# 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_1 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C28 H54 N6 Ti2' _chemical_formula_sum 'C28 H54 N6 Ti2' _chemical_formula_weight 570.51 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 8.67590(10) _cell_length_b 18.4936(4) _cell_length_c 10.1458(2) _cell_angle_alpha 90 _cell_angle_beta 109.043(3) _cell_angle_gamma 90 _cell_volume 1538.79(5) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 1.65 _cell_measurement_theta_max 26.05 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour purple _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.08 _exptl_crystal_density_diffrn 1.231 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 616 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.545 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; (See: Walker, N. & Stuart, D. (1983) Acta Cryst. A39, 158-166) ; _exptl_absorpt_correction_T_min 0.686 _exptl_absorpt_correction_T_max 0.915 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(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 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 4 _diffrn_standards_decay_% 0.1 _diffrn_reflns_av_R_equivalents 0.043 _diffrn_reflns_av_unetI/netI 0.0361 _diffrn_reflns_number 11893 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.39 _diffrn_reflns_theta_max 26.01 _diffrn_reflns_theta_full 26.01 _diffrn_measured_fraction_theta_full 0.988 _diffrn_measured_fraction_theta_max 0.988 _reflns_number_total 2994 _reflns_number_gt 2303 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'Stoe IPDS software (Stoe, 1996)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0524P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 2994 _refine_ls_number_parameters 167 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0523 _refine_ls_R_factor_gt 0.0353 _refine_ls_wR_factor_ref 0.0867 _refine_ls_wR_factor_gt 0.0812 _refine_ls_goodness_of_fit_ref 1.022 _refine_ls_restrained_S_all 1.022 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.289 _refine_diff_density_min -0.278 _refine_diff_density_rms 0.05 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 0.53018(4) 0.057118(19) 0.59577(3) 0.02102(11) Uani 1 1 d . . . N1 N 0.37194(17) 0.03475(9) 0.41936(16) 0.0226(3) Uani 1 1 d . . . N2 N 0.4398(2) 0.06523(10) 0.74321(17) 0.0309(4) Uani 1 1 d . . . N3 N 0.6631(2) 0.13931(10) 0.59539(19) 0.0329(4) Uani 1 1 d . . . C1 C 0.2662(2) 0.08255(10) 0.31210(19) 0.0212(4) Uani 1 1 d . . . C2 C 0.1199(2) 0.03877(11) 0.2203(2) 0.0260(4) Uani 1 1 d . . . H2A H 0.1592 -0.0015 0.1753 0.031 Uiso 1 1 calc R . . H2B H 0.0598 0.0178 0.279 0.031 Uiso 1 1 calc R . . C3 C 0.0055(2) 0.08735(12) 0.1083(2) 0.0307(4) Uani 1 1 d . . . H3 H -0.0888 0.0581 0.0495 0.037 Uiso 1 1 calc R . . C4 C 0.0976(3) 0.11874(13) 0.0167(2) 0.0372(5) Uani 1 1 d . . . H4A H 0.0236 0.1495 -0.0568 0.045 Uiso 1 1 calc R . . H4B H 0.1375 0.0791 -0.0292 0.045 Uiso 1 1 calc R . . C5 C 0.2420(3) 0.16377(12) 0.1062(2) 0.0346(5) Uani 1 1 d . . . H5 H 0.3023 0.1843 0.0459 0.042 Uiso 1 1 calc R . . C6 C 0.3571(2) 0.11488(12) 0.2187(2) 0.0299(4) Uani 1 1 d . . . H6A H 0.3985 0.0754 0.1735 0.036 Uiso 1 1 calc R . . H6B H 0.4516 0.1435 0.2763 0.036 Uiso 1 1 calc R . . C7 C 0.2015(2) 0.14470(11) 0.3794(2) 0.0285(4) Uani 1 1 d . . . H7A H 0.2941 0.1735 0.4391 0.034 Uiso 1 1 calc R . . H7B H 0.1416 0.1247 0.4392 0.034 Uiso 1 1 calc R . . C8 C 0.0874(2) 0.19364(12) 0.2674(2) 0.0316(5) Uani 1 1 d . . . H8 H 0.0465 0.2338 0.3132 0.038 Uiso 1 1 calc R . . C9 C -0.0571(2) 0.14897(12) 0.1769(2) 0.0331(5) Uani 1 1 d . . . H9A H -0.1188 0.1291 0.2354 0.04 Uiso 1 1 calc R . . H9B H -0.1314 0.1801 0.1044 0.04 Uiso 1 1 calc R . . C10 C 0.1807(3) 0.22533(12) 0.1762(2) 0.0372(5) Uani 1 1 d . . . H10A H 0.1082 0.2574 0.1045 0.045 Uiso 1 1 calc R . . H10B H 0.2741 0.2543 0.2344 0.045 Uiso 1 1 calc R . . C21 C 0.2790(3) 0.04155(17) 0.7389(3) 0.0499(7) Uani 1 1 d . . . H21A H 0.2219 0.0204 0.6474 0.075 Uiso 1 1 calc R . . H21B H 0.217 0.083 0.7548 0.075 Uiso 1 1 calc R . . H21C H 0.2894 0.0052 0.8116 0.075 Uiso 1 1 calc R . . C22 C 0.5299(3) 0.09592(16) 0.8773(2) 0.0477(6) Uani 1 1 d . . . H22A H 0.6368 0.1124 0.8761 0.072 Uiso 1 1 calc R . . H22B H 0.5445 0.0592 0.95 0.072 Uiso 1 1 calc R . . H22C H 0.4693 0.137 0.8967 0.072 Uiso 1 1 calc R . . C31 C 0.6316(3) 0.20989(13) 0.6420(3) 0.0486(6) Uani 1 1 d . . . H31A H 0.5386 0.207 0.6765 0.073 Uiso 1 1 calc R . . H31B H 0.6068 0.2441 0.564 0.073 Uiso 1 1 calc R . . H31C H 0.7281 0.2265 0.7172 0.073 Uiso 1 1 calc R . . C32 C 0.8023(3) 0.14076(16) 0.5461(3) 0.0550(7) Uani 1 1 d . . . H32A H 0.8184 0.0926 0.5125 0.082 Uiso 1 1 calc R . . H32B H 0.8999 0.1549 0.6227 0.082 Uiso 1 1 calc R . . H32C H 0.7825 0.1758 0.4699 0.082 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 0.02005(16) 0.02032(18) 0.02121(17) -0.00109(15) 0.00472(11) -0.00052(14) N1 0.0177(7) 0.0258(9) 0.0233(8) 0.0021(6) 0.0053(6) 0.0008(6) N2 0.0342(9) 0.0328(10) 0.0269(8) -0.0009(8) 0.0116(7) 0.0032(7) N3 0.0289(8) 0.0282(10) 0.0393(10) -0.0010(8) 0.0079(7) -0.0077(7) C1 0.0203(8) 0.0212(9) 0.0214(9) 0.0005(7) 0.0058(7) 0.0029(7) C2 0.0254(9) 0.0265(11) 0.0234(9) -0.0021(7) 0.0043(7) 0.0007(7) C3 0.0292(10) 0.0301(11) 0.0250(10) -0.0026(8) -0.0016(8) 0.0010(8) C4 0.0509(13) 0.0371(14) 0.0214(10) 0.0039(9) 0.0090(9) 0.0139(10) C5 0.0418(11) 0.0318(12) 0.0350(11) 0.0126(9) 0.0190(9) 0.0062(9) C6 0.0287(9) 0.0293(11) 0.0346(11) 0.0078(9) 0.0143(8) 0.0047(8) C7 0.0298(9) 0.0272(11) 0.0249(10) -0.0052(8) 0.0040(8) 0.0043(8) C8 0.0353(10) 0.0274(11) 0.0292(10) -0.0053(9) 0.0064(8) 0.0113(8) C9 0.0267(9) 0.0383(13) 0.0315(11) 0.0030(9) 0.0058(8) 0.0105(8) C10 0.0431(12) 0.0235(11) 0.0418(12) 0.0051(10) 0.0093(10) 0.0048(9) C21 0.0483(13) 0.068(2) 0.0405(13) 0.0005(12) 0.0245(11) -0.0113(12) C22 0.0522(14) 0.0627(18) 0.0258(11) -0.0032(11) 0.0097(10) 0.0032(12) C31 0.0426(13) 0.0282(13) 0.0752(18) -0.0049(12) 0.0198(12) -0.0052(9) C32 0.0539(15) 0.0467(17) 0.0763(19) -0.0052(14) 0.0377(14) -0.0161(12) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N2 1.9078(17) . ? Ti1 N3 1.9087(18) . ? Ti1 N1 1.9121(15) . ? Ti1 N1 1.9277(16) 3_656 ? Ti1 Ti1 2.8018(7) 3_656 ? N1 C1 1.468(2) . ? N1 Ti1 1.9277(16) 3_656 ? N2 C22 1.446(3) . ? N2 C21 1.450(3) . ? N3 C31 1.445(3) . ? N3 C32 1.450(3) . ? C1 C7 1.534(3) . ? C1 C2 1.537(3) . ? C1 C6 1.538(3) . ? C2 C3 1.532(3) . ? C2 H2A 0.99 . ? C2 H2B 0.99 . ? C3 C4 1.524(3) . ? C3 C9 1.525(3) . ? C3 H3 1 . ? C4 C5 1.532(3) . ? C4 H4A 0.99 . ? C4 H4B 0.99 . ? C5 C10 1.526(3) . ? C5 C6 1.540(3) . ? C5 H5 1 . ? C6 H6A 0.99 . ? C6 H6B 0.99 . ? C7 C8 1.536(3) . ? C7 H7A 0.99 . ? C7 H7B 0.99 . ? C8 C10 1.531(3) . ? C8 C9 1.531(3) . ? C8 H8 1 . ? C9 H9A 0.99 . ? C9 H9B 0.99 . ? C10 H10A 0.99 . ? C10 H10B 0.99 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 H22A 0.98 . ? C22 H22B 0.98 . ? C22 H22C 0.98 . ? C31 H31A 0.98 . ? C31 H31B 0.98 . ? C31 H31C 0.98 . ? C32 H32A 0.98 . ? C32 H32B 0.98 . ? C32 H32C 0.98 . ? 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 N2 Ti1 N3 110.00(8) . . ? N2 Ti1 N1 113.44(7) . . ? N3 Ti1 N1 114.84(7) . . ? N2 Ti1 N1 115.85(7) . 3_656 ? N3 Ti1 N1 114.81(7) . 3_656 ? N1 Ti1 N1 86.28(7) . 3_656 ? N2 Ti1 Ti1 124.85(6) . 3_656 ? N3 Ti1 Ti1 125.13(6) . 3_656 ? N1 Ti1 Ti1 43.36(5) . 3_656 ? N1 Ti1 Ti1 42.92(5) 3_656 3_656 ? C1 N1 Ti1 130.37(13) . . ? C1 N1 Ti1 131.04(12) . 3_656 ? Ti1 N1 Ti1 93.72(7) . 