Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2003 data_global _publ_contact_author_email MINDIOLA@INDIANA.EDU _publ_contact_author_name 'Prof Daniel Mindiola' _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_address ; Department of Chemistry Indiana University 800 E. Kirkwood Ave, Bloomington IN 47405 UNITED STATES OF AMERICA ; _publ_section_title ; Phosphaazaallene and phosphinylimide complexes stemming from a terminal and four-coordinate titanium phosphinidene ; loop_ _publ_author_name 'Daniel Mindiola' 'Falguni Basuli' 'John C. Huffman' 'Lori A. Watson' data_03117 _database_code_CSD 218483 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C65 H91 N4 P Ti' _chemical_formula_weight 1007.29 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 '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' 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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P-1 ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.696(2) _cell_length_b 13.078(4) _cell_length_c 20.218(4) _cell_angle_alpha 81.562(6) _cell_angle_beta 78.932(5) _cell_angle_gamma 80.736(5) _cell_volume 2974.1(11) _cell_formula_units_Z 2 _cell_measurement_temperature 115(2) _cell_measurement_reflns_used 727 _cell_measurement_theta_min 2.68 _cell_measurement_theta_max 25.70 _exptl_crystal_description irregular _exptl_crystal_colour 'deep red' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.125 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1092 _exptl_absorpt_coefficient_mu 0.212 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 115(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_details ' 0.30 degree frames measured for 15.17 seconds each' _diffrn_measurement_method '\w scans' _diffrn_measurement_device 'three-circle goniometer with fixed chi' _diffrn_measurement_device_type 'Bruker Platform goniometer' _diffrn_detector 'CCD area detector' _diffrn_detector_type 'Bruker SMART 6000' _diffrn_detector_area_resol_mean 44.52 _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 12447 _diffrn_reflns_av_R_equivalents 0.0531 _diffrn_reflns_av_sigmaI/netI 0.1228 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 27.54 _reflns_number_total 11628 _reflns_number_gt 6497 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SAINT (Bruker, 1999)' _computing_data_reduction 'SAINT (Bruker, 1999), XTEL (local package)' _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^)+(0.0752P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 11628 _refine_ls_number_parameters 669 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1244 _refine_ls_R_factor_gt 0.0648 _refine_ls_wR_factor_ref 0.1650 _refine_ls_wR_factor_gt 0.1421 _refine_ls_goodness_of_fit_ref 0.916 _refine_ls_restrained_S_all 0.916 _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 0.31164(5) 0.19670(5) 0.70780(3) 0.01732(15) Uani 1 1 d . . . N2 N 0.2905(2) 0.0582(2) 0.76661(12) 0.0194(6) Uani 1 1 d . . . C3 C 0.3785(3) -0.0124(3) 0.74095(16) 0.0222(7) Uani 1 1 d . . . C4 C 0.4883(3) 0.0125(3) 0.70532(16) 0.0230(7) Uani 1 1 d . . . H4 H 0.5334 -0.0398 0.6795 0.028 Uiso 1 1 calc R . . C5 C 0.5419(3) 0.1032(3) 0.70198(16) 0.0223(7) Uani 1 1 d . . . N6 N 0.4819(2) 0.1927(2) 0.72052(12) 0.0183(6) Uani 1 1 d . . . C7 C 0.1949(3) 0.0204(3) 0.81529(16) 0.0217(7) Uani 1 1 d . . . C8 C 0.0865(3) 0.0188(3) 0.79564(17) 0.0275(8) Uani 1 1 d . . . C9 C -0.0019(3) -0.0218(3) 0.84371(19) 0.0358(9) Uani 1 1 d . . . H9 H -0.0757 -0.0238 0.8312 0.043 Uiso 1 1 calc R . . C10 C 0.0150(3) -0.0593(3) 0.90937(19) 0.0347(9) Uani 1 1 d . . . H10 H -0.0458 -0.0885 0.9411 0.042 Uiso 1 1 calc R . . C11 C 0.1210(3) -0.0540(3) 0.92818(17) 0.0291(8) Uani 1 1 d . . . H11 H 0.1318 -0.0780 0.9735 0.035 Uiso 1 1 calc R . . C12 C 0.2126(3) -0.0140(3) 0.88204(16) 0.0223(7) Uani 1 1 d . . . C13 C 0.3258(3) -0.0085(3) 0.90662(16) 0.0259(8) Uani 1 1 d . . . H13 H 0.3818 0.0214 0.8675 0.031 Uiso 1 1 calc R . . C14 C 0.3044(3) 0.0620(3) 0.9624(2) 0.0409(10) Uani 1 1 d . . . H14A H 0.2700 0.1320 0.9454 0.061 Uiso 1 1 calc R . . H14B H 0.3793 0.0660 0.9763 0.061 Uiso 1 1 calc R . . H14C H 0.2503 0.0336 1.0015 0.061 Uiso 1 1 calc R . . C15 C 0.3833(4) -0.1156(4) 0.9329(2) 0.0503(12) Uani 1 1 d . . . H15A H 0.3303 -0.1457 0.9719 0.075 Uiso 1 1 calc R . . H15B H 0.4572 -0.1089 0.9469 0.075 Uiso 1 1 calc R . . H15C H 0.3994 -0.1612 0.8969 0.075 Uiso 1 1 calc R . . C16 C 0.0616(3) 0.0589(3) 0.72482(18) 0.0355(10) Uani 1 1 d . . . H16 H 0.1333 0.0864 0.6974 0.043 Uiso 1 1 calc R . . C17 C -0.0451(5) 0.1528(5) 0.7281(3) 0.0295(13) Uiso 0.65 1 d P . . H17A H -0.0634 0.1755 0.6825 0.044 Uiso 0.65 1 calc PR . . H17B H -0.0227 0.2113 0.7457 0.044 Uiso 0.65 1 calc PR . . H17C H -0.1145 0.1290 0.7582 0.044 Uiso 0.65 1 calc PR . . C18 C 0.0337(6) -0.0248(5) 0.6896(3) 0.0457(16) Uiso 0.65 1 d P . . H18A H 0.0950 -0.0852 0.6918 0.069 Uiso 0.65 1 calc PR . . H18B H 0.0302 0.0019 0.6420 0.069 Uiso 0.65 1 calc PR . . H18C H -0.0425 -0.0457 0.7120 0.069 Uiso 0.65 1 calc PR . . C19 C 0.3634(4) -0.1258(3) 0.75090(19) 0.0393(10) Uani 1 1 d . . . H19A H 0.3630 -0.1536 0.7987 0.059 Uiso 1 1 calc R . . H19B H 0.4286 -0.1645 0.7224 0.059 Uiso 1 1 calc R . . H19C H 0.2889 -0.1335 0.7381 0.059 Uiso 1 1 calc R . . C20 C 0.6725(3) 0.0944(3) 0.67439(18) 0.0313(9) Uani 1 1 d . . . H20A H 0.6849 0.1208 0.6260 0.047 Uiso 1 1 calc R . . H20B H 0.7076 0.0211 0.6804 0.047 Uiso 1 1 calc R . . H20C H 0.7096 0.1355 0.6989 0.047 Uiso 1 1 calc R . . C21 C 0.5438(3) 0.2771(3) 0.72736(16) 0.0212(7) Uani 1 1 d . . . C22 C 0.5793(3) 0.3477(3) 0.67057(17) 0.0232(8) Uani 1 1 d . . . C23 C 0.6418(3) 0.4256(3) 0.67931(18) 0.0324(9) Uani 1 1 d . . . H23 H 0.6665 0.4742 0.6415 0.039 Uiso 1 1 calc R . . C24 C 0.6685(3) 0.4335(3) 0.7423(2) 0.0395(10) Uani 1 1 d . . . H24 H 0.7135 0.4854 0.7471 0.047 Uiso 1 1 calc R . . C25 C 0.6295(3) 0.3655(3) 0.79731(19) 0.0355(9) Uani 1 1 d . . . H25 H 0.6456 0.3729 0.8405 0.043 Uiso 1 1 calc R . . C26 C 0.5671(3) 0.2864(3) 0.79173(17) 0.0259(8) Uani 1 1 d . . . C27 C 0.5252(3) 0.2122(3) 0.85361(17) 0.0297(9) Uani 1 1 d . . . H27 H 0.4511 0.1898 0.8464 0.036 Uiso 1 1 calc R . . C28 C 0.4966(4) 0.2642(3) 0.91947(18) 0.0436(11) Uani 1 1 d . . . H28A H 0.4607 0.2163 0.9567 0.065 Uiso 1 1 calc R . . H28B H 0.4416 0.3284 0.9134 0.065 Uiso 1 1 calc R . . H28C H 0.5691 0.2809 0.9302 0.065 Uiso 1 1 calc R . . C29 C 0.6146(4) 0.1149(3) 0.8612(2) 0.0447(11) Uani 1 1 d . . . H29A H 0.6271 0.0790 0.8206 0.067 Uiso 1 1 calc R . . H29B H 0.5851 0.0682 0.9012 0.067 Uiso 1 1 calc R . . H29C H 0.6892 0.1348 0.8668 0.067 Uiso 1 1 calc R . . C30 C 0.5478(3) 0.3447(3) 0.60155(16) 0.0245(8) Uani 1 1 d . . . H30 H 0.5238 0.2747 0.6015 0.029 Uiso 1 1 calc R . . C31 C 0.4431(3) 0.4268(3) 0.59017(17) 0.0305(9) Uani 1 1 d . . . H31A H 0.3786 0.4186 0.6286 0.046 Uiso 1 1 calc R . . H31B H 0.4172 0.4182 0.5482 0.046 Uiso 1 1 calc R . . H31C H 0.4661 0.4966 0.5864 0.046 Uiso 1 1 calc R . . C32 C 0.6516(3) 0.3581(3) 0.54340(17) 0.0340(9) Uani 1 1 d . . . H32A H 0.6282 0.3510 0.5004 0.051 Uiso 1 1 calc R . . H32B H 0.7180 0.3046 0.5515 0.051 Uiso 1 1 calc R . . H32C H 0.6749 0.4274 0.5411 0.051 Uiso 1 1 calc R . . N33 N 0.3047(2) 0.1954(2) 0.61405(13) 0.0217(6) Uani 1 1 d . . . C34 C 0.3075(3) 0.1873(3) 0.55210(16) 0.0225(7) Uani 1 1 d . . . C35 C 0.4164(3) 0.1955(3) 0.50023(16) 0.0240(8) Uani 1 1 d . . . C36 C 0.4159(3) 0.2670(3) 0.44241(17) 0.0305(9) Uani 1 1 d . . . H36 H 0.3445 0.3091 0.4346 0.037 Uiso 1 1 calc R . . C37 C 