 C3 H3 126.2 . . ? Ti1 C3 H3 115.3 . . ? C5 C4 C3 107.95(13) . . ? C5 C4 Ti1 76.43(8) . . ? C3 C4 Ti1 71.52(8) . . ? C5 C4 H4 126.0 . . ? C3 C4 H4 126.0 . . ? Ti1 C4 H4 118.0 . . ? C4 C5 C1 108.87(13) . . ? C4 C5 Ti1 69.58(8) . . ? C1 C5 Ti1 76.68(8) . . ? C4 C5 H5 125.6 . . ? C1 C5 H5 125.6 . . ? Ti1 C5 H5 119.9 . . ? C1 C6 C8 112.13(12) . . ? C1 C6 C7 106.74(11) . . ? C8 C6 C7 108.60(12) . . ? C1 C6 C9 109.53(11) . . ? C8 C6 C9 110.71(12) . . ? C7 C6 C9 109.00(11) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C10 C9 C6 113.46(12) . . ? C10 C9 H9A 108.9 . . ? C6 C9 H9A 108.9 . . ? C10 C9 H9B 108.9 . . ? C6 C9 H9B 108.9 . . ? H9A C9 H9B 107.7 . . ? N1 C10 C9 178.24(17) . . ? C15 C11 C12 107.90(12) . . ? C15 C11 C16 125.01(13) . . ? C12 C11 C16 126.94(13) . . ? C15 C11 Ti1 74.19(8) . . ? C12 C11 Ti1 72.48(7) . . ? C16 C11 Ti1 122.69(9) . . ? C13 C12 C11 107.93(12) . . ? C13 C12 C17 125.02(12) . . ? C11 C12 C17 126.69(13) . . ? C13 C12 Ti1 72.83(8) . . ? C11 C12 Ti1 73.01(7) . . ? C17 C12 Ti1 125.27(10) . . ? C12 C13 C14 108.01(12) . . ? C12 C13 C18 124.65(13) . . ? C14 C13 C18 126.40(13) . . ? C12 C13 Ti1 73.03(8) . . ? C14 C13 Ti1 72.18(8) . . ? C18 C13 Ti1 129.23(10) . . ? C15 C14 C13 107.65(12) . . ? C15 C14 C19 124.11(13) . . ? C13 C14 C19 127.52(13) . . ? C15 C14 Ti1 74.90(8) . . ? C13 C14 Ti1 73.11(8) . . ? C19 C14 Ti1 125.35(10) . . ? C11 C15 C14 108.39(12) . . ? C11 C15 C20 126.09(14) . . ? C14 C15 C20 125.12(14) . . ? C11 C15 Ti1 71.98(8) . . ? C14 C15 Ti1 71.03(8) . . ? C20 C15 Ti1 128.48(9) . . ? C11 C16 H16A 109.5 . . ? C11 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C11 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C12 C17 H17A 109.5 . . ? C12 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C12 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C13 C18 H18A 109.5 . . ? C13 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C13 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C14 C19 H19A 109.5 . . ? C14 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C14 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? C15 C20 H20A 109.5 . . ? C15 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C15 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.337 _refine_diff_density_min -0.205 _refine_diff_density_rms 0.046 #===END data_ml_51_lamac _database_code_depnum_ccdc_archive 'CCDC 920405' #TrackingRef 'ml_51_lamac.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C32 H37 N Ti' _chemical_formula_sum 'C32 H37 N Ti' _chemical_formula_weight 483.53 _chemical_compound_source 'synthesized by the authors' 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' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.7350(3) _cell_length_b 10.8552(3) _cell_length_c 17.3126(4) _cell_angle_alpha 90.00 _cell_angle_beta 97.8400(10) _cell_angle_gamma 90.00 _cell_volume 2557.11(11) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 8260 _cell_measurement_theta_min 2.59 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.43 _exptl_crystal_size_min 0.42 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.256 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1032 _exptl_absorpt_coefficient_mu 0.355 _exptl_absorpt_correction_type multiscans _exptl_absorpt_correction_T_min 0.8559 _exptl_absorpt_correction_T_max 0.8663 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16840 _diffrn_reflns_av_R_equivalents 0.0185 _diffrn_reflns_av_sigmaI/netI 0.0221 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 27.50 _reflns_number_total 5865 _reflns_number_gt 5064 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ? _computing_publication_material ? _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^+1.2154P] 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_number_reflns 5865 _refine_ls_number_parameters 314 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0386 _refine_ls_R_factor_gt 0.0304 _refine_ls_wR_factor_ref 0.0822 _refine_ls_wR_factor_gt 0.0776 _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_restrained_S_all 1.025 _refine_ls_shift/su_max 0.002 _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 Ti1 Ti 0.284984(15) 0.33497(2) 0.816675(12) 0.01324(7) Uani 1 1 d . . . N1 N 0.14756(7) 0.34901(10) 0.82612(6) 0.0152(2) Uani 1 1 d . . . C1 C 0.20354(9) 0.33126(12) 0.68205(7) 0.0176(3) Uani 1 1 d . . . C2 C 0.24192(10) 0.21284(13) 0.70034(7) 0.0217(3) Uani 1 1 d . . . H2 H 0.2045 0.1397 0.7030 0.026 Uiso 1 1 calc R . . C3 C 0.34564(11) 0.22145(15) 0.71409(8) 0.0277(3) Uani 1 1 d . . . H3 H 0.3899 0.1548 0.7266 0.033 Uiso 1 1 calc R . . C4 C 0.37179(10) 0.34440(15) 0.70618(8) 0.0281(3) Uani 1 1 d . . . H4 H 0.4368 0.3761 0.7118 0.034 Uiso 1 1 calc R . . C5 C 0.28416(10) 0.41376(14) 0.68827(7) 0.0218(3) Uani 1 1 d . . . H5 H 0.2802 0.5006 0.6816 0.026 Uiso 1 1 calc R . . C6 C 0.09727(10) 0.36602(12) 0.65669(7) 0.0197(3) Uani 1 1 d . . . C7 C 0.03172(11) 0.25175(14) 0.64733(8) 0.0272(3) Uani 1 1 d . . . H7A H 0.0525 0.1981 0.6071 0.041 Uiso 1 1 calc R . . H7B H -0.0367 0.2768 0.6320 0.041 Uiso 1 1 calc R . . H7C H 0.0374 0.2071 0.6969 0.041 Uiso 1 1 calc R . . C8 C 0.08960(12) 0.43280(16) 0.57800(8) 0.0310(3) Uani 1 1 d . . . H8A H 0.1300 0.5075 0.5836 0.047 Uiso 1 1 calc R . . H8B H 0.0209 0.4552 0.5608 0.047 Uiso 1 1 calc R . . H8C H 0.1130 0.3784 0.5393 0.047 Uiso 1 1 calc R . . C9 C 0.06123(9) 0.45562(13) 0.71687(8) 0.0203(3) Uani 1 1 d . . . H9A H 0.1042 0.5291 0.7236 0.024 Uiso 1 1 calc R . . H9B H -0.0067 0.4830 0.6984 0.024 Uiso 1 1 calc R . . C10 C 0.06457(9) 0.38741(12) 0.79358(7) 0.0163(2) Uani 1 1 d . . . C11 C -0.02885(9) 0.35665(12) 0.82523(8) 0.0178(3) Uani 1 1 d . . . C12 C -0.02358(10) 0.29972(13) 0.89808(8) 0.0233(3) Uani 1 1 d . . . H12 H 0.0389 0.2807 0.9263 0.028 Uiso 1 1 calc R . . C13 C -0.10783(11) 0.27058(15) 0.92979(9) 0.0296(3) Uani 1 1 d . . . H13 H -0.1027 0.2318 0.9794 0.036 Uiso 1 1 calc R . . C14 C -0.19967(11) 0.29769(15) 0.88956(10) 0.0306(3) Uani 1 1 d . . . H14 H -0.2574 0.2775 0.9114 0.037 Uiso 1 1 calc R . . C15 C -0.20667(10) 0.35408(14) 0.81779(9) 0.0283(3) Uani 1 1 d . . . H15 H -0.2695 0.3729 0.7902 0.034 Uiso 1 1 calc R . . C16 C -0.12212(10) 0.38369(13) 0.78537(8) 0.0231(3) Uani 1 1 d . . . H16 H -0.1278 0.4226 0.7358 0.028 Uiso 1 1 calc R . . C17 C 0.31082(9) 0.15051(12) 0.86810(7) 0.0174(2) Uani 1 1 d . . . C18 C 0.23358(10) 0.08782(12) 0.89634(8) 0.0210(3) Uani 1 1 d . . . H18 H 0.1714 0.1271 0.8935 0.025 Uiso 1 1 calc R . . C19 C 0.24472(11) -0.03008(13) 0.92834(9) 0.0284(3) Uani 1 1 d . . . H19 H 0.1903 -0.0695 0.9464 0.034 Uiso 1 1 calc R . . C20 C 0.33423(11) -0.09024(13) 0.93401(9) 0.0299(3) Uani 1 1 d . . . H20 H 0.3418 -0.1703 0.9562 0.036 Uiso 1 1 calc R . . C21 C 0.41252(11) -0.03187(13) 0.90688(9) 0.0266(3) Uani 1 1 d . . . H21 H 0.4746 -0.0717 0.9104 0.032 Uiso 1 1 calc R . . C22 C 0.40018(10) 0.08482(13) 0.87452(8) 0.0222(3) Uani 1 1 d . . . H22 H 0.4548 0.1225 0.8557 0.027 Uiso 1 1 calc R . . C23 C 0.28303(9) 0.52744(11) 0.88671(7) 0.0166(2) Uani 1 1 d . . . C24 C 0.29483(10) 0.43287(12) 0.94401(7) 0.0187(3) Uani 1 1 d . . . C25 C 0.38673(10) 0.37597(13) 0.94177(8) 0.0211(3) Uani 1 1 d . . . C26 C 0.43150(9) 0.43241(12) 0.88164(8) 0.0204(3) Uani 1 1 d . . . C27 C 0.36788(9) 0.52773(12) 0.84832(8) 0.0181(3) Uani 1 1 d . . . C28 C 0.20073(10) 0.61911(13) 0.87626(9) 0.0227(3) Uani 1 1 d . . . H28A H 0.2113 0.6810 0.9178 0.034 Uiso 1 1 calc R . . H28B H 0.1382 0.5767 0.8787 0.034 Uiso 1 1 calc R . . H28C H 0.1988 0.6596 0.8255 0.034 Uiso 1 1 calc R . . C29 C 0.22601(11) 0.40388(14) 1.00175(8) 0.0273(3) Uani 1 1 d . . . H29A H 0.2188 0.3144 1.0057 0.041 Uiso 1 1 calc R . . H29B H 0.1617 0.4410 0.9844 0.041 Uiso 1 1 calc R . . H29C H 0.2526 0.4373 1.0529 0.041 Uiso 1 1 calc R . . C30 C 0.43571(12) 0.28895(14) 1.00246(9) 0.0324(3) Uani 1 1 d . . . H30A H 0.4686 0.3362 1.0467 0.049 Uiso 1 1 calc R . . H30B H 0.4843 0.2391 0.9800 0.049 Uiso 1 1 calc R . . H30C H 0.3862 0.2348 1.0203 0.049 Uiso 