3_656 ? C22 N2 C21 111.48(18) . . ? C22 N2 Ti1 122.32(15) . . ? C21 N2 Ti1 126.19(15) . . ? C31 N3 C32 111.34(19) . . ? C31 N3 Ti1 122.69(15) . . ? C32 N3 Ti1 125.94(17) . . ? N1 C1 C7 110.61(15) . . ? N1 C1 C2 108.94(15) . . ? C7 C1 C2 108.35(14) . . ? N1 C1 C6 111.62(14) . . ? C7 C1 C6 108.61(16) . . ? C2 C1 C6 108.63(16) . . ? C3 C2 C1 110.32(16) . . ? C3 C2 H2A 109.6 . . ? C1 C2 H2A 109.6 . . ? C3 C2 H2B 109.6 . . ? C1 C2 H2B 109.6 . . ? H2A C2 H2B 108.1 . . ? C4 C3 C9 109.24(19) . . ? C4 C3 C2 109.54(16) . . ? C9 C3 C2 109.90(16) . . ? C4 C3 H3 109.4 . . ? C9 C3 H3 109.4 . . ? C2 C3 H3 109.4 . . ? C3 C4 C5 109.59(17) . . ? C3 C4 H4A 109.8 . . ? C5 C4 H4A 109.8 . . ? C3 C4 H4B 109.8 . . ? C5 C4 H4B 109.8 . . ? H4A C4 H4B 108.2 . . ? C10 C5 C4 109.87(18) . . ? C10 C5 C6 109.46(18) . . ? C4 C5 C6 109.10(18) . . ? C10 C5 H5 109.5 . . ? C4 C5 H5 109.5 . . ? C6 C5 H5 109.5 . . ? C1 C6 C5 110.22(16) . . ? C1 C6 H6A 109.6 . . ? C5 C6 H6A 109.6 . . ? C1 C6 H6B 109.6 . . ? C5 C6 H6B 109.6 . . ? H6A C6 H6B 108.1 . . ? C1 C7 C8 110.66(16) . . ? C1 C7 H7A 109.5 . . ? C8 C7 H7A 109.5 . . ? C1 C7 H7B 109.5 . . ? C8 C7 H7B 109.5 . . ? H7A C7 H7B 108.1 . . ? C10 C8 C9 109.62(17) . . ? C10 C8 C7 109.43(17) . . ? C9 C8 C7 109.25(18) . . ? C10 C8 H8 109.5 . . ? C9 C8 H8 109.5 . . ? C7 C8 H8 109.5 . . ? C3 C9 C8 109.43(15) . . ? C3 C9 H9A 109.8 . . ? C8 C9 H9A 109.8 . . ? C3 C9 H9B 109.8 . . ? C8 C9 H9B 109.8 . . ? H9A C9 H9B 108.2 . . ? C5 C10 C8 109.20(18) . . ? C5 C10 H10A 109.8 . . ? C8 C10 H10A 109.8 . . ? C5 C10 H10B 109.8 . . ? C8 C10 H10B 109.8 . . ? H10A C10 H10B 108.3 . . ? N2 C21 H21A 109.5 . . ? N2 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N2 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N2 C22 H22A 109.5 . . ? N2 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N2 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? N3 C31 H31A 109.5 . . ? N3 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? N3 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? N3 C32 H32A 109.5 . . ? N3 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? N3 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? _database_code_depnum_ccdc_archive 'CCDC 931095' ####################################################################### # # 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_[V(N-1-Ada)(NMe2)2]2 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C28 H54 N6 V2' _chemical_formula_sum 'C28 H54 N6 V2' _chemical_formula_weight 576.65 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'I 1 2/m 1' _symmetry_space_group_name_Hall '-I 2y' _symmetry_Int_Tables_number 12 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z+1/2' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 8.6878(10) _cell_length_b 12.6566(10) _cell_length_c 13.9992(16) _cell_angle_alpha 90 _cell_angle_beta 97.749(13) _cell_angle_gamma 90 _cell_volume 1525.3(3) _cell_formula_units_Z 2 _cell_measurement_temperature 190(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 1.65 _cell_measurement_theta_max 26.05 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour 'light purple' _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.12 _exptl_crystal_density_diffrn 1.256 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 620 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.639 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; (See: Walker, N. & Stuart, D. (1983) Acta Cryst. A39, 158-166) ; _exptl_absorpt_correction_T_min 0.454 _exptl_absorpt_correction_T_max 0.821 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 190(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 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 4 _diffrn_standards_decay_% 0.1 _diffrn_reflns_av_R_equivalents 0.0526 _diffrn_reflns_av_unetI/netI 0.0308 _diffrn_reflns_number 4442 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.61 _diffrn_reflns_theta_max 23.25 _diffrn_reflns_theta_full 23.25 _diffrn_measured_fraction_theta_full 0.989 _diffrn_measured_fraction_theta_max 0.989 _reflns_number_total 1137 _reflns_number_gt 1074 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'XRED (Stoe, 1.08, 1996)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0628P)^2^+3.3505P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 1137 _refine_ls_number_parameters 92 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0458 _refine_ls_R_factor_gt 0.0441 _refine_ls_wR_factor_ref 0.1149 _refine_ls_wR_factor_gt 0.1134 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.052 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.322 _refine_diff_density_min -0.317 _refine_diff_density_rms 0.062 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group V1 V 0.5 0.90121(5) 0 0.0251(3) Uani 1 2 d S . . N1 N 0.4282(3) 1 0.0816(2) 0.0263(7) Uani 1 2 d S . . N2 N 0.6669(3) 0.81851(18) 0.05505(16) 0.0339(6) Uani 1 1 d . . . C1 C 0.3731(4) 1 0.1761(3) 0.0264(8) Uani 1 2 d S . . C2 C 0.5126(6) 1 0.2534(3) 0.078(2) Uani 1 2 d S . . H2A H 0.577 1.0634 0.2466 0.093 Uiso 0.5 1 calc PR . . H2B H 0.577 0.9366 0.2466 0.093 Uiso 0.5 1 calc PR . . C3 C 0.4567(7) 1 0.3533(4) 0.117(4) Uani 1 2 d S . . H3 H 0.5484 1 0.4048 0.14 Uiso 1 2 calc SR . . C4 C 0.3582(6) 0.9015(5) 0.3632(3) 0.102(2) Uani 1 1 d . . . H4A H 0.4206 0.8373 0.3559 0.123 Uiso 1 1 calc R . . H4B H 0.3243 0.8999 0.428 0.123 Uiso 1 1 calc R . . C5 C 0.2192(5) 0.9033(2) 0.2873(3) 0.0568(10) Uani 1 1 d . . . H5 H 0.1549 0.8389 0.2941 0.068 Uiso 1 1 calc R . . C6 C 0.2724(5) 0.9034(2) 0.1867(3) 0.0508(9) Uani 1 1 d . . . H6A H 0.3323 0.8383 0.1781 0.061 Uiso 1 1 calc R . . H6B H 0.1806 0.9045 0.1364 0.061 Uiso 1 1 calc R . . C7 C 0.1232(5) 1 0.2992(3) 0.0461(11) Uani 1 2 d S . . H7A H 0.0295 1 0.2503 0.055 Uiso 1 2 calc SR . . H7B H 0.0891 1 0.3639 0.055 Uiso 1 2 calc SR . . C21 C 0.8295(4) 0.8461(3) 0.0775(3) 0.0564(9) Uani 1 1 d . . . H21A H 0.8502 0.9108 0.0429 0.085 Uiso 1 1 calc R . . H21B H 0.8935 0.7885 0.0576 0.085 Uiso 1 1 calc R . . H21C H 0.8549 0.8578 0.147 0.085 Uiso 1 1 calc R . . C22 C 0.6341(4) 0.7198(3) 0.1014(2) 0.0468(8) Uani 1 1 d . . . H22A H 0.5231 0.7036 0.0869 0.07 Uiso 1 1 calc R . . H22B H 0.6624 0.7265 0.1713 0.07 Uiso 1 1 calc R . . H22C H 0.6946 0.6627 0.0773 0.07 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 V1 0.0245(4) 0.0227(4) 0.0283(4) 0 0.0043(3) 0 N1 0.0232(15) 0.0276(17) 0.0284(16) 0 0.0044(12) 0 N2 0.0315(12) 0.0310(13) 0.0390(13) 0.0045(10) 0.0045(10) 0.0025(10) C1 0.0263(18) 0.0265(19) 0.0268(18) 0 0.0050(15) 0 C2 0.035(3) 0.168(7) 0.028(2) 0 0.001(2) 0 C3 0.046(3) 0.282(13) 0.020(2) 0 -0.001(2) 0 C4 0.120(4) 0.144(5) 0.056(2) 0.062(3) 0.057(3) 0.087(4) C5 0.091(3) 0.0295(18) 0.060(2) 0.0056(15) 0.047(2) -0.0033(17) C6 0.078(2) 0.0308(17) 0.052(2) -0.0051(14) 0.0385(19) -0.0091(16) C7 0.047(3) 0.054(3) 0.040(2) 0 0.019(2) 0 C21 0.0356(16) 0.055(2) 0.075(2) 0.0211(19) -0.0070(15) 0.0013(16) C22 0.0506(18) 0.0429(19) 0.0477(18) 0.0151(15) 0.0095(14) 0.0054(15) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag V1 N1 1.857(2) . ? V1 N1 1.857(2) 5_675 ? V1 N2 1.868(2) 2_655 ? V1 N2 1.868(2) . ? V1 V1 2.5006(12) 5_675 ? N1 C1 1.467(5) . ? N1 V1 1.857(2) 5_675 ? N2 C21 1.448(4) . ? N2 C22 1.454(4) . ? C1 C2 1.512(6) . ? C1 C6 1.522(4) . ? C1 C6 1.522(4) 6_575 ? C2 C3 1.541(7) . ? C2 H2A 0.99 . ? C2 H2B 0.99 . ? C3 C4 1.528(7) . ? C3 C4 1.528(7) 6_575 ? C3 H3 1 . ? C4 C5 1.498(7) . ? C4 H4A 0.99 . ? C4 H4B 0.99 . ? C5 C7 1.503(4) . ? C5 C6 1.541(4) . ? C5 H5 1 . ? C6 H6A 0.99 . ? C6 H6B 0.99 . ? C7 C5 1.503(4) 6_575 ? C7 H7A 0.99 . ? C7 H7B 0.99 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 H22A 0.98 . ? C22 H22B 0.98 . ? C22 H22C 0.98 . ? 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 V1 N1 95.35(13) . 5_675 ? N1 V1 N2 108.95(11) . 2_655 ? N1 V1 N2 115.45(11) 5_675 2_655 ? N1 V1 N2 115.45(11) . . ? N1 V1 N2 108.95(11) 5_675 . ? N2 V1 N2 111.84(15) 2_655 . ? N1 V1 V1 47.68(6) . 5_675 ? N1 V1 V1 47.68(6) 5_675 5_675 ? N2 V1 V1 124.08(7) 2_655 5_675 ? N2 V1 V1 124.08(7) . 5_675 ? C1 N1 V1 137.09(7) . 5_675 ? C1 N1 V1 137.09(7) . . ? V1 N1 V1 84.65(13) 5_675 . ? C21 N2 C22 110.8(2) . . ? C21 N2 V1 129.4(2) . . ? C22 N2 V1 118.54(19) . . ? N1 C1 C2 108.5(3) . . ? N1 C1 C6 110.5(2) . . ? C2 C1 C6 110.3(3) . . ? N1 C1 C6 110.5(2) . 6_575 ? C2 C1 C6 110.3(3) . 