0.5177(4) 0.2779(3) 0.39600(18) 0.0374(10) Uani 1 1 d . . . H37 H 0.5165 0.3281 0.3570 0.045 Uiso 1 1 calc R . . C38 C 0.6220(4) 0.2151(3) 0.4064(2) 0.0413(10) Uani 1 1 d . . . H38 H 0.6923 0.2228 0.3746 0.050 Uiso 1 1 calc R . . C39 C 0.6233(3) 0.1420(3) 0.4626(2) 0.0384(10) Uani 1 1 d . . . H39 H 0.6938 0.0974 0.4690 0.046 Uiso 1 1 calc R . . C40 C 0.5213(3) 0.1334(3) 0.51000(18) 0.0293(8) Uani 1 1 d . . . H40 H 0.5233 0.0844 0.5496 0.035 Uiso 1 1 calc R . . C41 C 0.2010(3) 0.1699(3) 0.52544(16) 0.0236(8) Uani 1 1 d . . . C42 C 0.2115(3) 0.1167(3) 0.46917(17) 0.0298(8) Uani 1 1 d . . . H42 H 0.2874 0.0923 0.4459 0.036 Uiso 1 1 calc R . . C43 C 0.1127(4) 0.0992(3) 0.4470(2) 0.0385(10) Uani 1 1 d . . . H43 H 0.1207 0.0605 0.4097 0.046 Uiso 1 1 calc R . . C44 C 0.0030(4) 0.1374(3) 0.4786(2) 0.0396(10) Uani 1 1 d . . . H44 H -0.0647 0.1267 0.4624 0.048 Uiso 1 1 calc R . . C45 C -0.0093(3) 0.1915(3) 0.5339(2) 0.0370(10) Uani 1 1 d . . . H45 H -0.0854 0.2181 0.5556 0.044 Uiso 1 1 calc R . . C46 C 0.0897(3) 0.2070(3) 0.55773(17) 0.0277(8) Uani 1 1 d . . . H46 H 0.0810 0.2431 0.5963 0.033 Uiso 1 1 calc R . . N47 N 0.2277(2) 0.3043(2) 0.74138(13) 0.0232(6) Uani 1 1 d . . . P48 P 0.18446(9) 0.43219(8) 0.75068(5) 0.0195(2) Uani 0.84 1 d P . . C49 C 0.2419(3) 0.4503(3) 0.8274(2) 0.0382(10) Uani 1 1 d . . . H49A H 0.1837 0.4311 0.8680 0.046 Uiso 1 1 calc R . . H49B H 0.3150 0.4008 0.8299 0.046 Uiso 1 1 calc R . . C50 C 0.2684(3) 0.5596(3) 0.83075(19) 0.0328(9) Uani 1 1 d . . . C51 C 0.3159(4) 0.5564(4) 0.8967(2) 0.0551(12) Uani 1 1 d . . . H51A H 0.3309 0.6263 0.9014 0.083 Uiso 1 1 calc R . . H51B H 0.3893 0.5080 0.8954 0.083 Uiso 1 1 calc R . . H51C H 0.2579 0.5328 0.9354 0.083 Uiso 1 1 calc R . . C52 C 0.3611(4) 0.5915(4) 0.7720(2) 0.0583(13) Uani 1 1 d . . . H52A H 0.3278 0.6048 0.7301 0.087 Uiso 1 1 calc R . . H52B H 0.4276 0.5354 0.7677 0.087 Uiso 1 1 calc R . . H52C H 0.3881 0.6551 0.7799 0.087 Uiso 1 1 calc R . . C53 C 0.1575(3) 0.6385(3) 0.8328(2) 0.0447(11) Uani 1 1 d . . . H53A H 0.1732 0.7046 0.8442 0.067 Uiso 1 1 calc R . . H53B H 0.0947 0.6118 0.8672 0.067 Uiso 1 1 calc R . . H53C H 0.1330 0.6500 0.7883 0.067 Uiso 1 1 calc R . . C54 C 0.0221(3) 0.4624(3) 0.77974(17) 0.0258(8) Uani 1 1 d . . . C55 C -0.0438(3) 0.4449(3) 0.84642(17) 0.0243(8) Uani 1 1 d . . . C56 C -0.1376(3) 0.5201(3) 0.86754(17) 0.0251(8) Uani 1 1 d . . . H56 H -0.1791 0.5100 0.9127 0.030 Uiso 1 1 calc R . . C57 C -0.1730(3) 0.6083(3) 0.82613(18) 0.0274(8) Uani 1 1 d . . . C58 C -0.1207(3) 0.6147(3) 0.75804(18) 0.0274(8) Uani 1 1 d . . . H58 H -0.1499 0.6706 0.7274 0.033 Uiso 1 1 calc R . . C59 C -0.0273(3) 0.5423(3) 0.73308(17) 0.0252(8) Uani 1 1 d . . . C60 C -0.0297(3) 0.3460(3) 0.89883(18) 0.0314(9) Uani 1 1 d . . . C61 C 0.0653(3) 0.2585(3) 0.8746(2) 0.0403(10) Uani 1 1 d . . . H61A H 0.0559 0.1944 0.9058 0.060 Uiso 1 1 calc R . . H61B H 0.1430 0.2783 0.8736 0.060 Uiso 1 1 calc R . . H61C H 0.0580 0.2467 0.8289 0.060 Uiso 1 1 calc R . . C62 C -0.0042(4) 0.3706(4) 0.96631(19) 0.0467(11) Uani 1 1 d . . . H62A H -0.0683 0.4211 0.9860 0.070 Uiso 1 1 calc R . . H62B H 0.0699 0.4001 0.9580 0.070 Uiso 1 1 calc R . . H62C H 0.0020 0.3063 0.9979 0.070 Uiso 1 1 calc R . . C63 C -0.1456(4) 0.3021(3) 0.9131(2) 0.0469(11) Uani 1 1 d . . . H63A H -0.1651 0.2889 0.8704 0.070 Uiso 1 1 calc R . . H63B H -0.2079 0.3524 0.9346 0.070 Uiso 1 1 calc R . . H63C H -0.1387 0.2366 0.9435 0.070 Uiso 1 1 calc R . . C64 C -0.2697(3) 0.6929(3) 0.8540(2) 0.0333(9) Uani 1 1 d . . . C65 C -0.2278(4) 0.7411(4) 0.9073(3) 0.0640(15) Uani 1 1 d . . . H65A H -0.1590 0.7756 0.8862 0.096 Uiso 1 1 calc R . . H65B H -0.2064 0.6864 0.9432 0.096 Uiso 1 1 calc R . . H65C H -0.2909 0.7926 0.9269 0.096 Uiso 1 1 calc R . . C66 C -0.3793(4) 0.6418(4) 0.8889(3) 0.0715(16) Uani 1 1 d . . . H66A H -0.4395 0.6943 0.9097 0.107 Uiso 1 1 calc R . . H66B H -0.3577 0.5858 0.9240 0.107 Uiso 1 1 calc R . . H66C H -0.4103 0.6126 0.8551 0.107 Uiso 1 1 calc R . . C67 C -0.3038(5) 0.7776(4) 0.8003(3) 0.0764(18) Uani 1 1 d . . . H67A H -0.3605 0.8322 0.8214 0.115 Uiso 1 1 calc R . . H67B H -0.3394 0.7486 0.7683 0.115 Uiso 1 1 calc R . . H67C H -0.2337 0.8076 0.7759 0.115 Uiso 1 1 calc R . . C68 C 0.0139(3) 0.5547(3) 0.65455(18) 0.0346(9) Uani 1 1 d . . . C69 C 0.1065(3) 0.6295(3) 0.6319(2) 0.0426(10) Uani 1 1 d . . . H69A H 0.1787 0.5989 0.6493 0.064 Uiso 1 1 calc R . . H69B H 0.0763 0.6962 0.6497 0.064 Uiso 1 1 calc R . . H69C H 0.1236 0.6410 0.5822 0.064 Uiso 1 1 calc R . . C70 C 0.0538(4) 0.4506(4) 0.6277(2) 0.0540(12) Uani 1 1 d . . . H70A H 0.0688 0.4612 0.5779 0.081 Uiso 1 1 calc R . . H70B H -0.0077 0.4055 0.6435 0.081 Uiso 1 1 calc R . . H70C H 0.1261 0.4176 0.6441 0.081 Uiso 1 1 calc R . . C71 C -0.0914(4) 0.6038(4) 0.6179(2) 0.0517(12) Uani 1 1 d . . . H71A H -0.0681 0.6000 0.5690 0.078 Uiso 1 1 calc R . . H71B H -0.1139 0.6770 0.6261 0.078 Uiso 1 1 calc R . . H71C H -0.1584 0.5654 0.6356 0.078 Uiso 1 1 calc R . . C17A C -0.0520(12) 0.0951(12) 0.7210(7) 0.054(4) Uiso 0.35 1 d P . . C18A C 0.1146(14) -0.0349(13) 0.6748(8) 0.063(4) Uiso 0.35 1 d P . . P48A P 0.1720(6) 0.3806(6) 0.8012(4) 0.0431(17) Uani 0.16 1 d P . . 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 0.0149(3) 0.0208(4) 0.0157(3) -0.0010(2) -0.0025(2) -0.0019(3) N2 0.0199(14) 0.0218(16) 0.0161(13) -0.0009(12) -0.0027(11) -0.0039(12) C3 0.0258(17) 0.0217(19) 0.0188(16) 0.0004(14) -0.0061(14) -0.0025(16) C4 0.0242(17) 0.0216(19) 0.0196(16) -0.0026(14) -0.0009(14) 0.0044(16) C5 0.0188(16) 0.028(2) 0.0183(16) 0.0003(15) -0.0041(13) 0.0000(16) N6 0.0169(13) 0.0221(16) 0.0151(13) 0.0006(12) -0.0038(11) -0.0014(12) C7 0.0216(16) 0.0204(19) 0.0213(16) -0.0005(14) 0.0017(14) -0.0056(15) C8 0.0223(17) 0.036(2) 0.0245(17) -0.0039(16) -0.0010(14) -0.0084(17) C9 0.0273(19) 0.047(3) 0.035(2) -0.0031(19) -0.0030(16) -0.0164(19) C10 0.031(2) 0.036(2) 0.033(2) 0.0019(18) 0.0054(17) -0.0133(19) C11 0.033(2) 0.029(2) 0.0208(17) 0.0018(16) 0.0025(15) -0.0055(18) C12 0.0237(17) 0.0174(19) 0.0232(17) -0.0024(14) -0.0003(14) 0.0002(15) C13 0.0256(18) 0.033(2) 0.0161(16) 0.0043(15) -0.0039(14) -0.0002(18) C14 0.037(2) 0.052(3) 0.038(2) -0.011(2) -0.0130(18) -0.003(2) C15 0.041(2) 0.052(3) 0.057(3) -0.006(2) -0.019(2) 0.010(2) C16 0.0293(19) 0.055(3) 0.0250(18) 0.0012(18) -0.0076(16) -0.017(2) C19 0.051(2) 0.028(2) 0.036(2) -0.0117(18) 0.0100(19) -0.011(2) C20 0.0191(17) 0.038(2) 0.033(2) -0.0035(18) -0.0018(15) 0.0014(17) C21 0.0149(15) 0.027(2) 0.0221(16) -0.0021(15) -0.0053(13) -0.0023(15) C22 0.0194(16) 0.026(2) 0.0245(17) -0.0014(15) -0.0041(14) -0.0055(15) C23 0.034(2) 0.034(2) 0.0303(19) 0.0014(17) -0.0037(16) -0.0160(18) C24 0.040(2) 0.047(3) 0.039(2) -0.0074(19) -0.0105(18) -0.023(2) C25 0.039(2) 0.047(3) 0.0276(19) -0.0050(18) -0.0148(17) -0.015(2) C26 0.0251(18) 0.030(2) 0.0258(18) -0.0035(15) -0.0085(15) -0.0072(16) C27 0.033(2) 0.034(2) 0.0243(18) 0.0027(16) -0.0124(16) -0.0075(19) C28 0.057(3) 0.051(3) 0.027(2) -0.0021(19) -0.0124(19) -0.014(2) C29 0.050(3) 0.051(3) 0.034(2) 0.002(2) -0.013(2) -0.013(2) C30 0.0257(18) 0.025(2) 0.0216(17) 0.0020(15) -0.0018(14) -0.0089(16) C31 0.033(2) 0.033(2) 0.0261(18) -0.0021(17) -0.0052(16) -0.0044(18) C32 0.031(2) 0.044(3) 0.0252(18) -0.0039(18) 0.0024(16) -0.0079(19) N33 0.0232(14) 0.0211(16) 0.0196(14) -0.0001(12) -0.0049(11) -0.0001(13) C34 0.0274(18) 0.0178(19) 0.0215(16) -0.0004(14) -0.0061(14) 0.0000(15) C35 0.0276(18) 0.027(2) 0.0177(16) -0.0046(15) 0.0007(14) -0.0085(17) C36 0.038(2) 0.031(2) 