1 1 calc R . . C31 C 0.53526(10) 0.40859(15) 0.86653(10) 0.0316(3) Uani 1 1 d . . . H31A H 0.5814 0.4395 0.9104 0.047 Uiso 1 1 calc R . . H31B H 0.5468 0.4509 0.8186 0.047 Uiso 1 1 calc R . . H31C H 0.5451 0.3198 0.8607 0.047 Uiso 1 1 calc R . . C32 C 0.39307(11) 0.62529(13) 0.79279(9) 0.0257(3) Uani 1 1 d . . . H32A H 0.3324 0.6613 0.7656 0.039 Uiso 1 1 calc R . . H32B H 0.4309 0.5884 0.7546 0.039 Uiso 1 1 calc R . . H32C H 0.4323 0.6898 0.8219 0.039 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 Ti1 0.01081(11) 0.01566(11) 0.01326(11) 0.00109(8) 0.00164(8) 0.00056(8) N1 0.0145(5) 0.0174(5) 0.0136(5) -0.0007(4) 0.0013(4) -0.0001(4) C1 0.0204(6) 0.0222(6) 0.0103(5) 0.0005(5) 0.0024(5) -0.0016(5) C2 0.0291(7) 0.0223(7) 0.0140(6) -0.0029(5) 0.0040(5) 0.0017(6) C3 0.0274(7) 0.0389(8) 0.0180(6) -0.0025(6) 0.0073(5) 0.0123(6) C4 0.0185(6) 0.0485(9) 0.0187(6) 0.0012(6) 0.0079(5) -0.0011(6) C5 0.0224(6) 0.0278(7) 0.0157(6) 0.0039(5) 0.0043(5) -0.0047(5) C6 0.0208(6) 0.0235(7) 0.0139(6) 0.0030(5) -0.0015(5) -0.0023(5) C7 0.0250(7) 0.0315(8) 0.0239(7) -0.0037(6) -0.0012(6) -0.0084(6) C8 0.0342(8) 0.0400(9) 0.0175(7) 0.0089(6) -0.0019(6) 0.0002(7) C9 0.0176(6) 0.0220(6) 0.0205(6) 0.0048(5) -0.0009(5) 0.0018(5) C10 0.0154(6) 0.0167(6) 0.0165(6) -0.0008(5) 0.0014(5) 0.0006(5) C11 0.0142(6) 0.0185(6) 0.0208(6) -0.0032(5) 0.0020(5) 0.0011(5) C12 0.0174(6) 0.0286(7) 0.0243(7) 0.0030(6) 0.0039(5) 0.0026(5) C13 0.0260(7) 0.0338(8) 0.0306(8) 0.0031(6) 0.0103(6) -0.0008(6) C14 0.0196(7) 0.0334(8) 0.0415(9) -0.0054(7) 0.0136(6) -0.0034(6) C15 0.0130(6) 0.0331(8) 0.0380(8) -0.0079(6) 0.0006(6) 0.0014(5) C16 0.0178(6) 0.0257(7) 0.0251(7) -0.0021(6) 0.0003(5) 0.0026(5) C17 0.0186(6) 0.0169(6) 0.0163(6) -0.0014(5) 0.0010(5) 0.0002(5) C18 0.0195(6) 0.0204(6) 0.0234(7) -0.0002(5) 0.0044(5) 0.0009(5) C19 0.0282(7) 0.0225(7) 0.0354(8) 0.0048(6) 0.0082(6) -0.0039(6) C20 0.0363(8) 0.0169(7) 0.0362(8) 0.0064(6) 0.0041(7) 0.0023(6) C21 0.0264(7) 0.0223(7) 0.0309(8) 0.0015(6) 0.0032(6) 0.0085(6) C22 0.0191(6) 0.0217(7) 0.0265(7) 0.0020(5) 0.0052(5) 0.0016(5) C23 0.0147(6) 0.0161(6) 0.0185(6) -0.0021(5) -0.0002(5) -0.0012(5) C24 0.0213(6) 0.0191(6) 0.0150(6) -0.0023(5) -0.0006(5) -0.0022(5) C25 0.0214(6) 0.0193(6) 0.0200(6) -0.0015(5) -0.0069(5) -0.0004(5) C26 0.0127(6) 0.0201(6) 0.0267(7) -0.0013(5) -0.0033(5) -0.0005(5) C27 0.0145(6) 0.0172(6) 0.0220(6) 0.0003(5) 0.0004(5) -0.0017(5) C28 0.0196(6) 0.0179(6) 0.0304(7) -0.0033(5) 0.0028(5) 0.0024(5) C29 0.0350(8) 0.0305(8) 0.0172(6) -0.0029(6) 0.0063(6) -0.0076(6) C30 0.0397(9) 0.0262(7) 0.0261(7) 0.0021(6) -0.0145(6) 0.0040(7) C31 0.0136(6) 0.0310(8) 0.0490(10) -0.0030(7) 0.0002(6) 0.0012(6) C32 0.0227(7) 0.0233(7) 0.0316(8) 0.0053(6) 0.0057(6) -0.0051(5) _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 Ti1 N1 1.9228(10) . ? Ti1 C17 2.2005(13) . ? Ti1 C5 2.3804(13) . ? Ti1 C4 2.3904(14) . ? Ti1 C3 2.4022(14) . ? Ti1 C27 2.4092(13) . ? Ti1 C26 2.4116(13) . ? Ti1 C2 2.4164(13) . ? Ti1 C23 2.4176(13) . ? Ti1 C24 2.4344(13) . ? Ti1 C1 2.4442(12) . ? Ti1 C25 2.4526(13) . ? N1 C10 1.2708(16) . ? C1 C2 1.4090(19) . ? C1 C5 1.4167(18) . ? C1 C6 1.5136(18) . ? C2 C3 1.415(2) . ? C2 H2 0.9500 . ? C3 C4 1.394(2) . ? C3 H3 0.9500 . ? C4 C5 1.418(2) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C7 1.5283(19) . ? C6 C8 1.5341(18) . ? C6 C9 1.5548(19) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 C10 1.5157(17) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C11 1.5000(17) . ? C11 C12 1.3976(19) . ? C11 C16 1.4009(18) . ? C12 C13 1.3835(19) . ? C12 H12 0.9500 . ? C13 C14 1.387(2) . ? C13 H13 0.9500 . ? C14 C15 1.377(2) . ? C14 H14 0.9500 . ? C15 C16 1.394(2) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 C18 1.4031(18) . ? C17 C22 1.4107(18) . ? C18 C19 1.3948(19) . ? C18 H18 0.9500 . ? C19 C20 1.384(2) . ? C19 H19 0.9500 . ? C20 C21 1.384(2) . ? C20 H20 0.9500 . ? C21 C22 1.3861(19) . ? C21 H21 0.9500 . ? C22 H22 0.9500 . ? C23 C27 1.4181(18) . ? C23 C24 1.4214(18) . ? C23 C28 1.4984(17) . ? C24 C25 1.4106(19) . ? C24 C29 1.4997(19) . ? C25 C26 1.4184(19) . ? C25 C30 1.5020(19) . ? C26 C27 1.4246(18) . ? C26 C31 1.5060(18) . ? C27 C32 1.5021(18) . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 H30A 0.9800 . ? C30 H30B 0.9800 . ? C30 H30C 0.9800 . ? C31 H31A 0.9800 . ? C31 H31B 0.9800 . ? C31 H31C 0.9800 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? 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 N1 Ti1 C17 98.26(5) . . ? N1 Ti1 C5 99.86(5) . . ? C17 Ti1 C5 133.22(5) . . ? N1 Ti1 C4 131.86(5) . . ? C17 Ti1 C4 107.00(5) . . ? C5 Ti1 C4 34.57(5) . . ? N1 Ti1 C3 123.16(5) . . ? C17 Ti1 C3 77.25(5) . . ? C5 Ti1 C3 56.76(5) . . ? C4 Ti1 C3 33.81(5) . . ? N1 Ti1 C27 110.53(4) . . ? C17 Ti1 C27 130.78(5) . . ? C5 Ti1 C27 80.92(5) . . ? C4 Ti1 C27 82.70(5) . . ? C3 Ti1 C27 114.38(5) . . ? N1 Ti1 C26 133.79(5) . . ? C17 Ti1 C26 97.60(5) . . ? C5 Ti1 C26 100.10(5) . . ? C4 Ti1 C26 83.04(5) . . ? C3 Ti1 C26 102.61(5) . . ? C27 Ti1 C26 34.37(4) . . ? N1 Ti1 C2 89.02(5) . . ? C17 Ti1 C2 81.12(5) . . ? C5 Ti1 C2 56.59(5) . . ? C4 Ti1 C2 56.54(5) . . ? C3 Ti1 C2 34.16(5) . . ? C27 Ti1 C2 136.09(5) . . ? C26 Ti1 C2 136.32(5) . . ? N1 Ti1 C23 79.09(4) . . ? C17 Ti1 C23 126.56(5) . . ? C5 Ti1 C23 99.14(5) . . ? C4 Ti1 C23 113.90(5) . . ? C3 Ti1 C23 147.44(5) . . ? C27 Ti1 C23 34.17(4) . . ? C26 Ti1 C23 56.82(4) . . ? C2 Ti1 C23 150.92(5) . . ? N1 Ti1 C24 79.76(4) . . ? C17 Ti1 C24 92.57(5) . . ? C5 Ti1 C24 132.96(5) . . ? C4 Ti1 C24 137.21(5) . . ? C3 Ti1 C24 155.70(5) . . ? C27 Ti1 C24 56.55(4) . . ? C26 Ti1 C24 56.39(5) . . ? C2 Ti1 C24 166.25(5) . . ? C23 Ti1 C24 34.07(4) . . ? N1 Ti1 C1 75.85(4) . . ? C17 Ti1 C1 113.48(5) . . ? C5 Ti1 C1 34.12(4) . . ? C4 Ti1 C1 56.70(5) . . ? C3 Ti1 C1 56.38(5) . . ? C27 Ti1 C1 111.82(4) . . ? C26 Ti1 C1 134.12(5) . . ? C2 Ti1 C1 33.69(4) . . ? C23 Ti1 C1 117.23(4) . . ? C24 Ti1 C1 146.35(4) . . ? N1 Ti1 C25 110.99(5) . . ? C17 Ti1 C25 76.52(5) . . ? C5 Ti1 C25 133.55(5) . . ? C4 Ti1 C25 114.36(5) . . ? C3 Ti1 C25 122.18(5) . . ? C27 Ti1 C25 56.42(4) . . ? C26 Ti1 C25 33.89(5) . . ? C2 Ti1 C25 151.73(5) . . ? C23 Ti1 C25 56.24(4) . . ? C24 Ti1 C25 33.55(4) . . ? C1 Ti1 C25 167.56(5) . . ? C10 N1 Ti1 145.07(9) . . ? C2 C1 C5 107.17(12) . . ? C2 C1 C6 127.52(12) . . ? C5 C1 C6 125.26(12) . . ? C2 C1 Ti1 72.07(7) . . ? C5 C1 Ti1 70.47(7) . . ? C6 C1 Ti1 124.77(8) . . ? C1 C2 C3 108.34(13) . . ? C1 C2 Ti1 74.23(7) . . ? C3 C2 Ti1 72.37(8) . . ? C1 C2 H2 125.8 . . ? C3 C2 H2 125.8 . . ? Ti1 C2 H2 119.4 . . ? C4 C3 C2 108.28(13) . . ? C4 C3 Ti1 72.63(8) . . ? C2 C3 Ti1 73.47(7) . . ? C4 C3 H3 125.9 . . ? C2 C3 H3 125.9 . . ? Ti1 C3 H3 119.8 . . ? C3 C4 C5 107.91(13) . . ? C3 C4 Ti1 73.56(8) . . ? C5 C4 Ti1 72.33(7) . . ? C3 C4 H4 126.0 . . ? C5 C4 H4 126.0 . . ? Ti1 C4 H4 119.9 . . ? C1 C5 C4 108.20(13) . . ? C1 C5 Ti1 75.41(7) . . ? C4 C5 Ti1 73.10(8) . . ? C1 C5 H5 125.9 . . ? C4 C5 H5 125.9 . . ? Ti1 C5 H5 117.6 . . ? C1 C6 C7 111.06(11) . . ? C1 C6 C8 108.78(11) . . ? C7 C6 C8 108.74(11) . . ? C1 C6 C9 110.13(10) . . ? C7 C6 C9 110.00(11) . . ? C8 C6 C9 108.05(11) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C10 C9 C6 107.89(10) . . ? C10 C9 H9A 110.1 . . ? C6 C9 H9A 110.1 . . ? C10 C9 H9B 110.1 . . ? C6 C9 H9B 110.1 . . ? H9A C9 H9B 108.4 . . ? N1 C10 C11 121.69(12) . . ? N1 C10 C9 117.82(11) . . ? C11 C10 C9 120.24(11) . . ? C12 C11 C16 117.94(12) . . ? C12 C11 C10 119.11(11) . . ? C16 C11 C10 122.95(12) . . ? C13 C12 C11 121.07(13) . . ? C13 C12 H12 119.5 . . ? C11 C12 H12 119.5 . . ? C12 C13 C14 120.33(14) . . ? C12 C13 H13 119.8 . . ? C14 C13 H13 119.8 . . ? C15 C14 C13 119.63(13) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C14 C15 C16 120.42(13) . . ? C14 C15 H15 119.8 . . ? C16 C15 H15 119.8 . . ? C15 C16 C11 120.61(13) . . ? C15 C16 H16 119.7 . . ? C11 C16 H16 119.7 . . ? C18 C17 C22 114.74(12) . . ? C18 C17 Ti1 119.63(9) . . ? C22 C17 Ti1 125.62(10) . . ? C19 C18 C17 122.43(13) . . ? C19 