6_575 ? C6 C1 C6 106.9(3) . 6_575 ? C1 C2 C3 109.2(4) . . ? C1 C2 H2A 109.8 . . ? C3 C2 H2A 109.8 . . ? C1 C2 H2B 109.8 . . ? C3 C2 H2B 109.8 . . ? H2A C2 H2B 108.3 . . ? C4 C3 C4 109.3(5) . 6_575 ? C4 C3 C2 109.3(3) . . ? C4 C3 C2 109.3(3) 6_575 . ? C4 C3 H3 109.6 . . ? C4 C3 H3 109.6 6_575 . ? C2 C3 H3 109.6 . . ? C5 C4 C3 109.3(3) . . ? C5 C4 H4A 109.8 . . ? C3 C4 H4A 109.8 . . ? C5 C4 H4B 109.8 . . ? C3 C4 H4B 109.8 . . ? H4A C4 H4B 108.3 . . ? C4 C5 C7 109.9(4) . . ? C4 C5 C6 109.6(3) . . ? C7 C5 C6 109.9(3) . . ? C4 C5 H5 109.1 . . ? C7 C5 H5 109.1 . . ? C6 C5 H5 109.1 . . ? C1 C6 C5 109.7(3) . . ? C1 C6 H6A 109.7 . . ? C5 C6 H6A 109.7 . . ? C1 C6 H6B 109.7 . . ? C5 C6 H6B 109.7 . . ? H6A C6 H6B 108.2 . . ? C5 C7 C5 109.0(4) 6_575 . ? C5 C7 H7A 109.9 6_575 . ? C5 C7 H7A 109.9 . . ? C5 C7 H7B 109.9 6_575 . ? C5 C7 H7B 109.9 . . ? H7A C7 H7B 108.3 . . ? N2 C21 H21A 109.5 . . ? N2 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N2 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N2 C22 H22A 109.5 . . ? N2 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N2 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? _database_code_depnum_ccdc_archive 'CCDC 931096' ####################################################################### # # 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_3 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C44 H54 N6 Si2 Ti2' _chemical_formula_sum 'C44 H54 N6 Si2 Ti2' _chemical_formula_weight 818.85 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 12.8129(18) _cell_length_b 15.846(3) _cell_length_c 11.4001(17) _cell_angle_alpha 90 _cell_angle_beta 108.955(16) _cell_angle_gamma 90 _cell_volume 2189.1(6) _cell_formula_units_Z 2 _cell_measurement_temperature 180 _cell_measurement_reflns_used 2400 _cell_measurement_theta_min 1.65 _cell_measurement_theta_max 26.05 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description platelet _exptl_crystal_colour yellow _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.125 _exptl_crystal_size_min 0.025 _exptl_crystal_density_diffrn 1.242 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 864 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.457 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; (See: Walker, N. & Stuart, D. (1983) Acta Cryst. A39, 158-166) ; _exptl_absorpt_correction_T_min 0.927 _exptl_absorpt_correction_T_max 0.985 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 4 _diffrn_standards_decay_% 0.1 _diffrn_reflns_av_R_equivalents 0.2704 _diffrn_reflns_av_unetI/netI 0.3163 _diffrn_reflns_number 14897 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.45 _diffrn_reflns_theta_max 24.71 _diffrn_reflns_theta_full 24.71 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 3712 _reflns_number_gt 1084 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'XRED (Stoe, 1.08, 1996)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 3712 _refine_ls_number_parameters 248 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.2369 _refine_ls_R_factor_gt 0.0674 _refine_ls_wR_factor_ref 0.1539 _refine_ls_wR_factor_gt 0.0964 _refine_ls_goodness_of_fit_ref 0.777 _refine_ls_restrained_S_all 0.777 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.324 _refine_diff_density_min -0.586 _refine_diff_density_rms 0.082 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' Si Si 0.0817 0.0704 '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' 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 C1 C 0.8037(7) -0.0333(6) 0.5192(7) 0.053(2) Uani 1 1 d . . . C2 C 0.7950(9) -0.1213(6) 0.5213(9) 0.058(3) Uani 1 1 d . . . H2 H 0.7606 -0.1468 0.5725 0.07 Uiso 1 1 calc R . . C3 C 0.8385(10) -0.1714(7) 0.4457(9) 0.069(3) Uani 1 1 d . . . H3 H 0.8322 -0.2298 0.4475 0.083 Uiso 1 1 calc R . . C4 C 0.8891(9) -0.1358(8) 0.3710(9) 0.069(3) Uani 1 1 d . . . H4 H 0.9195 -0.1698 0.3239 0.082 Uiso 1 1 calc R . . C5 C 0.8958(9) -0.0500(9) 0.3645(8) 0.071(3) Uani 1 1 d . . . H5 H 0.9281 -0.026 0.3102 0.086 Uiso 1 1 calc R . . C6 C 0.8542(8) 0.0029(6) 0.4392(8) 0.058(2) Uani 1 1 d . . . H6 H 0.8604 0.0613 0.4352 0.07 Uiso 1 1 calc R . . C7 C 0.7908(8) 0.1434(6) 0.6289(8) 0.056(2) Uani 1 1 d . . . C8 C 0.7577(9) 0.1983(6) 0.5261(8) 0.063(3) Uani 1 1 d . . . H8 H 0.7156 0.1773 0.4491 0.075 Uiso 1 1 calc R . . C9 C 0.7873(10) 0.2842(6) 0.5379(11) 0.074(3) Uani 1 1 d . . . H9 H 0.7618 0.3195 0.4694 0.088 Uiso 1 1 calc R . . C10 C 0.8533(9) 0.3169(7) 0.6492(10) 0.065(3) Uani 1 1 d . . . H10 H 0.8741 0.3734 0.6562 0.078 Uiso 1 1 calc R . . C11 C 0.8871(10) 0.2647(7) 0.7478(10) 0.067(3) Uani 1 1 d . . . H11 H 0.9316 0.2859 0.8236 0.081 Uiso 1 1 calc R . . C12 C 0.8570(8) 0.1796(6) 0.7393(9) 0.058(3) Uani 1 1 d . . . H12 H 0.8821 0.146 0.8098 0.07 Uiso 1 1 calc R . . C13 C 0.7912(7) -0.0146(6) 0.7792(7) 0.049(2) Uani 1 1 d . . . C14 C 0.7346(8) 0.0043(6) 0.8639(8) 0.057(2) Uani 1 1 d . . . H14 H 0.6742 0.0405 0.8399 0.068 Uiso 1 1 calc R . . C15 C 0.7678(9) -0.0305(6) 0.9827(7) 0.062(3) Uani 1 1 d . . . H15 H 0.727 -0.0192 1.0351 0.074 Uiso 1 1 calc R . . C16 C 0.8600(9) -0.0812(6) 1.0240(7) 0.064(3) Uani 1 1 d . . . H16 H 0.8825 -0.1032 1.104 0.077 Uiso 1 1 calc R . . C17 C 0.9182(9) -0.0987(6) 0.9437(7) 0.061(3) Uani 1 1 d . . . H17 H 0.9803 -0.1331 0.9694 0.073 Uiso 1 1 calc R . . C18 C 0.8838(7) -0.0650(6) 0.8245(7) 0.056(2) Uani 1 1 d . . . H18 H 0.9251 -0.0769 0.7728 0.067 Uiso 1 1 calc R . . C19 C 0.5793(10) 0.0882(6) 0.1872(9) 0.070(3) Uani 1 1 d . . . H19A H 0.5356 0.074 0.1039 0.105 Uiso 1 1 calc R . . H19B H 0.6562 0.0838 0.1959 0.105 Uiso 1 1 calc R . . H19C H 0.5631 0.145 0.2051 0.105 Uiso 1 1 calc R . . C20 C 0.5731(8) -0.0575(6) 0.2459(7) 0.059(2) Uani 1 1 d . . . H20A H 0.6494 -0.0646 0.2537 0.088 Uiso 1 1 calc R . . H20B H 0.528 -0.0708 0.1627 0.088 Uiso 1 1 calc R . . H20C H 0.5545 -0.0944 0.3028 0.088 Uiso 1 1 calc R . . C21 C 0.3795(8) 0.2066(6) 0.2782(8) 0.056(2) Uani 1 1 d . . . H21A H 0.417 0.2516 0.2522 0.084 Uiso 1 1 calc R . . H21B H 0.3137 0.228 0.2903 0.084 Uiso 1 1 calc R . . H21C H 0.3604 0.1634 0.2158 0.084 Uiso 1 1 calc R . . C22 C 0.4769(10) 0.2347(6) 0.4937(8) 0.065(3) Uani 1 1 d . . . H22A H 0.4101 0.2504 0.5089 0.097 Uiso 1 1 calc R . . H22B H 0.5087 0.2835 0.4687 0.097 Uiso 1 1 calc R . . H22C H 0.5282 0.2117 0.5681 0.097 Uiso 1 1 calc R . . N1 N 0.5998(6) 0.0274(4) 0.5624(5) 0.0464(17) Uani 1 1 d . . . N2 N 0.5535(6) 0.0302(4) 0.2740(6) 0.0487(18) Uani 1 1 d . . . N3 N 0.4520(6) 0.1710(4) 0.3949(6) 0.0508(19) Uani 1 1 d . . . Si1 Si 0.7421(2) 0.03131(15) 0.6188(2) 0.0474(6) Uani 1 1 d . . . Ti1 Ti 0.49811(14) 0.05709(10) 0.40428(13) 0.0450(4) 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 C1 0.042(5) 0.072(7) 0.043(4) 0.007(4) 0.009(4) -0.010(5) C2 0.065(7) 0.057(6) 0.056(5) -0.003(5) 0.025(5) -0.002(5) C3 0.081(8) 0.057(6) 0.070(6) -0.014(5) 0.027(6) 0.010(6) C4 0.063(7) 0.080(8) 0.069(6) -0.003(5) 0.030(5) 0.009(6) C5 0.063(7) 0.101(10) 0.060(5) -0.017(6) 0.035(5) -0.010(7) C6 0.049(6) 0.072(6) 0.056(5) 0.000(5) 0.021(4) -0.009(5) C7 0.054(6) 0.058(6) 0.061(6) 0.003(5) 0.025(5) 0.000(5) C8 0.073(8) 0.066(6) 0.044(5) 0.002(4) 0.009(5) -0.011(5) C9 0.073(8) 0.048(6) 0.108(9) 0.029(6) 0.041(7) 0.002(5) C10 0.059(7) 0.059(6) 0.080(7) -0.017(6) 0.028(6) -0.017(5) C11 0.071(7) 0.055(6) 0.077(6) -0.015(5) 0.025(5) -0.018(5) C12 0.051(6) 0.067(7) 0.059(6) -0.002(5) 0.021(5) 0.006(5) C13 0.043(5) 0.055(5) 0.051(4) -0.004(4) 0.016(4) -0.002(4) C14 0.058(7) 0.059(6) 0.051(5) 0.001(4) 0.016(4) 0.005(5) C15 0.075(7) 0.073(6) 0.039(4) -0.007(4) 0.020(4) -0.005(6) C16 0.071(8) 0.074(7) 0.042(5) 0.003(4) 0.010(5) 0.004(6) C17 0.064(7) 0.066(6) 0.045(4) 0.007(4) 0.010(5) 0.002(5) C18 0.048(6) 0.068(6) 0.050(4) 0.000(4) 0.014(4) 0.000(5) C19 0.087(8) 0.065(7) 0.070(6) 0.014(5) 0.042(6) 0.003(6) C20 0.070(6) 0.053(5) 0.055(4) -0.005(5) 0.021(4) -0.005(5) C21 0.061(7) 0.054(5) 0.052(5) 0.003(4) 0.017(5) 0.002(5) C22 0.081(8) 0.063(6) 0.049(5) -0.012(4) 0.021(5) -0.009(6) N1 0.051(4) 0.050(4) 0.041(3) -0.001(3) 0.018(3) 0.004(3) N2 0.059(5) 0.036(4) 0.053(4) 0.003(3) 0.020(3) 0.001(3) N3 0.055(5) 0.059(4) 0.040(4) 0.001(3) 0.016(4) 0.006(4) Si1 0.0440(15) 0.0521(15) 0.0443(12) -0.0005(10) 0.0121(10) -0.0023(12) Ti1 0.0471(9) 0.0457(8) 0.0421(7) 0.0014(7) 0.0146(6) 0.0007(8) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 C1 C2 1.400(14) . ? C1 C6 1.401(13) . ? C1 Si1 1.883(10) . ? C2 C3 1.413(14) . ? C3 C4 1.350(16) . ? C4 C5 1.366(16) . ? C5 C6 1.417(14) . ? C7 C12 1.393(13) . ? C7 C8 1.409(13) . ? C7 Si1 1.873(10) . ? C8 C9 1.409(13) . ? C9 C10 1.377(14) . ? C10 C11 1.349(14) . ? C11 C12 1.396(14) . ? C13 C18 1.384(12) . ? C13 C14 1.414(13) . ? C13 Si1 1.876(8) . ? C14 C15 1.395(11) . ? C15 C16 1.378(13) . ? C16 C17 1.384(13) . ? C17 C18 1.392(11) . ? C19 N2 1.465(11) . ? C20 N2 1.465(11) . ? C21 N3 1.465(10) . ? C22 N3 1.467(11) . ? N1 Si1 1.726(7) . ? N1 Ti1 1.908(6) . ? N1 Ti1 1.954(7) 3_656 ? N2 Ti1 1.892(7) . ? N3 Ti1 1.892(7) . ? Ti1 N1 1.954(7) 3_656 ? Ti1 Ti1 2.823(3) 3_656 ? 