0.0214(17) -0.0014(16) -0.0037(16) -0.0061(18) C37 0.054(3) 0.037(2) 0.0214(18) -0.0065(17) 0.0036(18) -0.014(2) C38 0.041(2) 0.050(3) 0.035(2) -0.017(2) 0.0113(18) -0.021(2) C39 0.032(2) 0.043(3) 0.041(2) -0.016(2) 0.0010(18) -0.0040(19) C40 0.033(2) 0.027(2) 0.0278(18) -0.0055(16) -0.0056(16) -0.0024(18) C41 0.0282(18) 0.023(2) 0.0202(16) 0.0019(15) -0.0075(14) -0.0051(16) C42 0.033(2) 0.029(2) 0.0284(19) -0.0037(16) -0.0096(16) -0.0031(18) C43 0.049(2) 0.038(3) 0.036(2) -0.0086(19) -0.0180(19) -0.011(2) C44 0.041(2) 0.040(3) 0.044(2) 0.007(2) -0.027(2) -0.015(2) C45 0.0268(19) 0.042(3) 0.040(2) 0.0026(19) -0.0080(17) -0.0016(19) C46 0.0257(18) 0.031(2) 0.0266(18) 0.0013(16) -0.0089(15) -0.0027(17) N47 0.0196(14) 0.0267(17) 0.0218(14) -0.0041(13) -0.0012(12) -0.0005(13) P48 0.0178(5) 0.0175(6) 0.0194(5) 0.0017(5) 0.0019(4) -0.0007(5) C49 0.031(2) 0.038(3) 0.047(2) -0.010(2) -0.0077(18) -0.0046(19) C50 0.034(2) 0.032(2) 0.034(2) -0.0057(17) -0.0024(17) -0.0120(18) C51 0.050(3) 0.061(3) 0.056(3) -0.012(2) -0.007(2) -0.012(2) C52 0.053(3) 0.054(3) 0.062(3) 0.003(3) 0.006(2) -0.019(2) C53 0.041(2) 0.036(3) 0.058(3) -0.015(2) -0.006(2) -0.006(2) C54 0.0236(17) 0.023(2) 0.0307(18) -0.0095(16) 0.0005(15) -0.0033(16) C55 0.0227(17) 0.022(2) 0.0296(18) -0.0046(16) -0.0099(15) 0.0002(16) C56 0.0225(17) 0.026(2) 0.0250(17) -0.0024(16) -0.0032(14) -0.0012(16) C57 0.0210(17) 0.026(2) 0.037(2) -0.0113(17) -0.0054(16) -0.0018(16) C58 0.0279(19) 0.022(2) 0.033(2) -0.0009(16) -0.0099(16) -0.0041(16) C59 0.0226(17) 0.023(2) 0.0291(18) 0.0027(16) -0.0023(15) -0.0072(16) C60 0.031(2) 0.031(2) 0.0276(19) 0.0009(17) -0.0040(16) 0.0024(18) C61 0.041(2) 0.037(3) 0.036(2) 0.0064(19) -0.0010(19) -0.002(2) C62 0.049(3) 0.064(3) 0.026(2) 0.002(2) -0.0071(19) -0.010(2) C63 0.041(2) 0.036(3) 0.061(3) 0.014(2) -0.014(2) -0.011(2) C64 0.0261(19) 0.026(2) 0.045(2) -0.0091(19) -0.0066(17) 0.0084(18) C65 0.055(3) 0.052(3) 0.091(4) -0.041(3) -0.020(3) 0.014(3) C66 0.034(2) 0.057(3) 0.115(5) -0.027(3) 0.008(3) 0.009(2) C67 0.085(4) 0.067(4) 0.061(3) -0.014(3) -0.011(3) 0.042(3) C68 0.038(2) 0.033(2) 0.0280(19) 0.0024(17) 0.0015(17) -0.0045(19) C69 0.038(2) 0.042(3) 0.042(2) 0.011(2) -0.0046(19) -0.006(2) C70 0.074(3) 0.053(3) 0.032(2) -0.005(2) -0.003(2) -0.009(3) C71 0.047(3) 0.073(4) 0.035(2) -0.002(2) -0.004(2) -0.016(3) P48A 0.041(4) 0.043(4) 0.042(4) -0.003(3) -0.002(3) -0.004(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 N47 1.728(3) . ? Ti1 N33 1.915(3) . ? Ti1 N2 2.038(3) . ? Ti1 N6 2.048(3) . ? N2 C3 1.345(4) . ? N2 C7 1.441(4) . ? C3 C4 1.408(4) . ? C3 C19 1.502(5) . ? C4 C5 1.416(5) . ? C5 N6 1.329(4) . ? C5 C20 1.515(4) . ? N6 C21 1.450(4) . ? C7 C12 1.402(4) . ? C7 C8 1.404(5) . ? C8 C9 1.391(5) . ? C8 C16 1.516(5) . ? C9 C10 1.386(5) . ? C10 C11 1.380(5) . ? C11 C12 1.394(4) . ? C12 C13 1.516(5) . ? C13 C15 1.520(5) . ? C13 C14 1.520(5) . ? C16 C18 1.498(7) . ? C16 C17 1.603(7) . ? C21 C22 1.404(4) . ? C21 C26 1.406(4) . ? C22 C23 1.395(5) . ? C22 C30 1.517(4) . ? C23 C24 1.389(5) . ? C24 C25 1.372(5) . ? C25 C26 1.388(5) . ? C26 C27 1.519(5) . ? C27 C29 1.521(6) . ? C27 C28 1.539(5) . ? C30 C31 1.523(5) . ? C30 C32 1.532(4) . ? N33 C34 1.266(4) . ? C34 C35 1.494(4) . ? C34 C41 1.509(5) . ? C35 C36 1.386(5) . ? C35 C40 1.389(5) . ? C36 C37 1.380(5) . ? C37 C38 1.389(6) . ? C38 C39 1.375(6) . ? C39 C40 1.388(5) . ? C41 C46 1.386(5) . ? C41 C42 1.395(5) . ? C42 C43 1.380(5) . ? C43 C44 1.369(6) . ? C44 C45 1.382(6) . ? C45 C46 1.390(5) . ? N47 P48 1.695(3) . ? P48 C49 1.863(4) . ? P48 C54 1.873(3) . ? C49 C50 1.525(5) . ? C50 C52 1.505(5) . ? C50 C53 1.520(5) . ? C50 C51 1.532(6) . ? C54 C55 1.425(5) . ? C54 C59 1.428(5) . ? C55 C56 1.396(5) . ? C55 C60 1.555(5) . ? C56 C57 1.378(5) . ? C57 C58 1.391(5) . ? C57 C64 1.536(5) . ? C58 C59 1.394(5) . ? C59 C68 1.560(5) . ? C60 C63 1.517(5) . ? C60 C61 1.527(5) . ? C60 C62 1.539(5) . ? C64 C67 1.496(6) . ? C64 C65 1.516(6) . ? C64 C66 1.541(6) . ? C68 C70 1.510(6) . ? C68 C69 1.535(5) . ? C68 C71 1.561(6) . ? 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 N47 Ti1 N33 113.00(12) . . ? N47 Ti1 N2 114.50(12) . . ? N33 Ti1 N2 114.30(11) . . ? N47 Ti1 N6 108.72(12) . . ? N33 Ti1 N6 110.42(11) . . ? N2 Ti1 N6 94.20(10) . . ? C3 N2 C7 118.0(3) . . ? C3 N2 Ti1 106.4(2) . . ? C7 N2 Ti1 133.9(2) . . ? N2 C3 C4 124.0(3) . . ? N2 C3 C19 119.9(3) . . ? C4 C3 C19 116.1(3) . . ? C3 C4 C5 130.1(3) . . ? N6 C5 C4 122.7(3) . . ? N6 C5 C20 120.9(3) . . ? C4 C5 C20 116.5(3) . . ? C5 N6 C21 120.1(3) . . ? C5 N6 Ti1 107.8(2) . . ? C21 N6 Ti1 129.7(2) . . ? C12 C7 C8 121.3(3) . . ? C12 C7 N2 118.7(3) . . ? C8 C7 N2 120.1(3) . . ? C9 C8 C7 118.0(3) . . ? C9 C8 C16 118.8(3) . . ? C7 C8 C16 123.2(3) . . ? C10 C9 C8 121.6(3) . . ? C11 C10 C9 119.3(3) . . ? C10 C11 C12 121.4(3) . . ? C11 C12 C7 118.3(3) . . ? C11 C12 C13 118.5(3) . . ? C7 C12 C13 123.2(3) . . ? C12 C13 C15 112.1(3) . . ? C12 C13 C14 111.2(3) . . ? C15 C13 C14 108.8(3) . . ? C18 C16 C8 112.5(4) . . ? C18 C16 C17 109.4(4) . . ? C8 C16 C17 110.1(3) . . ? C22 C21 C26 121.2(3) . . ? C22 C21 N6 120.2(3) . . ? C26 C21 N6 118.6(3) . . ? C23 C22 C21 118.1(3) . . ? C23 C22 C30 119.4(3) . . ? C21 C22 C30 122.5(3) . . ? C24 C23 C22 121.2(3) . . ? C25 C24 C23 119.4(4) . . ? C24 C25 C26 122.0(3) . . ? C25 C26 C21 118.1(3) . . ? C25 C26 C27 120.7(3) . . ? C21 C26 C27 121.2(3) . . ? C26 C27 C29 111.1(3) . . ? C26 C27 C28 112.6(3) . . ? C29 C27 C28 110.1(3) . . ? C22 C30 C31 110.2(3) . . ? C22 C30 C32 112.7(3) . . ? C31 C30 C32 110.6(3) . . ? C34 N33 Ti1 174.7(3) . . ? N33 C34 C35 122.2(3) . . ? N33 C34 C41 122.4(3) . . ? C35 C34 C41 115.4(3) . . ? C36 C35 C40 118.6(3) . . ? C36 C35 C34 120.9(3) . . ? C40 C35 C34 120.5(3) . . ? C37 C36 C35 120.9(4) . . ? C36 C37 C38 119.9(4) . . ? C39 C38 C37 119.9(4) . . ? C38 C39 C40 119.9(4) . . ? C39 C40 C35 120.7(3) . . ? C46 C41 C42 118.9(3) . . ? C46 C41 C34 119.4(3) . . ? C42 C41 C34 121.7(3) . . ? C43 C42 C41 120.5(4) . . ? C44 C43 C42 120.2(4) . . ? C43 C44 C45 120.1(3) . . ? C44 C45 C46 120.1(4) . . ? C41 C46 C45 120.2(4) . . ? P48 N47 Ti1 157.40(17) . . ? N47 P48 C49 104.11(16) . . ? N47 P48 C54 112.57(15) . . ? C49 P48 C54 101.24(17) . . ? C50 C49 P48 116.0(3) . . ? C52 C50 C53 110.6(3) . . ? C52 C50 C49 110.9(3) . . ? C53 C50 C49 111.1(3) . . ? C52 C50 C51 108.4(4) . . ? C53 C50 C51 108.4(3) . . ? C49 C50 C51 107.3(3) . . ? C55 C54 C59 117.7(3) . . ? C55 C54 P48 128.6(3) . . ? C59 C54 P48 110.0(2) . . ? C56 C55 C54 118.4(3) . . ? C56 C55 C60 114.0(3) . . ? C54 C55 C60 127.4(3) . . ? C57 C56 C55 123.3(3) . . ? C56 C57 C58 117.1(3) . . ? C56 C57 C64 120.8(3) . . ? C58 C57 C64 122.0(3) . . ? C57 C58 C59 122.5(3) . . ? C58 C59 C54 118.9(3) . . ? C58 C59 C68 116.1(3) . . ? C54 C59 C68 125.0(3) . . ? C63 C60 C61 106.6(3) . . ? C63 C60 C62 108.3(3) . . ? C61 C60 C62 107.1(3) . . ? C63 C60 C55 106.8(3) . . ? C61 C60 C55 115.1(3) . . ? C62 C60 C55 112.6(3) . . ? C67 C64 C65 108.8(4) . . ? C67 C64 C57 113.0(3) . . ? C65 C64 C57 109.3(3) . . ? C67 C64 C66 108.9(4) . . ? C65 C64 C66 107.8(4) . . ? C57 C64 C66 108.9(3) . . ? C70 C68 C69 112.3(3) . . ? C70 C68 C59 112.1(3) . . ? C69 C68 C59 112.1(3) . . ? C70 C68 C71 104.0(4) . . ? C69 C68 C71 105.6(3) . . ? C59 C68 C71 110.3(3) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N47 Ti1 N2 C3 -167.1(2) . . . . ? N33 Ti1 N2 C3 60.3(2) . . . . ? N6 Ti1 N2 C3 -54.3(2) . . . . ? N47 Ti1 N2 C7 28.5(3) . . . . ? N33 Ti1 N2 C7 -104.1(3) . . . . ? N6 Ti1 N2 C7 141.3(3) . . . . ? C7 N2 C3 C4 -165.3(3) . . . . ? Ti1 