C18 H18 118.8 . . ? C17 C18 H18 118.8 . . ? C20 C19 C18 120.63(13) . . ? C20 C19 H19 119.7 . . ? C18 C19 H19 119.7 . . ? C19 C20 C21 118.93(13) . . ? C19 C20 H20 120.5 . . ? C21 C20 H20 120.5 . . ? C20 C21 C22 119.85(13) . . ? C20 C21 H21 120.1 . . ? C22 C21 H21 120.1 . . ? C21 C22 C17 123.42(13) . . ? C21 C22 H22 118.3 . . ? C17 C22 H22 118.3 . . ? C27 C23 C24 107.82(11) . . ? C27 C23 C28 126.63(12) . . ? C24 C23 C28 125.18(12) . . ? C27 C23 Ti1 72.59(7) . . ? C24 C23 Ti1 73.61(7) . . ? C28 C23 Ti1 124.97(9) . . ? C25 C24 C23 108.31(11) . . ? C25 C24 C29 125.04(12) . . ? C23 C24 C29 126.48(12) . . ? C25 C24 Ti1 73.93(7) . . ? C23 C24 Ti1 72.32(7) . . ? C29 C24 Ti1 123.35(9) . . ? C24 C25 C26 108.07(12) . . ? C24 C25 C30 124.97(13) . . ? C26 C25 C30 125.97(13) . . ? C24 C25 Ti1 72.52(7) . . ? C26 C25 Ti1 71.47(7) . . ? C30 C25 Ti1 130.58(10) . . ? C25 C26 C27 107.91(11) . . ? C25 C26 C31 124.65(13) . . ? C27 C26 C31 126.67(13) . . ? C25 C26 Ti1 74.64(7) . . ? C27 C26 Ti1 72.72(7) . . ? C31 C26 Ti1 126.36(10) . . ? C23 C27 C26 107.85(11) . . ? C23 C27 C32 125.26(12) . . ? C26 C27 C32 126.09(12) . . ? C23 C27 Ti1 73.24(7) . . ? C26 C27 Ti1 72.91(7) . . ? C32 C27 Ti1 127.57(9) . . ? C23 C28 H28A 109.5 . . ? C23 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C23 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C24 C29 H29A 109.5 . . ? C24 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C24 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C25 C30 H30A 109.5 . . ? C25 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C25 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? C26 C31 H31A 109.5 . . ? C26 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? C26 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? C27 C32 H32A 109.5 . . ? C27 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C27 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? 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 C17 Ti1 N1 C10 -141.81(16) . . . . ? C5 Ti1 N1 C10 -5.12(17) . . . . ? C4 Ti1 N1 C10 -20.03(19) . . . . ? C3 Ti1 N1 C10 -61.68(18) . . . . ? C27 Ti1 N1 C10 78.80(17) . . . . ? C26 Ti1 N1 C10 109.27(16) . . . . ? C2 Ti1 N1 C10 -60.93(16) . . . . ? C23 Ti1 N1 C10 92.39(16) . . . . ? C24 Ti1 N1 C10 127.06(17) . . . . ? C1 Ti1 N1 C10 -29.56(16) . . . . ? C25 Ti1 N1 C10 139.53(16) . . . . ? N1 Ti1 C1 C2 -110.26(8) . . . . ? C17 Ti1 C1 C2 -17.27(9) . . . . ? C5 Ti1 C1 C2 116.35(12) . . . . ? C4 Ti1 C1 C2 78.23(9) . . . . ? C3 Ti1 C1 C2 37.43(8) . . . . ? C27 Ti1 C1 C2 142.96(8) . . . . ? C26 Ti1 C1 C2 111.19(9) . . . . ? C23 Ti1 C1 C2 -179.81(8) . . . . ? C24 Ti1 C1 C2 -155.07(9) . . . . ? C25 Ti1 C1 C2 124.8(2) . . . . ? N1 Ti1 C1 C5 133.39(9) . . . . ? C17 Ti1 C1 C5 -133.62(8) . . . . ? C4 Ti1 C1 C5 -38.12(8) . . . . ? C3 Ti1 C1 C5 -78.92(9) . . . . ? C27 Ti1 C1 C5 26.61(9) . . . . ? C26 Ti1 C1 C5 -5.16(11) . . . . ? C2 Ti1 C1 C5 -116.35(12) . . . . ? C23 Ti1 C1 C5 63.84(9) . . . . ? C24 Ti1 C1 C5 88.58(11) . . . . ? C25 Ti1 C1 C5 8.5(2) . . . . ? N1 Ti1 C1 C6 13.43(10) . . . . ? C17 Ti1 C1 C6 106.41(11) . . . . ? C5 Ti1 C1 C6 -119.97(14) . . . . ? C4 Ti1 C1 C6 -158.09(13) . . . . ? C3 Ti1 C1 C6 161.11(13) . . . . ? C27 Ti1 C1 C6 -93.35(11) . . . . ? C26 Ti1 C1 C6 -125.13(10) . . . . ? C2 Ti1 C1 C6 123.68(14) . . . . ? C23 Ti1 C1 C6 -56.13(12) . . . . ? C24 Ti1 C1 C6 -31.38(15) . . . . ? C25 Ti1 C1 C6 -111.5(2) . . . . ? C5 C1 C2 C3 -2.72(14) . . . . ? C6 C1 C2 C3 174.68(12) . . . . ? Ti1 C1 C2 C3 -64.84(9) . . . . ? C5 C1 C2 Ti1 62.12(9) . . . . ? C6 C1 C2 Ti1 -120.48(12) . . . . ? N1 Ti1 C2 C1 65.48(8) . . . . ? C17 Ti1 C2 C1 164.00(8) . . . . ? C5 Ti1 C2 C1 -37.03(7) . . . . ? C4 Ti1 C2 C1 -78.75(9) . . . . ? C3 Ti1 C2 C1 -115.65(12) . . . . ? C27 Ti1 C2 C1 -53.73(10) . . . . ? C26 Ti1 C2 C1 -104.28(9) . . . . ? C23 Ti1 C2 C1 0.34(14) . . . . ? C24 Ti1 C2 C1 100.6(2) . . . . ? C25 Ti1 C2 C1 -158.08(9) . . . . ? N1 Ti1 C2 C3 -178.87(9) . . . . ? C17 Ti1 C2 C3 -80.35(9) . . . . ? C5 