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 C2 C1 C6 118.4(9) . . ? C2 C1 Si1 118.7(8) . . ? C6 C1 Si1 122.9(7) . . ? C1 C2 C3 120.0(10) . . ? C4 C3 C2 121.0(10) . . ? C3 C4 C5 120.1(11) . . ? C4 C5 C6 120.9(10) . . ? C1 C6 C5 119.5(10) . . ? C12 C7 C8 115.3(9) . . ? C12 C7 Si1 122.6(7) . . ? C8 C7 Si1 122.0(7) . . ? C9 C8 C7 121.2(9) . . ? C10 C9 C8 121.1(10) . . ? C11 C10 C9 118.2(9) . . ? C10 C11 C12 121.8(9) . . ? C7 C12 C11 122.3(9) . . ? C18 C13 C14 115.7(7) . . ? C18 C13 Si1 124.3(7) . . ? C14 C13 Si1 120.0(7) . . ? C15 C14 C13 121.2(9) . . ? C16 C15 C14 121.3(9) . . ? C15 C16 C17 118.5(8) . . ? C16 C17 C18 120.1(9) . . ? C13 C18 C17 123.2(9) . . ? Si1 N1 Ti1 131.1(4) . . ? Si1 N1 Ti1 128.3(4) . 3_656 ? Ti1 N1 Ti1 93.9(3) . 3_656 ? C20 N2 C19 110.8(7) . . ? C20 N2 Ti1 121.3(5) . . ? C19 N2 Ti1 127.8(6) . . ? C21 N3 C22 110.4(7) . . ? C21 N3 Ti1 120.8(5) . . ? C22 N3 Ti1 128.7(6) . . ? N1 Si1 C7 110.3(4) . . ? N1 Si1 C13 109.2(4) . . ? C7 Si1 C13 108.0(4) . . ? N1 Si1 C1 110.7(3) . . ? C7 Si1 C1 110.9(4) . . ? C13 Si1 C1 107.7(4) . . ? N2 Ti1 N3 111.1(3) . . ? N2 Ti1 N1 111.8(3) . . ? N3 Ti1 N1 113.2(3) . . ? N2 Ti1 N1 115.3(3) . 3_656 ? N3 Ti1 N1 117.1(3) . 3_656 ? N1 Ti1 N1 86.1(3) . 3_656 ? N2 Ti1 Ti1 123.1(2) . 3_656 ? N3 Ti1 Ti1 125.6(2) . 3_656 ? N1 Ti1 Ti1 43.7(2) . 3_656 ? N1 Ti1 Ti1 42.41(17) 3_656 3_656 ? _database_code_depnum_ccdc_archive 'CCDC 931097' ####################################################################### # # 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_4 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C60 H64 N6 Si3 Ti2' _chemical_formula_sum 'C60 H64 N6 Si3 Ti2' _chemical_formula_weight 1049.24 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.3357(4) _cell_length_b 13.4320(5) _cell_length_c 19.7408(9) _cell_angle_alpha 92.607(4) _cell_angle_beta 104.677(4) _cell_angle_gamma 106.071(3) _cell_volume 2772.34(19) _cell_formula_units_Z 2 _cell_measurement_temperature 180 _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 3.0952 _cell_measurement_theta_max 32.1055 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description parallelepiped _exptl_crystal_colour red _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_diffrn 1.257 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1104 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.397 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; (See: Walker, N. & Stuart, D. (1983) Acta Cryst. A39, 158-166) ; _exptl_absorpt_correction_T_min 0.838 _exptl_absorpt_correction_T_max 0.921 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180 _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 'Oxford-Diffraction XCALIBUR' _diffrn_measurement_method \w-\f _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0242 _diffrn_reflns_av_unetI/netI 0.0356 _diffrn_reflns_number 21233 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 3.1 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 11316 _reflns_number_gt 8647 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd.' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd.' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd.' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0709P)^2^+0.3123P] 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_number_reflns 11316 _refine_ls_number_parameters 631 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0578 _refine_ls_R_factor_gt 0.0446 _refine_ls_wR_factor_ref 0.1296 _refine_ls_wR_factor_gt 0.1218 _refine_ls_goodness_of_fit_ref 1.128 _refine_ls_restrained_S_all 1.128 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.492 _refine_diff_density_min -0.511 _refine_diff_density_rms 0.057 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' Si Si 0.0817 0.0704 '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' 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 C1 C 0.8426(2) 0.34011(18) 0.15823(12) 0.0303(5) Uani 1 1 d . . . C2 C 0.8318(3) 0.4396(2) 0.17189(16) 0.0563(8) Uani 1 1 d . . . H2 H 0.8996 0.49 0.2033 0.068 Uiso 1 1 calc R . . C3 C 0.7220(3) 0.4645(3) 0.13952(18) 0.0695(10) Uani 1 1 d . . . H3 H 0.7172 0.5316 0.1486 0.083 Uiso 1 1 calc R . . C4 C 0.6213(3) 0.3912(3) 0.09449(16) 0.0565(8) Uani 1 1 d . . . H4 H 0.5471 0.4078 0.0736 0.068 Uiso 1 1 calc R . . C5 C 0.6289(3) 0.2928(3) 0.07985(16) 0.0554(8) Uani 1 1 d . . . H5 H 0.56 0.2428 0.0489 0.066 Uiso 1 1 calc R . . C6 C 0.7402(2) 0.2677(2) 0.11143(15) 0.0450(6) Uani 1 1 d . . . H6 H 0.7452 0.2011 0.1007 0.054 Uiso 1 1 calc R . . C7 C 1.1023(2) 0.37433(16) 0.13715(12) 0.0277(5) Uani 1 1 d . . . C8 C 1.2360(2) 0.40355(19) 0.16099(14) 0.0403(6) Uani 1 1 d . . . H8 H 1.2749 0.3963 0.2072 0.048 Uiso 1 1 calc R . . C9 C 1.3113(3) 0.4429(2) 0.11749(16) 0.0487(7) Uani 1 1 d . . . H9 H 1.3998 0.4619 0.1347 0.058 Uiso 1 1 calc R . . C10 C 1.2561(3) 0.4539(2) 0.04890(15) 0.0465(7) Uani 1 1 d . . . H10 H 1.307 0.4805 0.0197 0.056 Uiso 1 1 calc R . . C11 C 1.1255(3) 0.4255(2) 0.02371(14) 0.0457(6) Uani 1 1 d . . . H11 H 1.0877 0.4321 -0.0228 0.055 Uiso 1 1 calc R . . C12 C 1.0496(2) 0.38704(18) 0.06756(12) 0.0364(5) Uani 1 1 d . . . H12 H 0.9612 0.3693 0.0499 0.044 Uiso 1 1 calc R . . C13 C 1.0775(2) 0.39113(17) 0.28712(12) 0.0311(5) Uani 1 1 d . . . C14 C 1.0652(2) 0.3414(2) 0.34690(12) 0.0368(5) Uani 1 1 d . . . H14 H 1.0184 0.2713 0.3412 0.044 Uiso 1 1 calc R . . C15 C 1.1215(3) 0.3946(2) 0.41471(14) 0.0490(7) Uani 1 1 d . . . H15 H 1.1123 0.3601 0.4537 0.059 Uiso 1 1 calc R . . C56 C 0.5828(2) -0.0167(2) 0.13311(17) 0.0529(7) Uani 1 1 d . A . H56A H 0.5442 0.0278 0.1042 0.079 Uiso 1 1 calc R . . H56B H 0.577 -0.005 0.1803 0.079 Uiso 1 1 calc R . . H56C H 0.5389 -0.0884 0.1142 0.079 Uiso 1 1 calc R . . C16 C 1.1904(3) 0.4978(3) 0.42378(16) 0.0603(8) Uani 1 1 d . . . H16 H 1.2279 0.5335 0.4691 0.072 Uiso 1 1 calc R . . C17 C 1.2044(3) 0.5491(2) 0.36617(18) 0.0636(9) Uani 1 1 d . . . H17 H 1.2511 0.6193 0.3725 0.076 Uiso 1 1 calc R . . C57 C 1.1129(3) 0.1278(2) 0.06522(12) 0.0421(6) Uani 1 1 d . A . H57A H 1.1388 0.1917 0.0456 0.063 Uiso 1 1 calc R . . H57B H 1.0254 0.1138 0.0657 0.063 Uiso 1 1 calc R . . H57C H 1.1216 0.0715 0.0371 0.063 Uiso 1 1 calc R . . C18 C 1.1487(3) 0.49571(19) 0.29846(14) 0.0456(6) Uani 1 1 d . . . H18 H 1.1595 0.5309 0.2599 0.055 Uiso 1 1 calc R . . C19 C 1.0778(2) -0.18564(16) 0.17089(11) 0.0266(4) Uani 1 1 d . . . C20 C 1.1064(2) -0.27869(18) 0.18252(13) 0.0392(6) Uani 1 1 d . . . H20 H 1.0801 -0.3155 0.2175 0.047 Uiso 1 1 calc R . . C21 C 1.1730(3) -0.3183(2) 0.14336(14) 0.0444(6) Uani 1 1 d . . . H21 H 1.1909 -0.3807 0.1525 0.053 Uiso 1 1 calc R . . C22 C 1.2123(2) -0.2661(2) 0.09170(13) 0.0403(6) Uani 1 1 d . . . H22 H 1.2567 -0.2928 0.0655 