N2 C3 C4 27.3(4) . . . . ? C7 N2 C3 C19 13.4(4) . . . . ? Ti1 N2 C3 C19 -154.0(3) . . . . ? N2 C3 C4 C5 16.8(6) . . . . ? C19 C3 C4 C5 -162.0(4) . . . . ? C3 C4 C5 N6 -17.0(6) . . . . ? C3 C4 C5 C20 164.4(3) . . . . ? C4 C5 N6 C21 169.2(3) . . . . ? C20 C5 N6 C21 -12.2(4) . . . . ? C4 C5 N6 Ti1 -26.9(4) . . . . ? C20 C5 N6 Ti1 151.7(3) . . . . ? N47 Ti1 N6 C5 172.6(2) . . . . ? N33 Ti1 N6 C5 -62.9(2) . . . . ? N2 Ti1 N6 C5 55.0(2) . . . . ? N47 Ti1 N6 C21 -25.6(3) . . . . ? N33 Ti1 N6 C21 98.9(3) . . . . ? N2 Ti1 N6 C21 -143.2(3) . . . . ? C3 N2 C7 C12 76.3(4) . . . . ? Ti1 N2 C7 C12 -120.6(3) . . . . ? C3 N2 C7 C8 -104.0(4) . . . . ? Ti1 N2 C7 C8 59.1(4) . . . . ? C12 C7 C8 C9 -2.5(5) . . . . ? N2 C7 C8 C9 177.8(3) . . . . ? C12 C7 C8 C16 177.6(3) . . . . ? N2 C7 C8 C16 -2.1(5) . . . . ? C7 C8 C9 C10 0.4(6) . . . . ? C16 C8 C9 C10 -179.8(4) . . . . ? C8 C9 C10 C11 1.7(6) . . . . ? C9 C10 C11 C12 -1.7(6) . . . . ? C10 C11 C12 C7 -0.4(5) . . . . ? C10 C11 C12 C13 178.8(3) . . . . ? C8 C7 C12 C11 2.5(5) . . . . ? N2 C7 C12 C11 -177.8(3) . . . . ? C8 C7 C12 C13 -176.6(3) . . . . ? N2 C7 C12 C13 3.1(5) . . . . ? C11 C12 C13 C15 60.5(4) . . . . ? C7 C12 C13 C15 -120.4(4) . . . . ? C11 C12 C13 C14 -61.5(4) . . . . ? C7 C12 C13 C14 117.6(4) . . . . ? C9 C8 C16 C18 -61.7(5) . . . . ? C7 C8 C16 C18 118.2(5) . . . . ? C9 C8 C16 C17 60.7(5) . . . . ? C7 C8 C16 C17 -119.5(4) . . . . ? C5 N6 C21 C22 85.9(4) . . . . ? Ti1 N6 C21 C22 -74.0(4) . . . . ? C5 N6 C21 C26 -94.2(4) . . . . ? Ti1 N6 C21 C26 105.9(3) . . . . ? C26 C21 C22 C23 2.0(5) . . . . ? N6 C21 C22 C23 -178.1(3) . . . . ? C26 C21 C22 C30 -175.5(3) . . . . ? N6 C21 C22 C30 4.4(5) . . . . ? C21 C22 C23 C24 0.0(5) . . . . ? C30 C22 C23 C24 177.6(3) . . . . ? C22 C23 C24 C25 -2.1(6) . . . . ? C23 C24 C25 C26 2.2(6) . . . . ? C24 C25 C26 C21 -0.2(6) . . . . ? C24 C25 C26 C27 179.9(4) . . . . ? C22 C21 C26 C25 -2.0(5) . . . . ? N6 C21 C26 C25 178.1(3) . . . . ? C22 C21 C26 C27 177.9(3) . . . . ? N6 C21 C26 C27 -2.0(5) . . . . ? C25 C26 C27 C29 -92.6(4) . . . . ? C21 C26 C27 C29 87.5(4) . . . . ? C25 C26 C27 C28 31.4(5) . . . . ? C21 C26 C27 C28 -148.5(3) . . . . ? C23 C22 C30 C31 -77.9(4) . . . . ? C21 C22 C30 C31 99.6(4) . . . . ? C23 C22 C30 C32 46.2(5) . . . . ? C21 C22 C30 C32 -136.3(3) . . . . ? N47 Ti1 N33 C34 172(3) . . . . ? N2 Ti1 N33 C34 -54(3) . . . . ? N6 Ti1 N33 C34 50(3) . . . . ? Ti1 N33 C34 C35 -60(3) . . . . ? Ti1 N33 C34 C41 121(3) . . . . ? N33 C34 C35 C36 -125.0(4) . . . . ? C41 C34 C35 C36 54.4(4) . . . . ? N33 C34 C35 C40 53.2(5) . . . . ? C41 C34 C35 C40 -127.4(3) . . . . ? C40 C35 C36 C37 -1.2(5) . . . . ? C34 C35 C36 C37 177.1(3) . . . . ? C35 C36 C37 C38 1.3(6) . . . . ? C36 C37 C38 C39 0.4(6) . . . . ? C37 C38 C39 C40 -2.2(6) . . . . ? C38 C39 C40 C35 2.3(6) . . . . ? C36 C35 C40 C39 -0.6(5) . . . . ? C34 C35 C40 C39 -178.8(3) . . . . ? N33 C34 C41 C46 28.7(5) . . . . ? C35 C34 C41 C46 -150.7(3) . . . . ? N33 C34 C41 C42 -150.9(3) . . . . ? C35 C34 C41 C42 29.7(5) . . . . ? C46 C41 C42 C43 -1.5(5) . . . . ? C34 C41 C42 C43 178.1(3) . . . . ? C41 C42 C43 C44 2.5(6) . . . . ? C42 C43 C44 C45 -1.6(6) . . . . ? C43 C44 C45 C46 -0.2(6) . . . . ? C42 C41 C46 C45 -0.3(5) . . . . ? C34 C41 C46 C45 -179.9(3) . . . . ? C44 C45 C46 C41 1.1(6) . . . . ? N33 Ti1 N47 P48 -63.0(5) . . . . ? N2 Ti1 N47 P48 163.8(4) . . . . ? N6 Ti1 N47 P48 60.0(5) . . . . ? Ti1 N47 P48 C49 -102.3(5) . . . . ? Ti1 N47 P48 C54 148.9(4) . . . . ? N47 P48 C49 C50 152.6(3) . . . . ? C54 P48 C49 C50 -90.4(3) . . . . ? P48 C49 C50 C52 -60.9(4) . . . . ? P48 C49 C50 C53 62.6(4) . . . . ? P48 C49 C50 C51 -179.1(3) . . . . ? N47 P48 C54 C55 78.7(3) . . . . ? C49 P48 C54 C55 -31.9(4) . . . . ? N47 P48 C54 C59 -123.9(2) . . . . ? C49 P48 C54 C59 125.5(3) . . . . ? C59 C54 C55 C56 -14.5(5) . . . . ? P48 C54 C55 C56 141.5(3) . . . . ? C59 C54 C55 C60 160.9(3) . . . . ? P48 C54 C55 C60 -43.1(5) . . . . ? C54 C55 C56 C57 3.0(5) . . . . ? C60 C55 C56 C57 -173.0(3) . . . . ? C55 C56 C57 C58 7.9(5) . . . . ? C55 C56 C57 C64 -174.7(3) . . . . ? C56 C57 C58 C59 -7.2(5) . . . . ? C64 C57 C58 C59 175.4(3) . . . . ? C57 C58 C59 C54 -4.3(5) . . . . ? C57 C58 C59 C68 174.6(3) . . . . ? C55 C54 C59 C58 15.1(5) . . . . ? P48 C54 C59 C58 -145.1(3) . . . . ? C55 C54 C59 C68 -163.8(3) . . . . ? P48 C54 C59 C68 36.0(4) . . . . ? C56 C55 C60 C63 56.8(4) . . . . ? C54 C55 C60 C63 -118.7(4) . . . . ? C56 C55 C60 C61 174.9(3) . . . . ? C54 C55 C60 C61 -0.6(5) . . . . ? C56 C55 C60 C62 -61.9(4) . . . . ? C54 C55 C60 C62 122.5(4) . . . . ? C56 C57 C64 C67 -174.7(4) . . . . ? C58 C57 C64 C67 2.6(5) . . . . ? C56 C57 C64 C65 64.0(5) . . . . ? C58 C57 C64 C65 -118.6(4) . . . . ? C56 C57 C64 C66 -53.5(5) . . . . ? C58 C57 C64 C66 123.8(4) . . . . ? C58 C59 C68 C70 -144.9(4) . . . . ? C54 C59 C68 C70 34.1(5) . . . . ? C58 C59 C68 C69 87.8(4) . . . . ? C54 C59 C68 C69 -93.3(4) . . . . ? C58 C59 C68 C71 -29.5(4) . . . . ? C54 C59 C68 C71 149.4(4) . . . . ? _diffrn_measured_fraction_theta_max 0.848 _diffrn_reflns_theta_full 27.54 _diffrn_measured_fraction_theta_full 0.848 _refine_diff_density_max 0.734 _refine_diff_density_min -0.354 _refine_diff_density_rms 0.064 data_03118 _database_code_CSD 218484 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C77 H132 N5 P Ti' _chemical_formula_weight 1206.75 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 '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' 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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P-1 ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.297(2) _cell_length_b 13.182(3) _cell_length_c 24.843(5) _cell_angle_alpha 103.400(5) _cell_angle_beta 92.806(6) _cell_angle_gamma 91.863(6) _cell_volume 3908.8(13) _cell_formula_units_Z 2 _cell_measurement_temperature 127(2) _cell_measurement_reflns_used 957 _cell_measurement_theta_min 2.44 _cell_measurement_theta_max 23.76 _exptl_crystal_description 'irregular fragment' _exptl_crystal_colour red/purple _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.025 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1332 _exptl_absorpt_coefficient_mu 0.171 _exptl_absorpt_correction_type none _exptl_special_details ; ? ; _diffrn_ambient_temperature 127(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_details ' 0.30 degree frames measured for 10.17 seconds each' _diffrn_measurement_method '\w scans' _diffrn_measurement_device 'three-circle goniometer with fixed chi' _diffrn_measurement_device_type 'Bruker Platform goniometer' _diffrn_detector 'CCD area detector' _diffrn_detector_type 'Bruker SMART 6000' _diffrn_detector_area_resol_mean 44.52 _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 47023 _diffrn_reflns_av_R_equivalents 0.1163 _diffrn_reflns_av_sigmaI/netI 0.0933 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 1.97 _diffrn_reflns_theta_max 25.01 _reflns_number_total 13721 _reflns_number_gt 9219 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 1999)' _computing_cell_refinement 'SAINT (Bruker, 1999)' _computing_data_reduction 'SAINT (Bruker, 1999), XTEL (local package)' _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^)+(0.1473P)^2^+3.7128P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 13721 _refine_ls_number_parameters 767 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1241 _refine_ls_R_factor_gt 0.0869 _refine_ls_wR_factor_ref 0.2567 _refine_ls_wR_factor_gt 0.2321 _refine_ls_goodness_of_fit_ref 1.022 _refine_ls_restrained_S_all 