Ti1 C2 C3 78.62(9) . . . . ? C4 Ti1 C2 C3 36.90(9) . . . . ? C27 Ti1 C2 C3 61.92(11) . . . . ? C26 Ti1 C2 C3 11.37(12) . . . . ? C23 Ti1 C2 C3 115.99(11) . . . . ? C24 Ti1 C2 C3 -143.76(18) . . . . ? C1 Ti1 C2 C3 115.65(12) . . . . ? C25 Ti1 C2 C3 -42.43(14) . . . . ? C1 C2 C3 C4 1.27(15) . . . . ? Ti1 C2 C3 C4 -64.79(10) . . . . ? C1 C2 C3 Ti1 66.06(9) . . . . ? N1 Ti1 C3 C4 117.17(9) . . . . ? C17 Ti1 C3 C4 -151.21(9) . . . . ? C5 Ti1 C3 C4 37.76(8) . . . . ? C27 Ti1 C3 C4 -21.96(10) . . . . ? C26 Ti1 C3 C4 -56.15(9) . . . . ? C2 Ti1 C3 C4 115.83(12) . . . . ? C23 Ti1 C3 C4 -9.92(14) . . . . ? C24 Ti1 C3 C4 -84.14(14) . . . . ? C1 Ti1 C3 C4 78.92(9) . . . . ? C25 Ti1 C3 C4 -86.35(10) . . . . ? N1 Ti1 C3 C2 1.35(11) . . . . ? C17 Ti1 C3 C2 92.96(9) . . . . ? C5 Ti1 C3 C2 -78.07(9) . . . . ? C4 Ti1 C3 C2 -115.83(12) . . . . ? C27 Ti1 C3 C2 -137.79(8) . . . . ? C26 Ti1 C3 C2 -171.98(8) . . . . ? C23 Ti1 C3 C2 -125.74(10) . . . . ? C24 Ti1 C3 C2 160.03(10) . . . . ? C1 Ti1 C3 C2 -36.91(8) . . . . ? C25 Ti1 C3 C2 157.82(8) . . . . ? C2 C3 C4 C5 0.68(16) . . . . ? Ti1 C3 C4 C5 -64.66(10) . . . . ? C2 C3 C4 Ti1 65.34(9) . . . . ? N1 Ti1 C4 C3 -88.98(10) . . . . ? C17 Ti1 C4 C3 29.42(10) . . . . ? C5 Ti1 C4 C3 -115.50(13) . . . . ? C27 Ti1 C4 C3 159.92(9) . . . . ? C26 Ti1 C4 C3 125.27(9) . . . . ? C2 Ti1 C4 C3 -37.28(8) . . . . ? C23 Ti1 C4 C3 174.18(8) . . . . ? C24 Ti1 C4 C3 142.95(9) . . . . ? C1 Ti1 C4 C3 -77.90(9) . . . . ? C25 Ti1 C4 C3 111.99(9) . . . . ? N1 Ti1 C4 C5 26.52(12) . . . . ? C17 Ti1 C4 C5 144.92(8) . . . . ? C3 Ti1 C4 C5 115.50(13) . . . . ? C27 Ti1 C4 C5 -84.58(9) . . . . ? C26 Ti1 C4 C5 -119.23(9) . . . . ? C2 Ti1 C4 C5 78.22(9) . . . . ? C23 Ti1 C4 C5 -70.31(9) . . . . ? C24 Ti1 C4 C5 -101.55(10) . . . . ? C1 Ti1 C4 C5 37.60(8) . . . . ? C25 Ti1 C4 C5 -132.51(8) . . . . ? C2 C1 C5 C4 3.14(14) . . . . ? C6 C1 C5 C4 -174.33(12) . . . . ? Ti1 C1 C5 C4 66.31(9) . . . . ? C2 C1 C5 Ti1 -63.17(9) . . . . ? C6 C1 C5 Ti1 119.36(12) . . . . ? C3 C4 C5 C1 -2.38(15) . . . . ? Ti1 C4 C5 C1 -67.84(9) . . . . ? C3 C4 C5 Ti1 65.47(10) . . . . ? N1 Ti1 C5 C1 -45.66(9) . . . . ? C17 Ti1 C5 C1 65.66(10) . . . . ? C4 Ti1 C5 C1 114.61(12) . . . . ? C3 Ti1 C5 C1 77.71(9) . . . . ? C27 Ti1 C5 C1 -155.09(8) . . . . ? C26 Ti1 C5 C1 176.24(8) . . . . ? C2 Ti1 C5 C1 36.55(8) . . . . ? C23 Ti1 C5 C1 -126.06(8) . . . . ? C24 Ti1 C5 C1 -130.80(8) . . . . ? C25 Ti1 C5 C1 -177.49(7) . . . . ? N1 Ti1 C5 C4 -160.27(9) . . . . ? C17 Ti1 C5 C4 -48.95(11) . . . . ? C3 Ti1 C5 C4 -36.91(9) . . . . ? C27 Ti1 C5 C4 90.29(9) . . . . ? C26 Ti1 C5 C4 61.63(9) . . . . ? C2 Ti1 C5 C4 -78.06(9) . . . . ? C23 Ti1 C5 C4 119.32(9) . . . . ? C24 Ti1 C5 C4 114.58(9) . . . . ? C1 Ti1 C5 C4 -114.61(13) . . . . ? C25 Ti1 C5 C4 67.90(11) . . . . ? C2 C1 C6 C7 -3.71(18) . . . . ? C5 C1 C6 C7 173.24(12) . . . . ? Ti1 C1 C6 C7 -97.19(12) . . . . ? C2 C1 C6 C8 -123.36(14) . . . . ? C5 C1 C6 C8 53.59(17) . . . . ? Ti1 C1 C6 C8 143.17(10) . . . . ? C2 C1 C6 C9 118.40(14) . . . . ? C5 C1 C6 C9 -64.65(16) . . . . ? Ti1 C1 C6 C9 24.92(15) . . . . ? C1 C6 C9 C10 -63.81(13) . . . . ? C7 C6 C9 C10 58.92(13) . . . . ? C8 C6 C9 C10 177.49(11) . . . . ? Ti1 N1 C10 C11 171.10(11) . . . . ? Ti1 N1 C10 C9 -3.2(2) . . . . ? C6 C9 C10 N1 61.64(15) . . . . ? C6 C9 C10 C11 -112.70(12) . . . . ? N1 C10 C11 C12 9.35(19) . . . . ? C9 C10 C11 C12 -176.54(12) . . . . ? N1 C10 C11 C16 -171.40(13) . . . . ? C9 C10 C11 C16 2.71(19) . . . . ? C16 C11 C12 C13 0.2(2) . . . . ? C10 C11 C12 C13 179.48(13) . . . . ? C11 C12 C13 C14 -0.1(2) . . . . ? C12 C13 C14 C15 -0.1(2) . . . . ? C13 C14 C15 C16 0.2(2) . . . . ? C14 C15 C16 C11 0.0(2) . . . . ? C12 C11 C16 C15 -0.1(2) . . . . ? C10 C11 C16 C15 -179.41(13) . . . . ? N1 Ti1 C17 C18 -1.63(11) . . . . ? C5 Ti1 C17 C18 -113.59(11) . . . . ? C4 Ti1 C17 C18 -140.17(10) . . . . ? C3 Ti1 C17 C18 -123.90(11) . . . . ? C27 Ti1 C17 C18 124.77(10) . . . . ? C26 Ti1 C17 C18 134.82(10) . . . . ? C2 Ti1 C17 C18 -89.32(11) . . . . ? C23 