0.048 Uiso 1 1 calc R . . C23 C 1.1860(3) -0.1738(2) 0.07851(14) 0.0482(7) Uani 1 1 d . . . H23 H 1.2136 -0.1374 0.0437 0.058 Uiso 1 1 calc R . . C24 C 1.1181(3) -0.13477(19) 0.11716(13) 0.0407(6) Uani 1 1 d . . . H24 H 1.0991 -0.0731 0.1068 0.049 Uiso 1 1 calc R . . C25 C 1.0298(2) -0.16707(16) 0.31561(11) 0.0277(5) Uani 1 1 d . . . C26 C 0.9784(3) -0.26485(18) 0.33440(13) 0.0392(6) Uani 1 1 d . . . H26 H 0.9166 -0.3158 0.3004 0.047 Uiso 1 1 calc R . . C27 C 1.0174(3) -0.2883(2) 0.40311(14) 0.0486(7) Uani 1 1 d . . . H27 H 0.9818 -0.3543 0.4145 0.058 Uiso 1 1 calc R . . C28 C 1.1087(3) -0.2134(2) 0.45400(14) 0.0473(7) Uani 1 1 d . . . H28 H 1.1347 -0.2286 0.4999 0.057 Uiso 1 1 calc R . . C29 C 1.1612(3) -0.1168(2) 0.43686(14) 0.0500(7) Uani 1 1 d . . . H29 H 1.223 -0.0663 0.4712 0.06 Uiso 1 1 calc R . . C30 C 1.1225(2) -0.0936(2) 0.36827(13) 0.0396(6) Uani 1 1 d . . . H30 H 1.1594 -0.0276 0.3574 0.048 Uiso 1 1 calc R . . C31 C 0.8097(2) -0.21208(16) 0.18282(13) 0.0321(5) Uani 1 1 d . . . C32A C 0.7180(7) -0.2256(5) 0.2155(4) 0.0394(5) Uani 0.63 1 d P A 1 H32A H 0.7397 -0.2006 0.2631 0.047 Uiso 0.63 1 calc PR A 1 C33A C 0.5883(4) -0.2769(4) 0.1796(2) 0.0394(5) Uani 0.63 1 d P A 1 H33A H 0.5263 -0.2846 0.2038 0.047 Uiso 0.63 1 calc PR A 1 C34A C 0.5533(5) -0.3151(4) 0.1101(2) 0.0394(5) Uani 0.63 1 d P A 1 H34A H 0.4683 -0.3501 0.0869 0.047 Uiso 0.63 1 calc PR A 1 C35A C 0.6461(4) -0.3011(4) 0.0741(2) 0.0394(5) Uani 0.63 1 d P A 1 H35A H 0.6221 -0.3254 0.0263 0.047 Uiso 0.63 1 calc PR A 1 C36A C 0.7736(5) -0.2518(5) 0.1081(3) 0.0394(5) Uani 0.63 1 d P A 1 H36A H 0.8352 -0.244 0.0837 0.047 Uiso 0.63 1 calc PR A 1 C32B C 0.7224(12) -0.2096(8) 0.2283(6) 0.0394(5) Uani 0.37 1 d P A 2 H32B H 0.7569 -0.1717 0.273 0.047 Uiso 0.37 1 calc PR A 2 C33B C 0.5960(7) -0.2600(6) 0.2072(4) 0.0394(5) Uani 0.37 1 d P A 2 H33B H 0.5444 -0.2595 0.237 0.047 Uiso 0.37 1 calc PR A 2 C34B C 0.5449(8) -0.3135(6) 0.1379(4) 0.0394(5) Uani 0.37 1 d P A 2 H34B H 0.4578 -0.3478 0.1219 0.047 Uiso 0.37 1 calc PR A 2 C35B C 0.6184(7) -0.3164(6) 0.0946(4) 0.0394(5) Uani 0.37 1 d P A 2 H35B H 0.5827 -0.351 0.0489 0.047 Uiso 0.37 1 calc PR A 2 C36B C 0.7523(8) -0.2655(8) 0.1200(6) 0.0394(5) Uani 0.37 1 d P A 2 H36B H 0.8026 -0.2704 0.0901 0.047 Uiso 0.37 1 calc PR A 2 C58 C 1.3283(3) 0.1657(2) 0.13892(16) 0.0523(7) Uani 1 1 d . A . H58A H 1.3449 0.1081 0.1165 0.078 Uiso 1 1 calc R . . H58B H 1.38 0.1821 0.187 0.078 Uiso 1 1 calc R . . H58C H 1.3485 0.2254 0.1143 0.078 Uiso 1 1 calc R . . C37 C 1.4193(2) 0.07709(18) 0.35568(12) 0.0321(5) Uani 1 1 d . . . C38 C 1.3741(2) 0.01186(19) 0.29104(14) 0.0396(6) Uani 1 1 d . . . H38 H 1.3246 0.0326 0.2523 0.048 Uiso 1 1 calc R . . C39 C 1.4003(3) -0.0817(2) 0.28266(15) 0.0471(6) Uani 1 1 d . . . H39 H 1.3684 -0.123 0.2391 0.057 Uiso 1 1 calc R . . C40 C 1.4739(3) -0.1135(2) 0.33929(16) 0.0511(7) Uani 1 1 d . . . H40 H 1.4923 -0.1762 0.3341 0.061 Uiso 1 1 calc R . . C41 C 1.5205(3) -0.0518(2) 0.40396(15) 0.0511(7) Uani 1 1 d . . . H41 H 1.5698 -0.0735 0.4423 0.061 Uiso 1 1 calc R . . C42 C 1.4944(2) 0.0420(2) 0.41197(13) 0.0403(6) Uani 1 1 d . . . H42 H 1.5272 0.0829 0.4557 0.048 Uiso 1 1 calc R . . C43 C 1.3638(2) 0.2367(2) 0.45312(12) 0.0352(5) Uani 1 1 d . . . C44 C 1.2553(3) 0.1792(2) 0.47075(15) 0.0462(6) Uani 1 1 d . . . H44 H 1.1981 0.1222 0.4396 0.055 Uiso 1 1 calc R . . C45 C 1.2303(3) 0.2048(3) 0.53374(17) 0.0595(8) Uani 1 1 d . . . H45 H 1.1578 0.1646 0.5445 0.071 Uiso 1 1 calc R . . C46 C 1.3123(3) 0.2887(3) 0.57962(16) 0.0679(10) Uani 1 1 d . . . H46 H 1.2955 0.3062 0.6216 0.081 Uiso 1 1 calc R . . C47 C 1.4198(4) 0.3475(3) 0.56384(17) 0.0774(11) Uani 1 1 d . . . H47 H 1.4758 0.4048 0.5952 0.093 Uiso 1 1 calc R . . C48 C 1.4449(3) 0.3215(3) 0.50115(15) 0.0587(8) Uani 1 1 d . . . H48 H 1.518 0.3619 0.4911 0.07 Uiso 1 1 calc R . . C55 C 0.7288(3) -0.0154(2) 0.06405(13) 0.0460(6) Uani 1 1 d . A . H55A H 0.6839 -0.0873 0.0464 0.069 Uiso 1 1 calc R . . H55B H 0.8175 -0.002 0.0663 0.069 Uiso 1 1 calc R . . H55C H 0.6933 0.0285 0.0331 0.069 Uiso 1 1 calc R . . C49 C 1.5309(2) 0.30906(19) 0.35537(12) 0.0387(6) Uani 1 1 d . . . C50A C 1.6562(8) 0.3147(7) 0.4019(3) 0.0509(5) Uani 0.61 1 d P B 1 H50A H 1.6612 0.27 0.4364 0.061 Uiso 0.61 1 calc PR B 1 C51A C 1.7677(6) 0.3845(5) 0.3961(3) 0.0509(5) Uani 0.61 1 d P B 1 H51A H 1.8457 0.3905 0.4284 0.061 Uiso 0.61 1 calc PR B 1 C52A C 1.7610(5) 0.4451(4) 0.3414(3) 0.0509(5) Uani 0.61 1 d P B 1 H52A H 1.836 0.4889 0.3353 0.061 Uiso 0.61 1 calc PR B 1 C53A C 1.6453(5) 0.4419(4) 0.2955(3) 0.0509(5) Uani 0.61 1 d P B 1 H53A H 1.6412 0.4868 0.261 0.061 Uiso 0.61 1 calc PR B 1 C54A C 1.5331(5) 0.3690(4) 0.3020(3) 0.0509(5) Uani 0.61 1 d P B 1 H54A H 1.4567 0.3617 0.2679 0.061 Uiso 0.61 1 calc PR B 1 C50B C 1.6505(13) 0.3189(11) 0.3854(5) 0.0509(5) Uani 0.39 1 d P B 2 H50B H 1.6696 0.2703 0.4151 0.061 Uiso 0.39 1 calc PR B 2 C51B C 1.7540(9) 0.4001(8) 0.3751(5) 0.0509(5) Uani 0.39 1 d P B 2 H51B H 1.8386 0.4034 0.396 0.061 Uiso 0.39 1 calc PR B 2 C52B C 1.7232(8) 0.4736(7) 0.3328(5) 0.0509(5) Uani 0.39 1 d P B 2 H52B H 1.7882 0.5237 0.3217 0.061 Uiso 0.39 1 calc PR B 2 C53B C 1.6007(7) 0.4746(6) 0.3071(4) 0.0509(5) Uani 0.39 1 d P B 2 H53B H 1.5843 0.5277 0.2811 0.061 Uiso 0.39 1 calc PR B 2 C54B C 1.4977(8) 0.3972(6) 0.3189(4) 0.0509(5) Uani 0.39 1 d P B 2 H54B H 1.4143 0.4005 0.3048 0.061 Uiso 0.39 1 calc PR B 2 C59 C 0.7413(3) 0.1387(2) 0.29569(17) 0.0546(7) Uani 1 1 d . A . H59A H 0.6614 0.1018 0.3037 0.082 Uiso 1 1 calc R . . H59B H 0.7256 0.1645 0.2508 0.082 Uiso 1 1 calc R . . H59C H 0.7859 0.1961 0.3323 0.082 Uiso 1 1 calc R . . C60 C 0.8580(3) 0.0341(3) 0.36527(15) 0.0595(8) Uani 1 1 d . A . H60A H 0.9072 0.0938 0.3994 0.089 Uiso 1 1 calc R . . H60B H 0.9091 -0.0115 0.3628 0.089 Uiso 1 1 calc R . . H60C H 0.7838 -0.0025 0.379 0.089 Uiso 1 1 calc R . . N1 N 0.98775(16) 0.18618(13) 0.19947(9) 0.0225(4) Uani 1 1 d . . . N2 N 1.00090(16) -0.00438(13) 0.21939(9) 0.0229(4) Uani 1 1 d . . . N3 N 1.25121(19) 0.20074(15) 0.30041(10) 0.0351(4) Uani 1 1 d D . . H3N H 1.225(2) 0.2515(15) 0.3097(14) 0.042 Uiso 1 1 d D . . N4 N 0.71654(18) 0.00692(15) 0.13389(10) 0.0330(4) Uani 1 1 d . . . N5 N 1.19349(18) 0.13764(14) 0.13724(10) 0.0307(4) Uani 1 1 d . . . N6 N 0.81848(19) 0.06830(16) 0.29622(11) 0.0367(5) Uani 1 1 d . . . Si1 Si 1.00097(5) 0.31699(4) 0.19607(3) 0.02342(13) Uani 1 1 d . . . Si2 Si 0.98269(5) -0.13583(4) 0.22235(3) 0.02271(13) Uani 1 1 d . A . Si3 Si 1.38751(6) 0.20547(5) 0.36475(3) 0.02934(15) Uani 1 1 d . A . Ti1 Ti 1.12505(3) 0.12838(3) 0.215699(18) 0.02073(10) Uani 1 1 d . A . Ti2 Ti 0.86465(3) 0.05763(3) 0.21228(2) 0.02430(10) Uani 1 1 d . A . 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 C1 0.0289(11) 0.0373(12) 0.0309(12) 0.0113(10) 0.0119(9) 0.0152(10) C2 0.0603(18) 0.0560(17) 0.0547(18) -0.0049(14) -0.0021(15) 0.0393(15) C3 0.070(2) 0.078(2) 0.066(2) -0.0060(17) -0.0042(17) 0.056(2) C4 0.0437(16) 0.088(2) 0.0550(18) 0.0214(17) 0.0167(14) 0.0424(16) C5 0.0353(14) 0.0641(19) 0.0556(18) 0.0194(15) -0.0028(13) 0.0092(14) C6 0.0359(13) 0.0374(13) 0.0573(17) 0.0114(12) 0.0034(12) 0.0118(11) C7 0.0309(11) 0.0198(10) 0.0350(12) 0.0042(9) 0.0127(10) 0.0083(9) C8 0.0337(13) 0.0414(14) 0.0508(15) 0.0192(12) 0.0150(11) 0.0142(11) C9 0.0360(14) 0.0478(16) 0.0678(19) 0.0145(14) 0.0272(14) 0.0085(12) C10 0.0562(17) 0.0348(13) 0.0596(18) 0.0108(12) 0.0387(15) 0.0100(12) C11 0.0666(19) 0.0416(14) 0.0326(13) 0.0080(11) 0.0209(13) 0.0149(13) C12 0.0381(13) 0.0352(12) 0.0349(13) 0.0032(10) 0.0118(11) 0.0079(10) C13 0.0306(11) 0.0297(11) 0.0361(12) 0.0007(9) 0.0082(10) 0.0151(9) C14 0.0391(13) 0.0407(13) 0.0339(13) -0.0004(10) 0.0135(11) 0.0150(11) C15 0.0535(16) 0.0646(18) 0.0323(13) -0.0026(12) 0.0104(12) 0.0258(15) C56 0.0285(13) 0.0577(17) 0.0668(19) 0.0072(15) 0.0076(13) 0.0090(12) C16 0.064(2) 0.065(2) 0.0406(16) -0.0197(14) -0.0004(14) 