1.022 _refine_ls_shift/su_max 0.026 _refine_ls_shift/su_mean 0.001 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 1.07105(5) -0.00590(5) -0.22248(3) 0.0217(2) Uani 1 1 d . . . C2 C 0.8909(3) -0.0035(3) -0.22713(16) 0.0272(9) Uani 1 1 d . . . N3 N 0.7980(3) -0.0042(3) -0.23572(14) 0.0307(8) Uani 1 1 d . . . C4 C 0.6818(3) 0.0066(3) -0.24719(19) 0.0363(10) Uani 1 1 d . . . C5 C 0.6279(4) 0.0260(5) -0.1918(2) 0.0621(16) Uani 1 1 d . . . H5A H 0.6376 -0.0340 -0.1753 0.093 Uiso 1 1 calc R . . H5B H 0.5499 0.0356 -0.1979 0.093 Uiso 1 1 calc R . . H5C H 0.6617 0.0889 -0.1668 0.093 Uiso 1 1 calc R . . C6 C 0.6714(4) 0.1007(5) -0.2724(3) 0.0600(15) Uani 1 1 d . . . H6A H 0.7003 0.1635 -0.2455 0.090 Uiso 1 1 calc R . . H6B H 0.5945 0.1087 -0.2821 0.090 Uiso 1 1 calc R . . H6C H 0.7128 0.0905 -0.3058 0.090 Uiso 1 1 calc R . . C7 C 0.6371(4) -0.0925(4) -0.2875(2) 0.0525(13) Uani 1 1 d . . . H7A H 0.6729 -0.1006 -0.3225 0.079 Uiso 1 1 calc R . . H7B H 0.5584 -0.0882 -0.2942 0.079 Uiso 1 1 calc R . . H7C H 0.6512 -0.1527 -0.2717 0.079 Uiso 1 1 calc R . . N8 N 1.0638(3) 0.0013(2) -0.30375(13) 0.0244(7) Uani 1 1 d . . . C9 C 1.0094(3) 0.0757(3) -0.32428(16) 0.0275(9) Uani 1 1 d . . . C10 C 0.9782(4) 0.0643(3) -0.37927(17) 0.0338(10) Uani 1 1 d . . . H10 H 0.9897 -0.0016 -0.4031 0.041 Uiso 1 1 calc R . . C11 C 0.9300(4) 0.1411(3) -0.40495(18) 0.0361(10) Uani 1 1 d . . . N12 N 0.8920(3) 0.2261(3) -0.37621(16) 0.0410(9) Uani 1 1 d . . . C13 C 0.8577(4) 0.3053(3) -0.40235(18) 0.0384(11) Uani 1 1 d . . . C14 C 0.7465(4) 0.3210(4) -0.4073(2) 0.0449(12) Uani 1 1 d . . . C15 C 0.7129(4) 0.4040(4) -0.4289(2) 0.0472(12) Uani 1 1 d . . . H15 H 0.6376 0.4175 -0.4313 0.057 Uiso 1 1 calc R . . C16 C 0.7893(4) 0.4677(3) -0.4472(2) 0.0425(11) Uani 1 1 d . . . H16 H 0.7654 0.5211 -0.4643 0.051 Uiso 1 1 calc R . . C17 C 0.8966(4) 0.4531(3) -0.4406(2) 0.0411(11) Uani 1 1 d . . . H17 H 0.9475 0.4984 -0.4520 0.049 Uiso 1 1 calc R . . C18 C 0.9351(4) 0.3732(3) -0.41735(18) 0.0370(10) Uani 1 1 d . . . C19 C 1.0557(4) 0.3624(4) -0.4062(2) 0.0479(12) Uani 1 1 d . . . H19 H 1.0678 0.2878 -0.4060 0.058 Uiso 1 1 calc R . . C20 C 1.1263(6) 0.3923(7) -0.4493(3) 0.087(2) Uani 1 1 d . . . H20A H 1.1068 0.3461 -0.4857 0.131 Uiso 1 1 calc R . . H20B H 1.2032 0.3855 -0.4391 0.131 Uiso 1 1 calc R . . H20C H 1.1141 0.4648 -0.4508 0.131 Uiso 1 1 calc R . . C21 C 1.0936(5) 0.4295(5) -0.3495(3) 0.0667(16) Uani 1 1 d . . . H21A H 1.0916 0.5034 -0.3503 0.100 Uiso 1 1 calc R . . H21B H 1.1683 0.4131 -0.3401 0.100 Uiso 1 1 calc R . . H21C H 1.0453 0.4153 -0.3216 0.100 Uiso 1 1 calc R . . C22 C 0.6645(4) 0.2497(4) -0.3868(3) 0.0554(14) Uani 1 1 d . . . H22 H 0.6996 0.2325 -0.3530 0.067 Uiso 1 1 calc R . . C23 C 0.5584(5) 0.3018(6) -0.3697(3) 0.0759(19) Uani 1 1 d . . . H23A H 0.5749 0.3719 -0.3463 0.114 Uiso 1 1 calc R . . H23B H 0.5176 0.2600 -0.3489 0.114 Uiso 1 1 calc R . . H23C H 0.5145 0.3069 -0.4029 0.114 Uiso 1 1 calc R . . C24 C 0.6428(5) 0.1464(5) -0.4302(3) 0.0724(18) Uani 1 1 d . . . H24A H 0.6109 0.1605 -0.4645 0.109 Uiso 1 1 calc R . . H24B H 0.5922 0.1012 -0.4161 0.109 Uiso 1 1 calc R . . H24C H 0.7116 0.1117 -0.4377 0.109 Uiso 1 1 calc R . . C25 C 0.9294(5) 0.1160(4) -0.46766(19) 0.0468(12) Uani 1 1 d . . . H25A H 0.8838 0.1648 -0.4818 0.070 Uiso 1 1 calc R . . H25B H 0.9000 0.0444 -0.4827 0.070 Uiso 1 1 calc R . . H25C H 1.0040 0.1224 -0.4791 0.070 Uiso 1 1 calc R . . C26 C 0.9898(4) 0.1736(3) -0.28199(17) 0.0306(9) Uani 1 1 d . . . H26A H 1.0248 0.2335 -0.2925 0.046 Uiso 1 1 calc R . . H26B H 1.0206 0.1684 -0.2456 0.046 Uiso 1 1 calc R . . H26C H 0.9113 0.1831 -0.2802 0.046 Uiso 1 1 calc R . . C27 C 1.1078(3) -0.0814(3) -0.34497(16) 0.0255(8) Uani 1 1 d . . . C28 C 1.0541(3) -0.1797(3) -0.36201(16) 0.0290(9) Uani 1 1 d . . . C29 C 1.1032(4) -0.2580(3) -0.40014(18) 0.0345(10) Uani 1 1 d . . . H29 H 1.0684 -0.3255 -0.4112 0.041 Uiso 1 1 calc R . . C30 C 1.1998(4) -0.2394(3) -0.42180(18) 0.0376(10) Uani 1 1 d . . . H30 H 1.2322 -0.2937 -0.4472 0.045 Uiso 1 1 calc R . . C31 C 1.2505(4) -0.1398(3) -0.40617(18) 0.0362(10) Uani 1 1 d . . . H31 H 1.3168 -0.1267 -0.4220 0.043 Uiso 1 1 calc R . . C32 C 1.2066(3) -0.0594(3) -0.36823(17) 0.0289(9) Uani 1 1 d . . . C33 C 1.2617(3) 0.0491(3) -0.35482(19) 0.0351(10) Uani 1 1 d . . . H33 H 1.2188 0.0953 -0.3265 0.042 Uiso 1 1 calc R . . C34 C 1.2606(5) 0.0944(4) -0.4064(2) 0.0528(13) Uani 1 1 d . . . H34A H 1.3022 0.0505 -0.4348 0.079 Uiso 1 1 calc R . . H34B H 1.2938 0.1653 -0.3965 0.079 Uiso 1 1 calc R . . H34C H 1.1853 0.0963 -0.4208 0.079 Uiso 1 1 calc R . . C35 C 1.3779(4) 0.0500(4) -0.3302(2) 0.0401(11) Uani 1 1 d . . . H35A H 1.3776 0.0201 -0.2976 0.060 Uiso 1 1 calc R . . H35B H 1.4081 0.1220 -0.3193 0.060 Uiso 1 1 calc R . . H35C H 1.4228 0.0085 -0.3580 0.060 Uiso 1 1 calc R . . C36 C 0.9406(4) -0.2018(3) -0.3443(2) 0.0444(12) Uani 1 1 d . . . H36 H 0.9223 -0.1408 -0.3144 0.053 Uiso 1 1 calc R . . C37 C 0.8571(4) -0.2111(5) -0.3924(3) 0.0657(17) Uani 1 1 d . . . H37A H 0.8735 -0.2700 -0.4226 0.098 Uiso 1 1 calc R . . H37B H 0.8596 -0.1466 -0.4056 0.098 Uiso 1 1 calc R . . H37C H 0.7841 -0.2227 -0.3801 0.098 Uiso 1 1 calc R . . C38 C 0.9307(5) -0.2984(4) -0.3216(2) 0.0565(14) Uani 1 1 d . . . H38A H 0.8591 -0.3022 -0.3063 0.085 Uiso 1 1 calc R . . H38B H 0.9880 -0.2952 -0.2924 0.085 Uiso 1 1 calc R . . H38C H 0.9385 -0.3605 -0.3515 0.085 Uiso 1 1 calc R . . N40 N 1.1515(3) -0.1342(2) -0.21380(13) 0.0271(7) Uani 1 1 d . . . C41 C 1.0601(3) -0.1411(3) -0.19328(16) 0.0271(9) Uani 1 1 d . . . C42 C 1.0126(4) -0.2247(3) -0.16732(18) 0.0356(10) Uani 1 1 d . . . H42A H 1.0706 -0.2727 -0.1624 0.043 Uiso 1 1 calc R . . H42B H 0.9549 -0.2657 -0.1932 0.043 Uiso 1 1 calc R . . C43 C 0.9641(4) -0.1824(3) -0.11093(18) 0.0384(11) Uani 1 1 d . . . C44 C 0.8714(5) -0.1116(5) -0.1159(2) 0.0578(15) Uani 1 1 d . . . H44A H 0.8366 -0.0931 -0.0805 0.087 Uiso 1 1 calc R . . H44B H 0.8178 -0.1479 -0.1450 0.087 Uiso 1 1 calc R . . H44C H 0.9000 -0.0481 -0.1253 0.087 Uiso 1 1 calc R . . C45 C 1.0536(5) -0.1237(4) -0.0693(2) 0.0515(13) Uani 1 1 d . . . H45A H 1.0812 -0.0629 -0.0818 0.077 Uiso 1 1 calc R . . H45B H 1.1132 -0.1701 -0.0666 0.077 Uiso 1 1 calc R . . H45C H 1.0236 -0.1004 -0.0329 0.077 Uiso 1 1 calc R . . C47 C 1.2496(3) -0.2005(3) -0.21783(18) 0.0331(9) Uani 1 1 d . . . C48 C 1.3319(3) -0.1536(3) -0.25014(19) 0.0350(10) Uani 1 1 d . . . H48A H 1.3006 -0.1565 -0.2875 0.053 Uiso 1 1 calc R . . H48B H 1.3982 -0.1934 -0.2526 0.053 Uiso 1 1 calc R . . H48C H 1.3500 -0.0808 -0.2311 0.053 Uiso 1 1 calc R . . C49 C 1.2175(4) -0.3122(3) -0.2498(2) 0.0414(11) Uani 1 1 d . . . H49A H 1.1610 -0.3415 -0.2305 0.062 Uiso 1 1 calc R . . H49B H 1.2815 -0.3550 -0.2520 0.062 Uiso 1 1 calc R . . H49C H 1.1893 -0.3116 -0.2873 0.062 Uiso 1 1 calc R . . C50 C 1.2962(4) -0.1964(4) -0.1596(2) 0.0460(12) Uani 1 1 d . . . H50A H 1.3119 -0.1235 -0.1399 0.069 Uiso 1 1 calc R . . H50B H 1.3637 -0.2344 -0.1616 0.069 Uiso 1 1 calc R . . H50C H 1.2432 -0.2286 -0.1397 0.069 Uiso 1 1 calc R . . N51 N 1.0752(3) 0.1205(2) -0.16148(13) 0.0243(7) Uani 1 1 d . . . C52 C 1.1776(3) 0.1029(3) -0.17016(15) 0.0247(8) Uani 1 1 d . . . P53 P 1.31516(8) 0.12350(8) -0.16275(4) 0.0255(3) Uani 1 1 d . . . C54 C 1.3426(3) 0.2532(3) -0.11032(16) 0.0239(8) Uani 1 1 d . . . C55 C 1.3515(3) 0.2564(3) -0.05247(16) 0.0258(8) Uani 1 1 d . . . C56 C 1.3329(3) 0.3512(3) -0.01589(17) 0.0282(9) Uani 1 1 d . . . H56 H 1.3332 0.3532 0.0226 0.034 Uiso 1 1 calc R . . C57 C 1.3139(3) 