Ti1 C17 C18 80.87(11) . . . . ? C24 Ti1 C17 C18 78.40(11) . . . . ? C1 Ti1 C17 C18 -79.72(11) . . . . ? C25 Ti1 C17 C18 108.09(11) . . . . ? N1 Ti1 C17 C22 176.96(11) . . . . ? C5 Ti1 C17 C22 65.00(13) . . . . ? C4 Ti1 C17 C22 38.41(12) . . . . ? C3 Ti1 C17 C22 54.69(11) . . . . ? C27 Ti1 C17 C22 -56.65(13) . . . . ? C26 Ti1 C17 C22 -46.59(12) . . . . ? C2 Ti1 C17 C22 89.26(12) . . . . ? C23 Ti1 C17 C22 -100.54(12) . . . . ? C24 Ti1 C17 C22 -103.02(11) . . . . ? C1 Ti1 C17 C22 98.86(12) . . . . ? C25 Ti1 C17 C22 -73.32(11) . . . . ? C22 C17 C18 C19 0.1(2) . . . . ? Ti1 C17 C18 C19 178.87(11) . . . . ? C17 C18 C19 C20 0.5(2) . . . . ? C18 C19 C20 C21 -0.5(2) . . . . ? C19 C20 C21 C22 -0.2(2) . . . . ? C20 C21 C22 C17 0.8(2) . . . . ? C18 C17 C22 C21 -0.8(2) . . . . ? Ti1 C17 C22 C21 -179.43(11) . . . . ? N1 Ti1 C23 C27 -156.93(8) . . . . ? C17 Ti1 C23 C27 110.82(8) . . . . ? C5 Ti1 C23 C27 -58.56(8) . . . . ? C4 Ti1 C23 C27 -25.80(9) . . . . ? C3 Ti1 C23 C27 -19.78(12) . . . . ? C26 Ti1 C23 C27 37.58(7) . . . . ? C2 Ti1 C23 C27 -89.43(11) . . . . ? C24 Ti1 C23 C27 115.24(11) . . . . ? C1 Ti1 C23 C27 -89.22(8) . . . . ? C25 Ti1 C23 C27 78.48(8) . . . . ? N1 Ti1 C23 C24 87.83(8) . . . . ? C17 Ti1 C23 C24 -4.42(9) . . . . ? C5 Ti1 C23 C24 -173.80(7) . . . . ? C4 Ti1 C23 C24 -141.04(8) . . . . ? C3 Ti1 C23 C24 -135.02(9) . . . . ? C27 Ti1 C23 C24 -115.24(11) . . . . ? C26 Ti1 C23 C24 -77.66(8) . . . . ? C2 Ti1 C23 C24 155.32(9) . . . . ? C1 Ti1 C23 C24 155.54(7) . . . . ? C25 Ti1 C23 C24 -36.77(7) . . . . ? N1 Ti1 C23 C28 -33.99(11) . . . . ? C17 Ti1 C23 C28 -126.24(11) . . . . ? C5 Ti1 C23 C28 64.38(11) . . . . ? C4 Ti1 C23 C28 97.14(11) . . . . ? C3 Ti1 C23 C28 103.16(13) . . . . ? C27 Ti1 C23 C28 122.94(14) . . . . ? C26 Ti1 C23 C28 160.52(13) . . . . ? C2 Ti1 C23 C28 33.51(16) . . . . ? C24 Ti1 C23 C28 -121.82(14) . . . . ? C1 Ti1 C23 C28 33.72(12) . . . . ? C25 Ti1 C23 C28 -158.58(13) . . . . ? C27 C23 C24 C25 0.66(14) . . . . ? C28 C23 C24 C25 -172.72(12) . . . . ? Ti1 C23 C24 C25 65.70(9) . . . . ? C27 C23 C24 C29 176.16(12) . . . . ? C28 C23 C24 C29 2.8(2) . . . . ? Ti1 C23 C24 C29 -118.81(13) . . . . ? C27 C23 C24 Ti1 -65.04(9) . . . . ? C28 C23 C24 Ti1 121.58(12) . . . . ? N1 Ti1 C24 C25 158.60(8) . . . . ? C17 Ti1 C24 C25 60.66(8) . . . . ? C5 Ti1 C24 C25 -107.41(9) . . . . ? C4 Ti1 C24 C25 -57.98(11) . . . . ? C3 Ti1 C24 C25 -3.40(16) . . . . ? C27 Ti1 C24 C25 -78.28(8) . . . . ? C26 Ti1 C24 C25 -36.76(8) . . . . ? C2 Ti1 C24 C25 122.83(19) . . . . ? C23 Ti1 C24 C25 -115.79(11) . . . . ? C1 Ti1 C24 C25 -157.43(8) . . . . ? N1 Ti1 C24 C23 -85.62(8) . . . . ? C17 Ti1 C24 C23 176.44(8) . . . . ? C5 Ti1 C24 C23 8.37(10) . . . . ? C4 Ti1 C24 C23 57.81(10) . . . . ? C3 Ti1 C24 C23 112.39(13) . . . . ? C27 Ti1 C24 C23 37.51(7) . . . . ? C26 Ti1 C24 C23 79.03(8) . . . . ? C2 Ti1 C24 C23 -121.38(19) . . . . ? C1 Ti1 C24 C23 -41.64(11) . . . . ? C25 Ti1 C24 C23 115.79(11) . . . . ? N1 Ti1 C24 C29 36.87(11) . . . . ? C17 Ti1 C24 C29 -61.06(11) . . . . ? C5 Ti1 C24 C29 130.87(11) . . . . ? C4 Ti1 C24 C29 -179.70(10) . . . . ? C3 Ti1 C24 C29 -125.12(14) . . . . ? C27 Ti1 C24 C29 160.00(13) . . . . ? C26 Ti1 C24 C29 -158.48(13) . . . . ? C2 Ti1 C24 C29 1.1(3) . . . . ? C23 Ti1 C24 C29 122.49(14) . . . . ? C1 Ti1 C24 C29 80.85(14) . . . . ? C25 Ti1 C24 C29 -121.72(15) . . . . ? C23 C24 C25 C26 -1.60(15) . . . . ? C29 C24 C25 C26 -177.17(12) . . . . ? Ti1 C24 C25 C26 63.04(9) . . . . ? C23 C24 C25 C30 167.63(13) . . . . ? C29 C24 C25 C30 -7.9(2) . . . . ? Ti1 C24 C25 C30 -127.73(14) . . . . ? C23 C24 C25 Ti1 -64.64(9) . . . . ? C29 C24 C25 Ti1 119.79(13) . . . . ? N1 Ti1 C25 C24 -22.62(9) . . . . ? C17 Ti1 C25 C24 -116.43(8) . . . . ? C5 Ti1 C25 C24 105.53(9) . . . . ? C4 Ti1 C25 C24 140.78(8) . . . . ? C3 Ti1 C25 C24 178.35(8) . . . . ? C27 Ti1 C25 C24 78.69(8) . . . . ? C26 Ti1 C25 C24 116.66(11) . . . . ? C2 Ti1 C25 C24 -155.06(10) . . . . ? C23 Ti1 C25 C24 37.35(7) . . . . ? C1 Ti1 C25 C24 