0.0189(16) C17 0.069(2) 0.0379(15) 0.067(2) -0.0186(14) 0.0029(17) 0.0085(15) C57 0.0579(16) 0.0480(15) 0.0269(12) 0.0052(11) 0.0177(12) 0.0208(13) C18 0.0557(16) 0.0306(13) 0.0445(15) 0.0002(11) 0.0048(13) 0.0124(12) C19 0.0281(11) 0.0226(10) 0.0260(11) 0.0004(8) 0.0035(9) 0.0068(9) C20 0.0513(15) 0.0316(12) 0.0446(14) 0.0146(11) 0.0222(12) 0.0185(11) C21 0.0588(17) 0.0333(13) 0.0530(16) 0.0096(11) 0.0205(14) 0.0273(12) C22 0.0451(14) 0.0440(14) 0.0382(13) -0.0001(11) 0.0143(11) 0.0219(12) C23 0.0724(19) 0.0455(15) 0.0430(15) 0.0154(12) 0.0317(14) 0.0275(14) C24 0.0620(17) 0.0342(13) 0.0371(13) 0.0110(10) 0.0203(12) 0.0249(12) C25 0.0291(11) 0.0279(11) 0.0290(11) 0.0080(9) 0.0103(9) 0.0101(9) C26 0.0493(15) 0.0298(12) 0.0356(13) 0.0067(10) 0.0110(11) 0.0075(11) C27 0.0670(19) 0.0428(15) 0.0415(15) 0.0215(12) 0.0196(14) 0.0185(14) C28 0.0504(16) 0.0639(18) 0.0330(13) 0.0208(13) 0.0102(12) 0.0245(14) C29 0.0429(15) 0.0607(18) 0.0341(14) 0.0097(12) -0.0010(12) 0.0057(13) C30 0.0369(13) 0.0404(14) 0.0333(13) 0.0088(11) 0.0050(11) 0.0020(11) C31 0.0305(12) 0.0201(10) 0.0409(13) 0.0042(9) 0.0022(10) 0.0068(9) C32A 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C33A 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C34A 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C35A 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C36A 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C32B 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C33B 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C34B 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C35B 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C36B 0.0297(8) 0.0402(10) 0.0419(16) -0.0029(8) 0.0068(9) 0.0044(7) C58 0.0421(15) 0.0600(18) 0.0640(19) 0.0108(15) 0.0292(14) 0.0161(14) C37 0.0220(10) 0.0377(12) 0.0362(13) 0.0085(10) 0.0076(9) 0.0081(9) C38 0.0322(12) 0.0393(13) 0.0422(14) 0.0031(11) 0.0004(11) 0.0120(11) C39 0.0436(15) 0.0413(14) 0.0533(17) -0.0028(12) 0.0083(13) 0.0135(12) C40 0.0569(17) 0.0442(15) 0.0620(18) 0.0120(14) 0.0207(15) 0.0260(14) C41 0.0521(17) 0.0624(18) 0.0503(17) 0.0256(14) 0.0156(14) 0.0315(15) C42 0.0377(13) 0.0525(15) 0.0332(13) 0.0126(11) 0.0087(11) 0.0174(12) C43 0.0321(12) 0.0456(14) 0.0298(12) 0.0065(10) 0.0059(10) 0.0166(11) C44 0.0490(15) 0.0493(15) 0.0473(15) 0.0153(12) 0.0194(13) 0.0186(13) C45 0.064(2) 0.077(2) 0.0590(19) 0.0349(17) 0.0353(17) 0.0341(18) C46 0.074(2) 0.111(3) 0.0363(16) 0.0158(18) 0.0239(16) 0.046(2) C47 0.066(2) 0.112(3) 0.0448(18) -0.0192(18) 0.0158(17) 0.016(2) C48 0.0434(16) 0.082(2) 0.0436(16) -0.0104(15) 0.0152(13) 0.0069(15) C55 0.0443(15) 0.0499(15) 0.0346(14) 0.0004(11) 0.0044(12) 0.0060(12) C49 0.0424(14) 0.0378(13) 0.0268(12) -0.0038(10) 0.0080(10) 0.0003(11) C50A 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C51A 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C52A 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C53A 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C54A 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C50B 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C51B 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C52B 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C53B 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C54B 0.0431(10) 0.0511(11) 0.0548(13) 0.0101(10) 0.0149(10) 0.0063(8) C59 0.0556(17) 0.0490(16) 0.069(2) 0.0025(14) 0.0346(16) 0.0163(14) C60 0.067(2) 0.081(2) 0.0409(16) 0.0148(15) 0.0265(15) 0.0268(18) N1 0.0238(8) 0.0217(8) 0.0240(9) 0.0051(7) 0.0084(7) 0.0081(7) N2 0.0249(9) 0.0213(8) 0.0227(9) 0.0041(7) 0.0080(7) 0.0059(7) N3 0.0338(11) 0.0334(11) 0.0324(10) 0.0000(8) -0.0021(9) 0.0119(9) N4 0.0271(10) 0.0314(10) 0.0384(11) 0.0054(8) 0.0071(8) 0.0070(8) N5 0.0318(10) 0.0329(10) 0.0334(10) 0.0077(8) 0.0158(8) 0.0125(8) N6 0.0383(11) 0.0397(11) 0.0373(11) 0.0031(9) 0.0207(9) 0.0110(9) Si1 0.0243(3) 0.0212(3) 0.0266(3) 0.0034(2) 0.0076(2) 0.0092(2) Si2 0.0242(3) 0.0190(3) 0.0234(3) 0.0029(2) 0.0053(2) 0.0053(2) Si3 0.0244(3) 0.0324(3) 0.0264(3) 0.0030(2) 0.0019(2) 0.0057(2) Ti1 0.01993(18) 0.02059(18) 0.02146(19) 0.00311(14) 0.00509(14) 0.00622(14) Ti2 0.02281(19) 0.0243(2) 0.0270(2) 0.00346(15) 0.00983(16) 0.00628(15) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 C1 C6 1.378(3) . ? C1 C2 1.396(3) . ? C1 Si1 1.878(2) . ? C2 C3 1.384(4) . ? C3 C4 1.359(5) . ? C4 C5 1.371(4) . ? C5 C6 1.396(4) . ? C7 C12 1.391(3) . ? C7 C8 1.402(3) . ? C7 Si1 1.880(2) . ? C8 C9 1.382(3) . ? C9 C10 1.374(4) . ? C10 C11 1.372(4) . ? C11 C12 1.389(3) . ? C13 C18 1.388(3) . ? C13 C14 1.400(3) . ? C13 Si1 1.882(2) . ? C14 C15 1.392(3) . ? C15 C16 1.367(4) . ? C56 N4 1.457(3) . ? C16 C17 1.377(5) . ? C17 C18 1.391(4) . ? C57 N5 1.460(3) . ? C19 C20 1.390(3) . ? C19 C24 1.392(3) . ? C19 Si2 1.880(2) . ? C20 C21 1.390(3) . ? C21 C22 1.361(4) . ? C22 C23 1.374(4) . ? C23 C24 1.391(3) . ? C25 C26 1.390(3) . ? C25 C30 1.392(3) . ? C25 Si2 1.883(2) . ? C26 C27 1.395(3) . ? C27 C28 1.378(4) . ? C28 C29 1.367(4) . ? C29 C30 1.391(3) . ? C31 C36B 1.314(12) . ? C31 C32A 1.333(8) . ? C31 C36A 1.459(7) . ? C31 C32B 1.500(14) . ? C31 Si2 1.882(2) . ? C32A C33A 1.416(7) . ? C33A C34A 1.361(6) . ? C34A C35A 1.387(6) . ? C35A C36A 1.385(6) . ? C32B C33B 1.349(13) . ? C33B C34B 1.414(10) . ? C34B C35B 1.343(10) . ? C35B C36B 1.426(11) . ? C58 N5 1.460(3) . ? C37 C42 1.404(3) . ? C37 C38 1.406(3) . ? C37 Si3 1.867(2) . ? C38 C39 1.381(4) . ? C39 C40 1.377(4) . ? C40 C41 1.384(4) . ? C41 C42 1.383(4) . ? C43 C48 1.386(4) . ? C43 C44 1.395(4) . ? C43 Si3 1.878(2) . ? C44 C45 1.392(4) . ? C45 C46 1.362(5) . ? C46 C47 1.374(5) . ? C47 C48 1.389(4) . ? C55 N4 1.447(3) . ? C49 C50B 1.301(14) . ? C49 C54A 1.355(5) . ? C49 C50A 1.463(8) . ? C49 C54B 1.500(8) . ? C49 Si3 1.881(2) . ? C50A C51A 1.384(9) . ? C51A C52A 1.381(7) . ? C52A C53A 1.381(7) . ? C53A C54A 1.413(6) . ? C50B C51B 1.428(14) . ? C51B C52B 1.383(11) . ? C52B C53B 1.357(11) . ? C53B C54B 1.409(10) . ? C59 N6 1.454(3) . ? C60 N6 1.460(3) . ? N1 Si1 1.7275(17) . ? N1 Ti1 1.8885(17) . ? N1 Ti2 1.9691(16) . ? N2 Si2 1.7254(17) . ? N2 Ti2 1.9267(17) . ? N2 Ti1 1.9596(16) . ? N3 Si3 1.717(2) . ? N3 Ti1 1.9124(19) . ? N4 Ti2 1.9057(19) . ? N5 Ti1 1.8946(18) . ? N6 Ti2 1.8707(19) . ? Ti1 Ti2 2.8215(5) . ? 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 C6 C1 C2 117.6(2) . . ? C6 C1 Si1 123.54(18) . . ? C2 C1 Si1 118.46(19) . . ? C3 C2 C1 121.1(3) . . ? C4 C3 C2 120.2(3) . . ? C3 C4 C5 120.1(3) . . ? C4 C5 C6 119.9(3) . . ? C1 C6 C5 121.0(3) . . ? C12 C7 C8 116.6(2) . . ? C12 C7 Si1 122.30(17) . . ? C8 C7 Si1 121.11(18) . . ? C9 C8 C7 121.6(2) . . ? C10 C9 C8 120.3(3) . . ? C11 C10 C9 119.6(2) . . ? C10 C11 C12 120.2(2) . . ? C11 C12 C7 121.7(2) . . ? C18 C13 C14 117.1(2) . . ? C18 C13 Si1 122.39(19) . . ? C14 C13 Si1 120.54(17) . . ? C15 C14 C13 121.5(2) . . ? C16 C15 C14 119.8(3) . . ? C15 C16 C17 120.3(3) . . ? C16 C17 C18 119.9(3) . . ? C13 C18 C17 121.5(3) . . ? C20 C19 C24 116.4(2) . . ? C20 C19 Si2 121.23(17) . . ? C24 C19 Si2 122.30(17) . . ? C21 C20 C19 121.9(2) . . ? C22 C21 C20 120.2(2) . . ? C21 C22 C23 119.7(2) . . ? C22 C23 C24 120.1(2) . . ? C23 C24 C19 121.6(2) . . ? C26 C25 C30 117.1(2) . . ? C26 C25 Si2 122.01(17) . . ? C30 C25 Si2 120.83(16) . . ? C25 C26 C27 121.5(2) . . ? C28 C27 C26 119.8(2) . . ? C29 C28 C27 119.9(2) . . ? C28 C29 C30 120.3(3) . . ? C29 C30 C25 121.4(2) . . ? C36B C31 C32A 104.6(4) . . ? C32A C31 C36A 118.3(3) . . ? C36B C31 C32B 114.4(5) . . ? C36A C31 C32B 127.5(4) . . ? C36B C31 Si2 129.6(4) . . ? C32A C31 Si2 125.8(3) . . ? C36A C31 Si2 115.7(2) . . ? C32B C31 Si2 116.0(4) . . ? C31 C32A C33A 121.7(5) . . ? C34A C33A C32A 120.6(4) . . ? C33A C34A C35A 119.2(4) . . ? C36A C35A C34A 121.3(4) . . ? C35A C36A C31 118.8(4) . . ? C33B C32B C31 122.9(7) . . ? C32B C33B C34B 117.4(7) . . ? C35B C34B C33B 