0.4425(3) -0.03270(17) 0.0288(9) Uani 1 1 d . . . C58 C 1.3273(3) 0.4405(3) -0.08775(18) 0.0302(9) Uani 1 1 d . . . H58 H 1.3250 0.5041 -0.0995 0.036 Uiso 1 1 calc R . . C59 C 1.3444(3) 0.3476(3) -0.12726(17) 0.0275(9) Uani 1 1 d . . . C60 C 0.9201(4) -0.2782(4) -0.0909(2) 0.0484(12) Uani 1 1 d . . . H60A H 0.9809 -0.3209 -0.0843 0.073 Uiso 1 1 calc R . . H60B H 0.8683 -0.3200 -0.1193 0.073 Uiso 1 1 calc R . . H60C H 0.8833 -0.2542 -0.0564 0.073 Uiso 1 1 calc R . . C61 C 1.4691(4) 0.2959(4) -0.20573(18) 0.0377(10) Uani 1 1 d . . . H61A H 1.4527 0.2211 -0.2099 0.057 Uiso 1 1 calc R . . H61B H 1.5292 0.3191 -0.1778 0.057 Uiso 1 1 calc R . . H61C H 1.4899 0.3086 -0.2413 0.057 Uiso 1 1 calc R . . C62 C 1.2714(4) 0.3196(4) -0.22974(19) 0.0420(11) Uani 1 1 d . . . H62A H 1.2904 0.3306 -0.2659 0.063 Uiso 1 1 calc R . . H62B H 1.2075 0.3594 -0.2175 0.063 Uiso 1 1 calc R . . H62C H 1.2547 0.2452 -0.2329 0.063 Uiso 1 1 calc R . . C63 C 1.3962(5) 0.4718(4) -0.1889(2) 0.0493(13) Uani 1 1 d . . . H63A H 1.4257 0.4737 -0.2245 0.074 Uiso 1 1 calc R . . H63B H 1.4505 0.5024 -0.1588 0.074 Uiso 1 1 calc R . . H63C H 1.3301 0.5119 -0.1842 0.074 Uiso 1 1 calc R . . C64 C 1.2801(3) 0.5401(3) 0.00872(19) 0.0352(10) Uani 1 1 d . . . C65 C 1.1716(4) 0.5135(4) 0.0307(3) 0.0605(16) Uani 1 1 d . . . H65A H 1.1160 0.4953 0.0000 0.091 Uiso 1 1 calc R . . H65B H 1.1494 0.5740 0.0583 0.091 Uiso 1 1 calc R . . H65C H 1.1798 0.4542 0.0479 0.091 Uiso 1 1 calc R . . C66 C 1.3665(5) 0.5742(4) 0.0562(2) 0.0544(14) Uani 1 1 d . . . H66A H 1.3403 0.6322 0.0841 0.082 Uiso 1 1 calc R . . H66B H 1.4337 0.5968 0.0419 0.082 Uiso 1 1 calc R . . H66C H 1.3811 0.5155 0.0731 0.082 Uiso 1 1 calc R . . C67 C 1.2627(5) 0.6329(4) -0.0186(2) 0.0577(14) Uani 1 1 d . . . H67A H 1.2051 0.6135 -0.0483 0.087 Uiso 1 1 calc R . . H67B H 1.3306 0.6505 -0.0341 0.087 Uiso 1 1 calc R . . H67C H 1.2412 0.6933 0.0093 0.087 Uiso 1 1 calc R . . C68 C 1.3876(3) 0.1633(3) -0.02799(17) 0.0310(9) Uani 1 1 d . . . C69 C 1.2987(4) 0.0763(3) -0.03325(18) 0.0353(10) Uani 1 1 d . . . H69A H 1.3294 0.0175 -0.0207 0.053 Uiso 1 1 calc R . . H69B H 1.2716 0.0530 -0.0721 0.053 Uiso 1 1 calc R . . H69C H 1.2386 0.1031 -0.0103 0.053 Uiso 1 1 calc R . . C70 C 1.4894(4) 0.1178(3) -0.05723(18) 0.0351(10) Uani 1 1 d . . . H70A H 1.5182 0.0646 -0.0393 0.053 Uiso 1 1 calc R . . H70B H 1.5452 0.1738 -0.0545 0.053 Uiso 1 1 calc R . . H70C H 1.4694 0.0862 -0.0963 0.053 Uiso 1 1 calc R . . C71 C 1.4225(4) 0.1993(4) 0.03372(19) 0.0413(11) Uani 1 1 d . . . H71A H 1.3585 0.2206 0.0549 0.062 Uiso 1 1 calc R . . H71B H 1.4754 0.2585 0.0394 0.062 Uiso 1 1 calc R . . H71C H 1.4559 0.1417 0.0464 0.062 Uiso 1 1 calc R . . C72 C 1.0225(3) 0.2071(3) -0.12186(16) 0.0277(9) Uani 1 1 d . . . C73 C 0.8994(3) 0.1915(3) -0.13112(19) 0.0352(10) Uani 1 1 d . . . H73A H 0.8778 0.1943 -0.1692 0.053 Uiso 1 1 calc R . . H73B H 0.8646 0.2469 -0.1052 0.053 Uiso 1 1 calc R . . H73C H 0.8765 0.1235 -0.1249 0.053 Uiso 1 1 calc R . . C74 C 1.0563(4) 0.2029(4) -0.06271(17) 0.0364(10) Uani 1 1 d . . . H74A H 1.0349 0.1343 -0.0567 0.055 Uiso 1 1 calc R . . H74B H 1.0202 0.2573 -0.0367 0.055 Uiso 1 1 calc R . . H74C H 1.1355 0.2145 -0.0566 0.055 Uiso 1 1 calc R . . C75 C 1.0587(3) 0.3117(3) -0.13281(19) 0.0337(10) Uani 1 1 d . . . H75A H 1.1383 0.3201 -0.1284 0.051 Uiso 1 1 calc R . . H75B H 1.0265 0.3682 -0.1064 0.051 Uiso 1 1 calc R . . H75C H 1.0345 0.3140 -0.1707 0.051 Uiso 1 1 calc R . . C76 C 1.5869(7) -0.1687(9) -0.4592(4) 0.116(3) Uani 1 1 d . . . H76A H 1.5369 -0.1203 -0.4381 0.173 Uiso 1 1 calc R . . H76B H 1.5925 -0.1549 -0.4961 0.173 Uiso 1 1 calc R . . H76C H 1.6590 -0.1588 -0.4397 0.173 Uiso 1 1 calc R . . C77 C 1.5450(9) -0.2771(8) -0.4648(4) 0.116(3) Uani 1 1 d . . . H77A H 1.6017 -0.3248 -0.4809 0.139 Uiso 1 1 calc R . . H77B H 1.4808 -0.2903 -0.4915 0.139 Uiso 1 1 calc R . . C78 C 1.5127(6) -0.3045(6) -0.4123(3) 0.082(2) Uani 1 1 d . . . H78A H 1.5789 -0.2995 -0.3874 0.099 Uiso 1 1 calc R . . H86 H 1.4630 -0.2513 -0.3939 0.099 Uiso 1 1 calc R . . C79 C 1.4589(7) -0.4084(6) -0.4182(4) 0.093(3) Uani 1 1 d . . . H79A H 1.5085 -0.4619 -0.4363 0.112 Uiso 1 1 calc R . . H79B H 1.3925 -0.4137 -0.4431 0.112 Uiso 1 1 calc R . . C80 C 1.4270(9) -0.4333(8) -0.3641(5) 0.130(4) Uani 1 1 d . . . H80A H 1.4928 -0.4408 -0.3418 0.195 Uiso 1 1 calc R . . H80B H 1.3824 -0.4986 -0.3722 0.195 Uiso 1 1 calc R . . H80C H 1.3851 -0.3765 -0.3436 0.195 Uiso 1 1 calc R . . C81 C 1.8162(12) 0.4102(11) -0.2337(6) 0.174(5) Uiso 1 1 d . . . H81A H 1.8951 0.4111 -0.2257 0.261 Uiso 1 1 calc R . . H81B H 1.7935 0.3477 -0.2624 0.261 Uiso 1 1 calc R . . H81C H 1.7785 0.4095 -0.1999 0.261 Uiso 1 1 calc R . . C82 C 1.7917(15) 0.4933(14) -0.2510(8) 0.200(6) Uiso 1 1 d . . . H82A H 1.7694 0.4714 -0.2910 0.240 Uiso 1 1 calc R . . H82B H 1.8584 0.5391 -0.2472 0.240 Uiso 1 1 calc R . . C83 C 1.7097(12) 0.5517(11) -0.2241(6) 0.154(4) Uiso 1 1 d . . . H83A H 1.6437 0.5045 -0.2312 0.185 Uiso 1 1 calc R . . H83B H 1.7301 0.5629 -0.1840 0.185 Uiso 1 1 calc R . . C84 C 1.6758(12) 0.6452(11) -0.2310(6) 0.170(5) Uiso 1 1 d . . . H84A H 1.6539 0.6366 -0.2707 0.204 Uiso 1 1 calc R . . H84B H 1.7394 0.6954 -0.2225 0.204 Uiso 1 1 calc R . . C85 C 1.5877(9) 0.6926(9) -0.1994(5) 0.129(3) Uiso 1 1 d . . . H85A H 1.5186 0.6556 -0.2148 0.194 Uiso 1 1 calc R . . H85B H 1.5847 0.7659 -0.2012 0.194 Uiso 1 1 calc R . . H85C H 1.5998 0.6886 -0.1607 0.194 Uiso 1 1 calc R . . C93 C 1.3678(4) 0.3567(3) -0.18735(18) 0.0333(10) 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 0.0218(4) 0.0211(3) 0.0214(4) 0.0025(3) 0.0061(3) 0.0018(3) C2 0.024(2) 0.028(2) 0.028(2) 0.0033(16) 0.0081(16) 0.0002(16) N3 0.031(2) 0.0284(18) 0.0306(19) 0.0014(14) 0.0102(15) 0.0034(14) C4 0.024(2) 0.041(2) 0.041(3) 0.004(2) 0.0087(18) 0.0009(18) C5 0.032(3) 0.092(4) 0.058(4) 0.004(3) 0.018(2) 0.008(3) C6 0.034(3) 0.063(4) 0.088(4) 0.029(3) -0.005(3) 0.003(2) C7 0.031(3) 0.054(3) 0.064(3) -0.004(3) 0.002(2) -0.007(2) N8 0.0266(17) 0.0243(16) 0.0209(17) 0.0018(13) 0.0038(13) 0.0025(13) C9 0.026(2) 0.027(2) 0.028(2) 0.0027(16) 0.0080(17) 0.0001(16) C10 0.046(3) 0.023(2) 0.029(2) -0.0002(17) -0.0001(19) 0.0075(18) C11 0.042(3) 0.032(2) 0.033(2) 0.0027(18) 0.0017(19) 0.0073(19) N12 0.054(2) 0.034(2) 0.038(2) 0.0101(17) 0.0074(18) 0.0180(18) C13 0.051(3) 0.032(2) 0.032(2) 0.0065(19) 0.005(2) 0.016(2) C14 0.048(3) 0.039(3) 0.051(3) 0.017(2) 0.003(2) 0.007(2) C15 0.040(3) 0.044(3) 0.060(3) 0.016(2) 0.004(2) 0.015(2) C16 0.057(3) 0.026(2) 0.046(3) 0.012(2) 0.000(2) 0.005(2) C17 0.050(3) 0.031(2) 0.041(3) 0.006(2) 0.000(2) 0.002(2) C18 0.049(3) 0.029(2) 0.030(2) -0.0006(18) 0.006(2) 0.0082(19) C19 0.049(3) 0.042(3) 0.054(3) 0.013(2) -0.001(2) 0.007(2) C20 0.057(4) 0.143(7) 0.070(4) 0.034(5) 0.020(3) 0.032(4) C21 0.061(4) 0.075(4) 0.061(4) 0.017(3) -0.015(3) -0.010(3) C22 0.050(3) 0.054(3) 0.072(4) 0.032(3) 0.008(3) 0.011(2) C23 0.066(4) 0.084(5) 0.094(5) 0.046(4) 0.031(4) 0.017(3) C24 0.058(4) 0.061(4) 0.107(5) 0.036(4) 0.007(4) 0.002(3) C25 0.070(3) 0.041(3) 0.028(2) 0.003(2) -0.005(2) 0.019(2) C26 0.040(2) 0.028(2) 0.024(2) 0.0040(17) 0.0053(17) 0.0047(17) C27 0.028(2) 0.027(2) 0.0199(19) 0.0008(15) -0.0003(16) 0.0073(16) C28 0.033(2) 0.030(2) 0.022(2) 0.0013(16) 0.0043(17) 0.0026(17) C29 0.041(3) 0.027(2) 0.031(2) -0.0013(17) 0.0000(19) 0.0054(18) C30 0.041(3) 0.036(2) 0.034(2) 0.0016(19) 0.007(2) 0.0134(19) C31 0.033(2) 0.041(2) 0.034(2) 0.0074(19) 0.0059(19) 0.0075(19) C32 0.026(2) 0.034(2) 0.027(2) 0.0077(17) -0.0009(17) 0.0041(17) C33 