99.0(2) . . . . ? N1 Ti1 C25 C26 -139.28(8) . . . . ? C17 Ti1 C25 C26 126.92(9) . . . . ? C5 Ti1 C25 C26 -11.12(11) . . . . ? C4 Ti1 C25 C26 24.13(9) . . . . ? C3 Ti1 C25 C26 61.69(10) . . . . ? C27 Ti1 C25 C26 -37.96(7) . . . . ? C2 Ti1 C25 C26 88.28(12) . . . . ? C23 Ti1 C25 C26 -79.31(8) . . . . ? C24 Ti1 C25 C26 -116.66(11) . . . . ? C1 Ti1 C25 C26 -17.7(2) . . . . ? N1 Ti1 C25 C30 98.81(14) . . . . ? C17 Ti1 C25 C30 5.01(14) . . . . ? C5 Ti1 C25 C30 -133.04(13) . . . . ? C4 Ti1 C25 C30 -97.78(14) . . . . ? C3 Ti1 C25 C30 -60.22(15) . . . . ? C27 Ti1 C25 C30 -159.88(16) . . . . ? C26 Ti1 C25 C30 -121.91(17) . . . . ? C2 Ti1 C25 C30 -33.6(2) . . . . ? C23 Ti1 C25 C30 158.78(16) . . . . ? C24 Ti1 C25 C30 121.43(17) . . . . ? C1 Ti1 C25 C30 -139.6(2) . . . . ? C24 C25 C26 C27 1.91(15) . . . . ? C30 C25 C26 C27 -167.18(13) . . . . ? Ti1 C25 C26 C27 65.64(9) . . . . ? C24 C25 C26 C31 172.39(13) . . . . ? C30 C25 C26 C31 3.3(2) . . . . ? Ti1 C25 C26 C31 -123.89(14) . . . . ? C24 C25 C26 Ti1 -63.72(9) . . . . ? C30 C25 C26 Ti1 127.19(14) . . . . ? N1 Ti1 C26 C25 57.53(10) . . . . ? C17 Ti1 C26 C25 -51.66(8) . . . . ? C5 Ti1 C26 C25 171.83(8) . . . . ? C4 Ti1 C26 C25 -157.97(9) . . . . ? C3 Ti1 C26 C25 -130.22(8) . . . . ? C27 Ti1 C26 C25 114.80(11) . . . . ? C2 Ti1 C26 C25 -136.73(8) . . . . ? C23 Ti1 C26 C25 77.45(8) . . . . ? C24 Ti1 C26 C25 36.38(8) . . . . ? C1 Ti1 C26 C25 174.77(7) . . . . ? N1 Ti1 C26 C27 -57.27(10) . . . . ? C17 Ti1 C26 C27 -166.46(8) . . . . ? C5 Ti1 C26 C27 57.03(8) . . . . ? C4 Ti1 C26 C27 87.23(8) . . . . ? C3 Ti1 C26 C27 114.98(8) . . . . ? C2 Ti1 C26 C27 108.47(9) . . . . ? C23 Ti1 C26 C27 -37.35(7) . . . . ? C24 Ti1 C26 C27 -78.43(8) . . . . ? C1 Ti1 C26 C27 59.97(10) . . . . ? C25 Ti1 C26 C27 -114.80(11) . . . . ? N1 Ti1 C26 C31 179.53(11) . . . . ? C17 Ti1 C26 C31 70.34(13) . . . . ? C5 Ti1 C26 C31 -66.17(13) . . . . ? C4 Ti1 C26 C31 -35.97(13) . . . . ? C3 Ti1 C26 C31 -8.22(13) . . . . ? C27 Ti1 C26 C31 -123.20(16) . . . . ? C2 Ti1 C26 C31 -14.73(15) . . . . ? C23 Ti1 C26 C31 -160.55(14) . . . . ? C24 Ti1 C26 C31 158.37(14) . . . . ? C1 Ti1 C26 C31 -63.23(14) . . . . ? C25 Ti1 C26 C31 122.00(16) . . . . ? C24 C23 C27 C26 0.52(14) . . . . ? C28 C23 C27 C26 173.78(12) . . . . ? Ti1 C23 C27 C26 -65.20(9) . . . . ? C24 C23 C27 C32 -169.75(12) . . . . ? C28 C23 C27 C32 3.5(2) . . . . ? Ti1 C23 C27 C32 124.54(13) . . . . ? C24 C23 C27 Ti1 65.71(9) . . . . ? C28 C23 C27 Ti1 -121.03(13) . . . . ? C25 C26 C27 C23 -1.50(14) . . . . ? C31 C26 C27 C23 -171.73(13) . . . . ? Ti1 C26 C27 C23 65.41(9) . . . . ? C25 C26 C27 C32 168.66(13) . . . . ? C31 C26 C27 C32 -1.6(2) . . . . ? Ti1 C26 C27 C32 -124.42(14) . . . . ? C25 C26 C27 Ti1 -66.91(9) . . . . ? C31 C26 C27 Ti1 122.86(14) . . . . ? N1 Ti1 C27 C23 24.26(8) . . . . ? C17 Ti1 C27 C23 -97.47(8) . . . . ? C5 Ti1 C27 C23 121.46(8) . . . . ? C4 Ti1 C27 C23 156.35(8) . . . . ? C3 Ti1 C27 C23 168.46(7) . . . . ? C26 Ti1 C27 C23 -115.31(11) . . . . ? C2 Ti1 C27 C23 135.52(8) . . . . ? C24 Ti1 C27 C23 -37.39(7) . . . . ? C1 Ti1 C27 C23 106.71(8) . . . . ? C25 Ti1 C27 C23 -77.90(8) . . . . ? N1 Ti1 C27 C26 139.57(8) . . . . ? C17 Ti1 C27 C26 17.85(10) . . . . ? C5 Ti1 C27 C26 -123.23(8) . . . . ? C4 Ti1 C27 C26 -88.33(8) . . . . ? C3 Ti1 C27 C26 -76.22(9) . . . . ? C2 Ti1 C27 C26 -109.17(9) . . . . ? C23 Ti1 C27 C26 115.31(11) . . . . ? C24 Ti1 C27 C26 77.92(8) . . . . ? C1 Ti1 C27 C26 -137.97(8) . . . . ? C25 Ti1 C27 C26 37.42(8) . . . . ? N1 Ti1 C27 C32 -97.67(11) . . . . ? C17 Ti1 C27 C32 140.60(11) . . . . ? C5 Ti1 C27 C32 -0.48(11) . . . . ? C4 Ti1 C27 C32 34.42(11) . . . . ? C3 Ti1 C27 C32 46.53(12) . . . . ? C26 Ti1 C27 C32 122.76(15) . . . . ? C2 Ti1 C27 C32 13.59(14) . . . . ? C23 Ti1 C27 C32 -121.93(14) . . . . ? C24 Ti1 C27 C32 -159.32(13) . . . . ? C1 Ti1 C27 C32 -15.22(12) . . . . ? C25 Ti1 C27 C32 160.17(13) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.310 _refine_diff_density_min -0.293 _refine_diff_density_rms 0.045 #===END