122.0(7) . . ? C34B C35B C36B 118.6(7) . . ? C31 C36B C35B 124.5(7) . . ? C42 C37 C38 116.0(2) . . ? C42 C37 Si3 122.11(19) . . ? C38 C37 Si3 121.82(17) . . ? C39 C38 C37 122.7(2) . . ? C40 C39 C38 119.5(3) . . ? C39 C40 C41 119.9(3) . . ? C42 C41 C40 120.4(2) . . ? C41 C42 C37 121.6(2) . . ? C48 C43 C44 116.6(2) . . ? C48 C43 Si3 122.9(2) . . ? C44 C43 Si3 120.3(2) . . ? C45 C44 C43 121.8(3) . . ? C46 C45 C44 119.9(3) . . ? C45 C46 C47 119.9(3) . . ? C46 C47 C48 120.0(3) . . ? C43 C48 C47 121.7(3) . . ? C50B C49 C54A 104.6(5) . . ? C54A C49 C50A 115.2(4) . . ? C50B C49 C54B 118.6(6) . . ? C50A C49 C54B 125.2(5) . . ? C50B C49 Si3 127.2(5) . . ? C54A C49 Si3 125.8(3) . . ? C50A C49 Si3 118.1(3) . . ? C54B C49 Si3 113.3(3) . . ? C51A C50A C49 122.1(5) . . ? C52A C51A C50A 118.7(5) . . ? C51A C52A C53A 121.4(5) . . ? C52A C53A C54A 118.5(5) . . ? C49 C54A C53A 123.5(4) . . ? C49 C50B C51B 123.6(9) . . ? C52B C51B C50B 117.2(8) . . ? C53B C52B C51B 121.8(8) . . ? C52B C53B C54B 121.6(8) . . ? C53B C54B C49 115.9(6) . . ? Si1 N1 Ti1 125.42(9) . . ? Si1 N1 Ti2 139.03(10) . . ? Ti1 N1 Ti2 93.99(7) . . ? Si2 N2 Ti2 124.13(9) . . ? Si2 N2 Ti1 142.68(10) . . ? Ti2 N2 Ti1 93.11(7) . . ? Si3 N3 Ti1 147.80(13) . . ? C55 N4 C56 111.1(2) . . ? C55 N4 Ti2 120.40(16) . . ? C56 N4 Ti2 128.51(18) . . ? C57 N5 C58 110.8(2) . . ? C57 N5 Ti1 121.78(15) . . ? C58 N5 Ti1 127.05(17) . . ? C59 N6 C60 112.9(2) . . ? C59 N6 Ti2 112.55(17) . . ? C60 N6 Ti2 133.84(18) . . ? N1 Si1 C1 112.58(9) . . ? N1 Si1 C7 111.16(9) . . ? C1 Si1 C7 105.41(10) . . ? N1 Si1 C13 109.80(9) . . ? C1 Si1 C13 109.50(10) . . ? C7 Si1 C13 108.23(10) . . ? N2 Si2 C19 112.46(9) . . ? N2 Si2 C31 109.40(9) . . ? C19 Si2 C31 107.38(10) . . ? N2 Si2 C25 111.91(9) . . ? C19 Si2 C25 108.40(9) . . ? C31 Si2 C25 107.05(10) . . ? N3 Si3 C37 108.28(10) . . ? N3 Si3 C43 108.56(11) . . ? C37 Si3 C43 112.38(11) . . ? N3 Si3 C49 112.03(11) . . ? C37 Si3 C49 107.50(11) . . ? C43 Si3 C49 108.14(11) . . ? N1 Ti1 N5 109.92(8) . . ? N1 Ti1 N3 108.82(8) . . ? N5 Ti1 N3 111.47(9) . . ? N1 Ti1 N2 86.86(7) . . ? N5 Ti1 N2 117.04(8) . . ? N3 Ti1 N2 119.35(8) . . ? N1 Ti1 Ti2 44.12(5) . . ? N5 Ti1 Ti2 126.90(6) . . ? N3 Ti1 Ti2 120.48(7) . . ? N2 Ti1 Ti2 42.99(5) . . ? N6 Ti2 N4 110.60(9) . . ? N6 Ti2 N2 113.64(8) . . ? N4 Ti2 N2 118.07(8) . . ? N6 Ti2 N1 113.27(8) . . ? N4 Ti2 N1 113.71(8) . . ? N2 Ti2 N1 85.56(7) . . ? N6 Ti2 Ti1 119.25(7) . . ? N4 Ti2 Ti1 129.97(6) . . ? N2 Ti2 Ti1 43.91(5) . . ? N1 Ti2 Ti1 41.89(5) . . ? _database_code_depnum_ccdc_archive 'CCDC 931098' ####################################################################### # # 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_5 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C34 H51 N9 Ti3' _chemical_formula_sum 'C34 H51 N9 Ti3' _chemical_formula_weight 729.54 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 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 10.501(2) _cell_length_b 27.443(5) _cell_length_c 13.322(3) _cell_angle_alpha 90 _cell_angle_beta 90.77(3) _cell_angle_gamma 90 _cell_volume 3838.8(13) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 1.65 _cell_measurement_theta_max 26.05 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour brown _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.1 _exptl_crystal_density_diffrn 1.262 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1536 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.644 _exptl_absorpt_correction_type refdelf _exptl_absorpt_process_details ; (See: Walker, N. & Stuart, D. (1983) Acta Cryst. A39, 158-166) ; _exptl_absorpt_correction_T_min 0.483 _exptl_absorpt_correction_T_max 0.834 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(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 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 4 _diffrn_standards_decay_% 0.1 _diffrn_reflns_av_R_equivalents 0.0342 _diffrn_reflns_av_unetI/netI 0.0234 _diffrn_reflns_number 29677 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -33 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 26.06 _diffrn_reflns_theta_full 26.06 _diffrn_measured_fraction_theta_full 0.99 _diffrn_measured_fraction_theta_max 0.99 _reflns_number_total 7499 _reflns_number_gt 6411 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'Stoe IPDS software (Stoe, 1996)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0512P)^2^+1.5786P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 7499 _refine_ls_number_parameters 425 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0403 _refine_ls_R_factor_gt 0.033 _refine_ls_wR_factor_ref 0.0906 _refine_ls_wR_factor_gt 0.0862 _refine_ls_goodness_of_fit_ref 1.044 _refine_ls_restrained_S_all 1.044 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.555 _refine_diff_density_min -0.373 _refine_diff_density_rms 0.053 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.89608(17) 0.13730(7) 0.61765(12) 0.0264(4) Uani 1 1 d . . . C2 C 0.92636(19) 0.09604(8) 0.56135(14) 0.0347(4) Uani 1 1 d . . . H2 H 0.8927 0.0652 0.5795 0.042 Uiso 1 1 calc R . . C3 C 1.0053(2) 0.09989(11) 0.47909(15) 0.0485(6) Uani 1 1 d . . . H3 H 1.0255 0.0716 0.4415 0.058 Uiso 1 1 calc R . . C4 C 1.0547(2) 0.14419(12) 0.45127(17) 0.0573(7) Uani 1 1 d . . . H4 H 1.1066 0.1467 0.3936 0.069 Uiso 1 1 calc R . . C5 C 1.0285(2) 0.18480(11) 0.50757(19) 0.0525(6) Uani 1 1 d . . . H5 H 1.0641 0.2153 0.4895 0.063 Uiso 1 1 calc R . . C6 C 0.9505(2) 0.18171(8) 0.59055(16) 0.0376(5) Uani 1 1 d . . . H6 H 0.9339 0.21 0.6292 0.045 Uiso 1 1 calc R . . C7 C 0.82078(19) 0.13918(7) 1.00687(13) 0.0289(4) Uani 1 1 d . . . C8 C 0.9285(3) 0.12347(9) 1.06052(16) 0.0478(6) Uani 1 1 d . . . H8 H 0.9931 0.1059 1.0268 0.057 Uiso 1 1 calc R . . C9 C 0.9427(3) 0.13319(10) 1.16231(17) 0.0587(7) Uani 1 1 d . . . H9 H 1.016 0.1218 1.1977 0.07 Uiso 1 1 calc R . . C10 C 0.8511(3) 0.15935(9) 1.21220(16) 0.0551(7) Uani 1 1 d . . . H10 H 0.861 0.1663 1.2817 0.066 Uiso 1 1 calc R . . C11 C 0.7453(3) 0.17526(11) 1.16015(18) 0.0579(7) Uani 1 1 d . . . H11 H 0.6817 0.1932 1.1943 0.069 Uiso 1 1 calc R . . C12 C 0.7299(2) 0.16558(9) 1.05827(16) 0.0434(5) Uani 1 1 d . . . H12 H 0.6563 0.1772 1.0235 0.052 Uiso 1 1 calc R . . C13 C 0.63199(17) 0.00048(6) 0.73915(12) 0.0226(3) Uani 1 1 d . . . C14 C 0.5324(2) -0.01539(7) 0.79948(14) 0.0320(4) Uani 1 1 d . . . H14 H 0.4862 0.0077 0.8376 0.038 Uiso 1 1 calc R . . C15 C 0.4998(2) -0.06429(7) 0.80471(15) 0.0376(5) Uani 1 1 d . . . H15 H 0.4318 -0.0743 0.8463 0.045 Uiso 1 1 calc R . . C16 C 0.5652(2) -0.09850(7) 0.75007(15) 0.0363(5) Uani 1 1 d . . . H16 H 0.5444 -0.1321 0.7553 0.044 Uiso 1 1 calc R . . C17 C 0.6610(2) -0.08347(7) 0.68776(16) 0.0351(4) Uani 1 1 d . . . H17 H 0.705 -0.1068 0.6485 0.042 Uiso 1 1 calc R . . C18 C 0.69407(18) -0.03471(7) 0.68168(14) 0.0280(4) Uani 1 1 d . . . H18 H 0.76 -0.025 0.6378 0.034 Uiso 1 1 calc R . . C19 C 0.48099(17) 0.16959(6) 0.82967(13) 0.0254(4) Uani 1 1 d . . . C20 C 0.4110(2) 0.21306(8) 0.82788(18) 0.0421(5) Uani 1 1 d . . . H20 H 0.4334 0.2381 0.7822 0.051 Uiso 1 1 calc R . . C21 C 0.3096(3) 0.21995(10) 0.8920(2) 0.0589(7) Uani 1 1 d . . . H21 H 0.263 0.2496 0.8893 0.071 Uiso 1 1 calc R . . C22 C 0.2755(2) 0.18438(11) 0.9592(2) 0.0569(7) Uani 1 1 d . . . H22 H 0.2062 0.1895 1.0031 0.068 Uiso 1 1 calc R . . C23 C 0.3431(2) 0.14127(10) 0.96231(16) 0.0479(6) Uani 1 1 d . . . H23 H 0.3201 0.1166 1.0087 0.057 Uiso 1 1 calc R . . C24 C 0.4444(2) 0.13364(8) 0.89823(14) 0.0337(4) Uani 1 1 d . . . H24 H 0.4895 0.1037 0.9009 0.04 Uiso 1 1 calc R . . C25 C 0.7569(4) 0.28131(9) 0.7488(3) 0.0895(12) Uani 1 1 d . . . H25A H 0.7378 0.3079 0.7953 0.134 Uiso 1 1 calc R . . H25B H 0.6781 0.2705 0.7155 0.134 Uiso 1 1 calc R . . H25C H 0.8169 0.2928 0.6983 0.134 Uiso 1 1 calc R . . C26 C 0.9262(4) 0.25451(15) 0.8575(3) 0.1038(15) Uani 1 1 d . . . H26A H 0.9927 0.263 0.8096 0.156 Uiso 