0.031(2) 0.037(2) 0.037(2) 0.0076(19) 0.0077(19) -0.0020(18) C34 0.061(3) 0.047(3) 0.054(3) 0.023(3) -0.003(3) -0.011(2) C35 0.034(2) 0.048(3) 0.039(3) 0.012(2) 0.005(2) -0.007(2) C36 0.046(3) 0.032(2) 0.048(3) -0.010(2) 0.018(2) -0.004(2) C37 0.035(3) 0.061(4) 0.106(5) 0.029(3) 0.008(3) 0.004(3) C38 0.055(3) 0.063(3) 0.046(3) 0.007(3) 0.003(2) -0.024(3) N40 0.0283(18) 0.0258(17) 0.0269(18) 0.0048(14) 0.0051(14) 0.0008(13) C41 0.029(2) 0.0214(19) 0.029(2) 0.0025(16) 0.0037(17) -0.0005(15) C42 0.039(3) 0.034(2) 0.034(2) 0.0082(19) 0.0110(19) 0.0008(19) C43 0.050(3) 0.036(2) 0.031(2) 0.0091(19) 0.015(2) -0.001(2) C44 0.065(4) 0.066(4) 0.051(3) 0.024(3) 0.034(3) 0.016(3) C45 0.075(4) 0.048(3) 0.029(3) 0.003(2) 0.015(2) -0.014(3) C47 0.031(2) 0.035(2) 0.033(2) 0.0060(18) 0.0059(18) 0.0066(18) C48 0.029(2) 0.034(2) 0.043(3) 0.0088(19) 0.0096(19) 0.0076(18) C49 0.048(3) 0.029(2) 0.047(3) 0.005(2) 0.016(2) 0.007(2) C50 0.050(3) 0.054(3) 0.036(3) 0.010(2) 0.008(2) 0.012(2) N51 0.0223(17) 0.0235(16) 0.0246(17) -0.0001(13) 0.0045(13) 0.0017(13) C52 0.033(2) 0.0226(19) 0.0183(19) 0.0038(15) 0.0042(16) 0.0033(16) P53 0.0215(5) 0.0251(5) 0.0268(5) -0.0012(4) 0.0065(4) 0.0017(4) C54 0.0173(19) 0.0263(19) 0.024(2) -0.0023(15) 0.0054(15) 0.0007(15) C55 0.0176(19) 0.027(2) 0.030(2) 0.0009(16) 0.0062(16) -0.0016(15) C56 0.026(2) 0.032(2) 0.024(2) -0.0014(16) 0.0057(16) -0.0013(16) C57 0.023(2) 0.025(2) 0.034(2) -0.0041(17) 0.0081(17) -0.0017(15) C58 0.025(2) 0.026(2) 0.037(2) 0.0033(17) 0.0028(17) -0.0007(16) C59 0.022(2) 0.029(2) 0.030(2) 0.0024(17) 0.0027(16) -0.0005(16) C60 0.059(3) 0.052(3) 0.035(3) 0.012(2) 0.011(2) -0.011(2) C61 0.037(2) 0.046(3) 0.032(2) 0.011(2) 0.0114(19) -0.002(2) C62 0.045(3) 0.051(3) 0.032(2) 0.014(2) 0.004(2) 0.001(2) C63 0.064(3) 0.040(3) 0.047(3) 0.016(2) 0.011(2) -0.005(2) C64 0.030(2) 0.025(2) 0.044(3) -0.0072(18) 0.0112(19) 0.0008(17) C65 0.049(3) 0.037(3) 0.085(4) -0.015(3) 0.038(3) -0.001(2) C66 0.059(3) 0.044(3) 0.048(3) -0.014(2) 0.007(3) 0.003(2) C67 0.070(4) 0.035(3) 0.061(4) -0.007(2) 0.017(3) 0.009(2) C68 0.032(2) 0.030(2) 0.031(2) 0.0060(17) 0.0053(18) 0.0031(17) C69 0.043(3) 0.032(2) 0.033(2) 0.0110(18) 0.0088(19) 0.0027(19) C70 0.035(2) 0.036(2) 0.034(2) 0.0067(19) 0.0029(19) 0.0085(19) C71 0.049(3) 0.039(2) 0.036(3) 0.008(2) 0.006(2) 0.004(2) C72 0.025(2) 0.026(2) 0.026(2) -0.0066(16) 0.0071(16) 0.0046(16) C73 0.030(2) 0.034(2) 0.037(2) -0.0049(18) 0.0124(18) 0.0050(17) C74 0.037(2) 0.042(2) 0.028(2) -0.0016(18) 0.0132(18) 0.0063(19) C75 0.028(2) 0.030(2) 0.039(2) -0.0010(18) 0.0091(18) 0.0030(17) C76 0.091(6) 0.160(10) 0.104(7) 0.056(7) -0.018(5) -0.018(6) C77 0.162(10) 0.115(7) 0.072(6) 0.028(5) -0.013(6) 0.011(7) C78 0.063(4) 0.100(6) 0.074(5) 0.002(4) -0.006(3) 0.005(4) C79 0.078(5) 0.076(5) 0.112(7) -0.002(4) -0.016(4) 0.030(4) C80 0.144(9) 0.117(8) 0.136(9) 0.032(7) 0.060(7) 0.022(7) C93 0.034(2) 0.035(2) 0.031(2) 0.0084(18) 0.0044(18) -0.0014(18) _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 N51 1.973(3) . ? Ti1 N40 2.036(3) . ? Ti1 N8 2.041(3) . ? Ti1 C52 2.077(4) . ? Ti1 C41 2.078(4) . ? Ti1 C2 2.214(4) . ? C2 N3 1.151(5) . ? N3 C4 1.462(6) . ? C4 C7 1.518(7) . ? C4 C6 1.519(7) . ? C4 C5 1.527(7) . ? N8 C9 1.382(5) . ? N8 C27 1.450(5) . ? C9 C10 1.373(6) . ? C9 C26 1.498(5) . ? C10 C11 1.445(6) . ? C11 N12 1.295(6) . ? C11 C25 1.515(6) . ? N12 C13 1.416(6) . ? C13 C14 1.393(7) . ? C13 C18 1.408(7) . ? C14 C15 1.392(7) . ? C14 C22 1.539(7) . ? C15 C16 1.400(7) . ? C16 C17 1.347(7) . ? C17 C18 1.397(6) . ? C18 C19 1.513(7) . ? C19 C21 1.521(8) . ? C19 C20 1.524(8) . ? C22 C23 1.527(8) . ? C22 C24 1.535(9) . ? C27 C28 1.399(6) . ? C27 C32 1.421(6) . ? C28 C29 1.404(6) . ? C28 C36 1.523(6) . ? C29 C30 1.366(6) . ? C30 C31 1.396(6) . ? C31 C32 1.388(6) . ? C32 C33 1.520(6) . ? C33 C35 1.526(6) . ? C33 C34 1.533(7) . ? C36 C38 1.511(7) . ? C36 C37 1.517(8) . ? N40 C41 1.267(5) . ? N40 C47 1.506(5) . ? C41 C42 1.514(6) . ? C42 C43 1.540(6) . ? C43 C44 1.514(7) . ? C43 C45 1.530(7) . ? C43 C60 1.551(6) . ? C47 C50 1.519(6) . ? C47 C48 1.523(6) . ? C47 C49 1.531(6) . ? N51 C52 1.308(5) . ? N51 C72 1.510(5) . ? C52 P53 1.698(4) . ? P53 C54 1.903(4) . ? C54 C59 1.403(6) . ? C54 C55 1.427(6) . ? C55 C56 1.398(5) . ? C55 C68 1.558(6) . ? C56 C57 1.385(6) . ? C57 C58 1.380(6) . ? C57 C64 1.532(5) . ? C58 C59 1.409(6) . ? C59 C93 1.565(6) . ? C61 C93 1.534(6) . ? C62 C93 1.535(7) . ? C63 C93 1.555(6) . ? C64 C66 1.524(7) . ? C64 C65 1.526(6) . ? C64 C67 1.546(7) . ? C68 C71 1.531(6) . ? C68 C69 1.536(6) . ? C68 C70 1.546(6) . ? C72 C73 1.519(6) . ? C72 C74 1.521(6) . ? C72 C75 1.523(6) . ? C76 C77 1.477(12) . ? C77 C78 1.499(11) . ? C78 C79 1.474(11) . ? C79 C80 1.521(12) . ? C81 C82 1.305(17) . ? C82 C83 1.390(18) . ? C83 C84 1.359(15) . ? C84 C85 1.443(15) . ? 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 N51 Ti1 N40 120.78(14) . . ? N51 Ti1 N8 122.17(13) . . ? N40 Ti1 N8 109.53(13) . . ? N51 Ti1 C52 37.56(14) . . ? N40 Ti1 C52 96.28(14) . . ? N8 Ti1 C52 115.55(14) . . ? N51 Ti1 C41 111.68(15) . . ? N40 Ti1 C41 35.85(14) . . ? N8 Ti1 C41 125.90(14) . . ? C52 Ti1 C41 109.67(15) . . ? N51 Ti1 C2 88.90(14) . . ? N40 Ti1 C2 122.35(14) . . ? N8 Ti1 C2 86.97(14) . . ? C52 Ti1 C2 126.39(15) . . ? C41 Ti1 C2 89.31(15) . . ? N3 C2 Ti1 172.5(3) . . ? C2 N3 C4 173.8(4) . . ? N3 C4 C7 108.3(4) . . ? N3 C4 C6 107.1(4) . . ? C7 C4 C6 111.2(4) . . ? N3 C4 C5 107.3(4) . . ? C7 C4 C5 112.6(4) . . ? C6 C4 C5 110.2(4) . . ? C9 N8 C27 115.6(3) . . ? C9 N8 Ti1 124.3(2) . . ? C27 N8 Ti1 119.8(2) . . ? C10 C9 N8 123.7(4) . . ? C10 C9 C26 121.4(4) . . ? N8 C9 C26 114.8(3) . . ? C9 C10 C11 127.3(4) . . ? N12 C11 C10 122.2(4) . . ? N12 C11 C25 122.7(4) . . ? C10 C11 C25 115.0(4) . . ? C11 N12 C13 120.4(4) . . ? C14 C13 C18 121.1(4) . . ? C14 C13 N12 118.4(4) . . ? C18 C13 N12 120.2(4) . . ? C15 C14 C13 118.6(5) . . ? C15 C14 C22 121.7(5) . . ? C13 C14 C22 119.7(4) . . ? C14 C15 C16 120.5(5) . . ? C17 C16 C15 120.0(4) . . ? C16 C17 C18 121.9(4) . . ? C17 C18 C13 117.8(4) . . ? C17 C18 C19 121.5(4) . . ? C13 C18 C19 120.6(4) . . ? C18 C19 C21 110.2(4) . . ? C18 C19 C20 113.6(4) . . ? C21 C19 C20 108.4(5) . . ? C23 C22 C24 111.4(5) . . ? C23 C22 C14 113.4(4) . . ? C24 C22 C14 110.4(5) . . ? C28 C27 C32 120.7(3) . . ? C28 C27 N8 121.2(3) . . ? C32 C27 N8 118.1(3) . . ? C27 C28 C29 118.5(4) . . ? C27 C28 C36 122.3(3) . . ? C29 C28 C36 119.0(4) . . ? C30 C29 C28 121.7(4) . . ? C29 C30 C31 119.2(4) . . ? C32 C31 C30 121.9(4) . . ? C31 C32 C27 117.9(4) . . ? C31 C32 C33 119.9(4) . . ? C27 C32 C33 122.2(4) . . ? C32 C33 C35 112.2(4) . . ? C32 C33 C34 110.8(4) . . ? C35 C33 C34 110.3(4) . . ? C38 C36 C37 109.1(4) . . ? C38 C36 C28 114.1(4) . . ? C37 C36 C28 110.3(4) . . ? C41 N40 C47 132.6(3) . . ? C41 N40 Ti1 73.9(2) . . ? C47 N40 Ti1 153.4(3) . . ? N40 C41 C42 130.2(4) . . ? N40 C41 Ti1 70.3(2) . . ? C42 C41 Ti1 159.6(3) . . ? C41 C42 C43 114.3(3) . . ? C44 C43 C45 110.2(4) . . ? C44 C43 C42 111.5(4) . . ? C45 C43 C42 109.5(4) . . ? C44 C43 C60 109.2(4) . . ? C45 C43 C60 109.3(4) . . ? C42 C43 C60 107.0(4) . . ? N40 C47 C50 108.5(3) . . ? N40 C47 C48 107.0(3) . . ? C50 C47 C48 110.4(4) . . ? N40 C47 C49 109.9(4) . . ? C50 C47 C49 112.0(4) . . ? C48 C47 C49 108.8(3) . . ? C52 N51 C72 131.3(3) . . ? C52 N51 Ti1 75.5(2) . . ? C72 N51 Ti1 153.1(3) . . ? N51 C52 P53 158.1(3) . . ? N51 C52 Ti1 66.9(2) . . ? P53 C52 Ti1 135.0(2) . . ? C52 P53 C54 106.36(17) . . ? C59 C54 C55 118.8(3) . . ? C59 C54 P53 120.9(3) . . ? C55 C54 P53 120.1(3) . . ? C56 C55 C54 117.3(4) . . ? C56 C55 C68 118.6(4) . . ? C54 C55 C68 124.0(3) . . ? C57 C56 C55 123.6(4) . . ? C58 C57 C56 116.7(3) . . ? C58 C57 C64 122.6(4) . . ? C56 C57 C64 120.6(4) . . ? C57 C58 C59 122.5(4) . . ? C54 C59 C58 118.5(4) . . ? C54 C59 C93 123.8(3) . . ? C58 C59 C93 117.6(4) . . ? C66 C64 C65 110.5(4) . . ? C66 C64 C57 110.6(4) . . ? C65 C64 C57 107.9(3) . . ? C66 C64 C67 108.1(4) . . ? C65 C64 C67 107.5(4) . . ? C57 C64 C67 112.2(4) . . ? C71 C68 C69 106.6(3) . . ? C71 C68 C70 106.1(4) . . ? C69 C68 C70 109.7(3) . . ? C71 C68 C55 111.5(3) . . ? C69 C68 C55 114.0(3) . . ? C70 C68 C55 108.5(3) . . ? N51 C72 C73 109.0(3) . . ? N51 C72 C74 109.0(3) . . ? C73 C72 C74 109.6(3) . . ? N51 C72 C75 109.2(3) . . ? C73 C72 C75 109.6(3) . . ? C74 C72 C75 110.4(3) . . ? C76 C77 C78 115.8(8) . . ? C79 C78 C77 116.4(7) . . ? C78 C79 C80 114.9(7) . . ? C81 C82 C83 116.1(16) . . ? C84 C83 C82 127.5(14) . . ? C83 C84 C85 118.9(13) . . ? C61 C93 C62 110.5(4) . . ? C61 C93 C63 105.9(4) . . ? C62 C93 C63 106.3(4) . . ? C61 C93 C59 109.0(3) . . ? C62 C93 C59 113.8(3) . . ? C63 C93 C59 111.1(4) . . ? 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 N51 Ti1 C2 N3 134(3) . . . . ? N40 Ti1 C2 N3 -99(3) . . . . ? N8 Ti1 C2 N3 12(3) . . . . ? C52 Ti1 C2 N3 132(3) . . . . ? C41 Ti1 C2 N3 -114(3) . . . . ? Ti1 C2 N3 C4 -81(5) . . . . ? C2 N3 C4 C7 137(4) . . . . ? C2 N3 C4 C6 17(4) . . . . ? C2 N3 C4 C5 -101(4) . . . . ? N51 Ti1 N8 C9 -33.9(4) . . . . ? N40 Ti1 N8 C9 176.3(3) . . . . ? C52 Ti1 N8 C9 -76.4(3) . . . . ? C41 Ti1 N8 C9 139.9(3) . . . . ? C2 Ti1 N8 C9 52.9(3) . . . . ? N51 Ti1 N8 C27 152.8(3) . . . . ? N40 Ti1 N8 C27 2.9(3) . . . . ? C52 Ti1 N8 C27 110.3(3) . . . . ? C41 Ti1 N8 C27 -33.5(3) . . . . ? C2 Ti1 N8 C27 -120.4(3) . . . . ? C27 N8 C9 C10 12.8(6) . . . . ? Ti1 N8 C9 C10 -160.8(3) . . . . ? C27 N8 C9 C26 -165.0(3) . . . . ? Ti1 N8 C9 C26 21.4(5) . . . . ? N8 C9 C10 C11 -174.2(4) . . . . ? C26 C9 C10 C11 3.5(7) . . . . ? C9 C10 C11 N12 -12.9(8) . . . . ? C9 C10 C11 C25 165.8(4) . . . . ? C10 C11 N12 C13 172.2(4) . . . . ? C25 C11 N12 C13 -6.5(7) . . . . ? C11 N12 C13 C14 109.0(5) . . . . ? C11 N12 C13 C18 -77.8(6) . . . . ? C18 C13 C14 C15 1.8(7) . . . . ? N12 C13 C14 C15 175.0(4) . . . . ? C18 C13 C14 C22 -175.8(5) . . . . ? N12 C13 C14 C22 -2.7(7) . . . . ? C13 C14 C15 C16 2.3(8) . . . . ? C22 C14 C15 C16 179.9(5) . . . . ? C14 C15 C16 C17 -4.3(8) . . . . ? C15 C16 C17 C18 2.1(7) . . . . ? C16 C17 C18 C13 1.9(7) . . . . ? C16 C17 C18 C19 -175.4(4) . . . . ? C14 C13 C18 C17 -3.9(7) . . . . ? N12 C13 C18 C17 -177.0(4) . . . . ? C14 C13 C18 C19 173.4(4) . . . . ? N12 C13 C18 C19 0.4(6) . . . . ? C17 C18 C19 C21 86.6(6) . . . . ? C13 C18 C19 C21 -90.7(5) . . . . ? C17 C18 C19 C20 -35.2(7) . . . . ? C13 C18 C19 C20 147.5(5) . . . . ? C15 C14 C22 C23 -24.3(8) . . . . ? C13 C14 C22 C23 153.3(5) . . . . ? C15 C14 C22 C24 101.5(6) . . . . ? C13 C14 C22 C24 -80.9(6) . . . . ? C9 N8 C27 C28 -100.7(4) . . . . ? Ti1 N8 C27 C28 73.2(4) . . . . ? C9 N8 C27 C32 78.6(4) . . . . ? Ti1 N8 C27 C32 -107.5(3) . . . . ? C32 C27 C28 C29 3.7(6) . . . . ? N8 C27 C28 C29 -177.1(4) . . . . ? C32 C27 C28 C36 -171.2(4) . . . . ? N8 C27 C28 C36 8.0(6) . . . . ? C27 C28 C29 C30 -1.8(6) . . . . ? C36 C28 C29 C30 173.3(4) . . . . ? C28 C29 C30 C31 -0.8(7) . . . . ? C29 C30 C31 C32 1.5(7) . . . . ? C30 C31 C32 C27 0.4(6) . . . . ? C30 C31 C32 C33 -176.8(4) . . . . ? C28 C27 C32 C31 -3.0(6) . . . . ? N8 C27 C32 C31 177.7(4) . . . . ? C28 C27 C32 C33 174.1(4) . . . . ? N8 C27 C32 C33 -5.1(6) . . . . ? C31 C32 C33 C35 -60.7(5) . . . . ? C27 C32 C33 C35 122.2(4) . . . . ? C31 C32 C33 C34 63.0(5) . . . . ? C27 C32 C33 C34 -114.1(5) . . . . ? C27 C28 C36 C38 -130.4(4) . . . . ? C29 C28 C36 C38 54.6(6) . . . . ? C27 C28 C36 C37 106.3(5) . . . . ? C29 C28 C36 C37 -68.6(5) . . . . ? N51 Ti1 N40 C41 84.8(3) . . . . ? N8 Ti1 N40 C41 -124.8(2) . . . . ? C52 Ti1 N40 C41 115.2(2) . . . . ? C2 Ti1 N40 C41 -25.7(3) . . . . ? N51 Ti1 N40 C47 -89.7(6) . . . . ? N8 Ti1 N40 C47 60.6(6) . . . . ? C52 Ti1 N40 C47 -59.3(6) . . . . ? C41 Ti1 N40 C47 -174.5(7) . . . . ? C2 Ti1 N40 C47 159.7(6) . . . . ? C47 N40 C41 C42 -3.9(7) . . . . ? Ti1 N40 C41 C42 179.4(5) . . . . ? C47 N40 C41 Ti1 176.7(4) . . . . ? N51 Ti1 C41 N40 -113.0(2) . . . . ? N8 Ti1 C41 N40 72.7(3) . . . . ? C52 Ti1 C41 N40 -72.8(3) . . . . ? C2 Ti1 C41 N40 158.5(2) . . . . ? N51 Ti1 C41 C42 68.3(9) . . . . ? N40 Ti1 C41 C42 -178.8(10) . . . . ? N8 Ti1 C41 C42 -106.0(9) . . . . ? C52 Ti1 C41 C42 108.5(9) . . . . ? C2 Ti1 C41 C42 -20.3(9) . . . . ? N40 C41 C42 C43 131.0(5) . . . . ? Ti1 C41 C42 C43 -50.5(11) . . . . ? C41 C42 C43 C44 60.7(5) . . . . ? C41 C42 C43 C45 -61.5(5) . . . . ? C41 C42 C43 C60 -179.9(4) . . . . ? C41 N40 C47 C50 -63.8(6) . . . . ? Ti1 N40 C47 C50 109.1(6) . . . . ? C41 N40 C47 C48 177.1(4) . . . . ? Ti1 N40 C47 C48 -10.0(8) . . . . ? C41 N40 C47 C49 59.0(6) . . . . ? Ti1 N40 C47 C49 -128.1(5) . . . . ? N40 Ti1 N51 C52 55.5(3) . . . . ? N8 Ti1 N51 C52 -91.0(2) . . . . ? C41 Ti1 N51 C52 94.4(2) . . . . ? C2 Ti1 N51 C52 -176.8(2) . . . . ? N40 Ti1 N51 C72 -128.3(6) . . . . ? N8 Ti1 N51 C72 85.1(6) . . . . ? C52 Ti1 N51 C72 176.2(7) . . . . ? C41 Ti1 N51 C72 -89.4(6) . . . . ? C2 Ti1 N51 C72 -0.6(6) . . . . ? C72 N51 C52 P53 -1.8(11) . . . . ? Ti1 N51 C52 P53 175.9(8) . . . . ? C72 N51 C52 Ti1 -177.7(4) . . . . ? N40 Ti1 C52 N51 -134.5(2) . . . . ? N8 Ti1 C52 N51 110.3(2) . . . . ? C41 Ti1 C52 N51 -100.3(2) . . . . ? C2 Ti1 C52 N51 4.0(3) . . . . ? N51 Ti1 C52 P53 -177.8(4) . . . . ? N40 Ti1 C52 P53 47.6(3) . . . . ? N8 Ti1 C52 P53 -67.5(3) . . . . ? C41 Ti1 C52 P53 81.9(3) . . . . ? C2 Ti1 C52 P53 -173.8(2) . . . . ? N51 C52 P53 C54 -2.2(9) . . . . ? Ti1 C52 P53 C54 172.4(3) . . . . ? C52 P53 C54 C59 -86.9(3) . . . . ? C52 P53 C54 C55 87.3(3) . . . . ? C59 C54 C55 C56 16.5(5) . . . . ? P53 C54 C55 C56 -157.8(3) . . . . ? C59 C54 C55 C68 -159.6(4) . . . . ? P53 C54 C55 C68 26.2(5) . . . . ? C54 C55 C56 C57 -4.6(6) . . . . ? C68 C55 C56 C57 171.7(4) . . . . ? C55 C56 C57 C58 -7.8(6) . . . . ? C55 C56 C57 C64 172.3(4) . . . . ? C56 C57 C58 C59 8.7(6) . . . . ? C64 C57 C58 C59 -171.5(4) . . . . ? C55 C54 C59 C58 -15.8(5) . . . . ? P53 C54 C59 C58 158.5(3) . . . . ? C55 C54 C59 C93 162.3(4) . . . . ? P53 C54 C59 C93 -23.5(5) . . . . ? C57 C58 C59 C54 3.0(6) . . . . ? C57 C58 C59 C93 -175.2(4) . . . . ? C58 C57 C64 C66 -120.4(5) . . . . ? C56 C57 C64 C66 59.4(5) . . . . ? C58 C57 C64 C65 118.7(5) . . . . ? C56 C57 C64 C65 -61.5(6) . . . . ? C58 C57 C64 C67 0.4(6) . . . . ? C56 C57 C64 C67 -179.8(4) . . . . ? C56 C55 C68 C71 -13.3(5) . . . . ? C54 C55 C68 C71 162.7(4) . . . . ? C56 C55 C68 C69 107.6(4) . . . . ? C54 C55 C68 C69 -76.4(5) . . . . ? C56 C55 C68 C70 -129.8(4) . . . . ? C54 C55 C68 C70 46.2(5) . . . . ? C52 N51 C72 C73 177.4(4) . . . . ? Ti1 N51 C72 C73 2.4(7) . . . . ? C52 N51 C72 C74 -62.9(5) . . . . ? Ti1 N51 C72 C74 122.0(5) . . . . ? C52 N51 C72 C75 57.7(5) . . . . ? Ti1 N51 C72 C75 -117.3(5) . . . . ? C76 C77 C78 C79 173.1(8) . . . . ? C77 C78 C79 C80 -179.8(8) . . . . ? C81 C82 C83 C84 173.9(16) . . . . ? C82 C83 C84 C85 179.1(16) . . . . ? C54 C59 C93 C61 -47.7(5) . . . . ? C58 C59 C93 C61 130.3(4) . . . . ? C54 C59 C93 C62 76.0(5) . . . . ? C58 C59 C93 C62 -105.9(4) . . . . ? C54 C59 C93 C63 -164.0(4) . . . . ? C58 C59 C93 C63 14.1(5) . . . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 1.629 _refine_diff_density_min -0.586 _refine_diff_density_rms 0.088