1 1 calc R . . H26B H 0.9552 0.2272 0.8994 0.156 Uiso 1 1 calc R . . H26C H 0.9084 0.2827 0.9001 0.156 Uiso 1 1 calc R . . C27 C 0.8684(2) -0.02344(8) 0.93939(17) 0.0415(5) Uani 1 1 d . . . H27A H 0.8902 -0.0282 1.0105 0.062 Uiso 1 1 calc R . . H27B H 0.9464 -0.0233 0.8998 0.062 Uiso 1 1 calc R . . H27C H 0.8128 -0.05 0.9164 0.062 Uiso 1 1 calc R . . C28 C 0.6991(2) 0.02664(9) 0.99714(15) 0.0400(5) Uani 1 1 d . . . H28A H 0.643 -0.0017 0.9896 0.06 Uiso 1 1 calc R . . H28B H 0.6506 0.0565 0.9836 0.06 Uiso 1 1 calc R . . H28C H 0.7338 0.0277 1.0658 0.06 Uiso 1 1 calc R . . C29 C 1.09703(19) 0.08884(8) 0.79348(16) 0.0366(4) Uani 1 1 d . . . H29A H 1.1685 0.0721 0.8266 0.055 Uiso 1 1 calc R . . H29B H 1.0699 0.1164 0.8349 0.055 Uiso 1 1 calc R . . H29C H 1.1238 0.1008 0.7278 0.055 Uiso 1 1 calc R . . C30 C 1.0312(2) 0.01125(8) 0.72792(16) 0.0366(4) Uani 1 1 d . . . H30A H 1.06 0.0199 0.6605 0.055 Uiso 1 1 calc R . . H30B H 0.9591 -0.0113 0.7226 0.055 Uiso 1 1 calc R . . H30C H 1.1011 -0.0043 0.7653 0.055 Uiso 1 1 calc R . . C31 C 0.6481(2) 0.15189(8) 0.47114(15) 0.0368(5) Uani 1 1 d . . . H31A H 0.7335 0.1538 0.4426 0.055 Uiso 1 1 calc R . . H31B H 0.6343 0.18 0.5151 0.055 Uiso 1 1 calc R . . H31C H 0.5843 0.152 0.4168 0.055 Uiso 1 1 calc R . . C32 C 0.6485(2) 0.06386(8) 0.46671(15) 0.0374(5) Uani 1 1 d . . . H32A H 0.577 0.0624 0.4188 0.056 Uiso 1 1 calc R . . H32B H 0.6477 0.0348 0.5095 0.056 Uiso 1 1 calc R . . H32C H 0.7287 0.0652 0.4301 0.056 Uiso 1 1 calc R . . C33 C 0.3564(2) 0.14249(8) 0.60453(16) 0.0365(4) Uani 1 1 d . . . H33A H 0.3855 0.1422 0.5349 0.055 Uiso 1 1 calc R . . H33B H 0.3837 0.1728 0.6371 0.055 Uiso 1 1 calc R . . H33C H 0.2633 0.1403 0.6053 0.055 Uiso 1 1 calc R . . C34 C 0.3680(2) 0.05462(8) 0.61211(16) 0.0377(5) Uani 1 1 d . . . H34A H 0.2749 0.0547 0.6068 0.057 Uiso 1 1 calc R . . H34B H 0.396 0.0269 0.6532 0.057 Uiso 1 1 calc R . . H34C H 0.4042 0.0518 0.5449 0.057 Uiso 1 1 calc R . . N1 N 0.80823(14) 0.13522(5) 0.69641(10) 0.0219(3) Uani 1 1 d . . . N2 N 0.80837(15) 0.12969(6) 0.90377(11) 0.0266(3) Uani 1 1 d . . . N3 N 0.66990(14) 0.04945(5) 0.73606(10) 0.0228(3) Uani 1 1 d . . . N4 N 0.58282(14) 0.16315(5) 0.76427(11) 0.0241(3) Uani 1 1 d . . . N5 N 0.81336(19) 0.24084(6) 0.80416(14) 0.0410(4) Uani 1 1 d . . . N6 N 0.80277(15) 0.02291(6) 0.92677(11) 0.0282(3) Uani 1 1 d . . . N7 N 0.99175(15) 0.05512(6) 0.78030(11) 0.0269(3) Uani 1 1 d . . . N8 N 0.63666(15) 0.10727(5) 0.52880(11) 0.0261(3) Uani 1 1 d . . . N9 N 0.41188(15) 0.10039(5) 0.65934(11) 0.0272(3) Uani 1 1 d . . . H9A H 0.3804 0.1011 0.7243 0.033 Uiso 1 1 calc R . . Ti1 Ti 0.75504(3) 0.175039(11) 0.80097(2) 0.02225(9) Uani 1 1 d . . . Ti2 Ti 0.82465(3) 0.070347(11) 0.82410(2) 0.02098(9) Uani 1 1 d . . . Ti3 Ti 0.62419(3) 0.107320(10) 0.67077(2) 0.01941(8) 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 C1 0.0219(9) 0.0379(10) 0.0194(8) 0.0025(7) -0.0002(6) 0.0020(8) C2 0.0316(10) 0.0481(12) 0.0244(9) -0.0037(8) -0.0004(8) 0.0080(9) C3 0.0345(12) 0.0864(18) 0.0247(10) -0.0071(11) 0.0019(9) 0.0197(12) C4 0.0305(12) 0.111(2) 0.0302(11) 0.0204(13) 0.0105(9) 0.0139(14) C5 0.0336(12) 0.0756(17) 0.0485(13) 0.0304(13) 0.0087(10) -0.0009(12) C6 0.0298(10) 0.0436(12) 0.0395(11) 0.0129(9) 0.0044(8) -0.0008(9) C7 0.0404(11) 0.0263(9) 0.0200(8) -0.0033(7) 0.0000(7) -0.0048(8) C8 0.0651(16) 0.0495(13) 0.0287(10) -0.0086(9) -0.0108(10) 0.0189(12) C9 0.087(2) 0.0579(15) 0.0303(11) -0.0051(10) -0.0219(12) 0.0128(14) C10 0.086(2) 0.0576(15) 0.0217(10) -0.0090(9) -0.0035(11) -0.0138(14) C11 0.0584(16) 0.0768(18) 0.0388(13) -0.0277(12) 0.0159(11) -0.0070(14) C12 0.0402(12) 0.0559(14) 0.0341(11) -0.0162(10) 0.0014(9) 0.0001(10) C13 0.0275(9) 0.0179(8) 0.0222(8) 0.0002(6) -0.0041(7) -0.0002(7) C14 0.0446(12) 0.0234(9) 0.0281(9) -0.0031(7) 0.0082(8) -0.0016(8) C15 0.0525(13) 0.0284(10) 0.0319(10) 0.0034(8) 0.0067(9) -0.0098(9) C16 0.0502(13) 0.0186(8) 0.0399(11) 0.0022(8) -0.0093(9) -0.0029(8) C17 0.0374(11) 0.0227(9) 0.0450(11) -0.0081(8) -0.0070(9) 0.0073(8) C18 0.0261(9) 0.0251(9) 0.0329(9) -0.0034(7) -0.0022(7) 0.0032(7) C19 0.0251(9) 0.0248(8) 0.0261(8) -0.0085(7) -0.0001(7) -0.0018(7) C20 0.0396(12) 0.0286(10) 0.0584(13) -0.0084(9) 0.0124(10) 0.0043(9) C21 0.0480(15) 0.0468(14) 0.0826(19) -0.0238(13) 0.0212(13) 0.0084(11) C22 0.0412(14) 0.0749(18) 0.0550(15) -0.0283(13) 0.0213(11) -0.0073(13) C23 0.0438(13) 0.0680(16) 0.0322(11) -0.0026(10) 0.0085(9) -0.0175(12) C24 0.0335(10) 0.0373(10) 0.0301(9) 0.0001(8) 0.0010(8) -0.0040(8) C25 0.079(2) 0.0257(12) 0.164(4) 0.0190(17) 0.026(2) -0.0012(13) C26 0.117(3) 0.108(3) 0.086(2) 0.009(2) -0.029(2) -0.083(3) C27 0.0465(13) 0.0356(11) 0.0425(12) 0.0110(9) 0.0038(10) 0.0081(10) C28 0.0421(12) 0.0480(12) 0.0301(10) 0.0104(9) 0.0072(9) 0.0050(10) C29 0.0263(10) 0.0459(12) 0.0375(10) -0.0017(9) 0.0003(8) -0.0058(9) C30 0.0300(10) 0.0384(11) 0.0414(11) -0.0055(9) 0.0024(8) 0.0063(9) C31 0.0427(12) 0.0395(11) 0.0282(9) 0.0084(8) -0.0017(8) 0.0018(9) C32 0.0432(12) 0.0414(11) 0.0274(9) -0.0110(8) -0.0079(8) 0.0072(9) C33 0.0303(10) 0.0404(11) 0.0386(11) 0.0014(9) -0.0078(8) 0.0041(9) C34 0.0342(11) 0.0364(11) 0.0423(11) -0.0068(9) -0.0045(9) -0.0091(9) N1 0.0236(7) 0.0220(7) 0.0201(7) 0.0003(5) 0.0012(5) -0.0015(6) N2 0.0316(8) 0.0282(8) 0.0201(7) -0.0039(6) -0.0004(6) -0.0014(6) N3 0.0273(8) 0.0188(7) 0.0223(7) -0.0012(5) 0.0000(6) -0.0010(6) N4 0.0272(8) 0.0188(7) 0.0263(7) -0.0013(5) 0.0025(6) 0.0001(6) N5 0.0502(11) 0.0273(9) 0.0456(10) -0.0097(7) 0.0082(8) -0.0133(8) N6 0.0293(8) 0.0305(8) 0.0250(7) 0.0039(6) -0.0005(6) 0.0022(6) N7 0.0240(8) 0.0304(8) 0.0263(7) -0.0001(6) -0.0006(6) -0.0002(6) N8 0.0289(8) 0.0272(8) 0.0222(7) -0.0013(6) -0.0019(6) 0.0010(6) N9 0.0264(8) 0.0286(8) 0.0265(7) -0.0025(6) -0.0006(6) -0.0029(6) Ti1 0.02663(17) 0.01807(15) 0.02208(16) -0.00336(11) 0.00120(12) -0.00349(12) Ti2 0.02270(16) 0.02162(16) 0.01860(15) -0.00135(11) 0.00027(11) 0.00056(12) Ti3 0.02313(17) 0.01660(15) 0.01846(15) -0.00115(10) -0.00088(11) 0.00015(11) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 C6 1.396(3) . ? C1 C2 1.397(3) . ? C1 N1 1.408(2) . ? C2 C3 1.387(3) . ? C2 H2 0.95 . ? C3 C4 1.375(4) . ? C3 H3 0.95 . ? C4 C5 1.374(4) . ? C4 H4 0.95 . ? C5 C6 1.387(3) . ? C5 H5 0.95 . ? C6 H6 0.95 . ? C7 C12 1.387(3) . ? C7 C8 1.398(3) . ? C7 N2 1.402(2) . ? C8 C9 1.388(3) . ? C8 H8 0.95 . ? C9 C10 1.379(4) . ? C9 H9 0.95 . ? C10 C11 1.373(4) . ? C10 H10 0.95 . ? C11 C12 1.390(3) . ? C11 H11 0.95 . ? C12 H12 0.95 . ? C13 C14 1.397(3) . ? C13 C18 1.399(2) . ? C13 N3 1.402(2) . ? C14 C15 1.387(3) . ? C14 H14 0.95 . ? C15 C16 1.377(3) . ? C15 H15 0.95 . ? C16 C17 1.376(3) . ? C16 H16 0.95 . ? C17 C18 1.385(3) . ? C17 H17 0.95 . ? C18 H18 0.95 . ? C19 N4 1.400(2) . ? C19 C20 1.401(3) . ? C19 C24 1.402(3) . ? C20 C21 1.387(3) . ? C20 H20 0.95 . ? C21 C22 1.376(4) . ? C21 H21 0.95 . ? C22 C23 1.380(4) . ? C22 H22 0.95 . ? C23 C24 1.389(3) . ? C23 H23 0.95 . ? C24 H24 0.95 . ? C25 N5 1.455(4) . ? C25 H25A 0.98 . ? C25 H25B 0.98 . ? C25 H25C 0.98 . ? C26 N5 1.424(4) . ? C26 H26A 0.98 . ? C26 H26B 0.98 . ? C26 H26C 0.98 . ? C27 N6 1.455(2) . ? C27 H27A 0.98 . ? C27 H27B 0.98 . ? C27 H27C 0.98 . ? C28 N6 1.450(3) . ? C28 H28A 0.98 . ? C28 H28B 0.98 . ? C28 H28C 0.98 . ? C29 N7 1.450(3) . ? C29 H29A 0.98 . ? C29 H29B 0.98 . ? C29 H29C 0.98 . ? C30 N7 1.455(2) . ? C30 H30A 0.98 . ? C30 H30B 0.98 . ? C30 H30C 0.98 . ? C31 N8 1.451(2) . ? C31 H31A 0.98 . ? C31 H31B 0.98 . ? C31 H31C 0.98 . ? C32 N8 1.457(2) . ? C32 H32A 0.98 . ? C32 H32B 0.98 . ? C32 H32C 0.98 . ? C33 N9 1.482(2) . ? C33 H33A 0.98 . ? C33 H33B 0.98 . ? C33 H33C 0.98 . ? C34 N9 1.476(2) . ? C34 H34A 0.98 . ? C34 H34B 0.98 . ? C34 H34C 0.98 . ? N1 Ti1 1.8622(14) . ? N1 Ti3 2.1024(15) . ? N1 Ti2 2.4668(14) . ? N2 Ti1 1.9279(16) . ? N2 Ti2 1.9527(15) . ? N3 Ti3 1.8702(14) . ? N3 Ti2 2.0723(16) . ? N4 Ti1 1.8954(16) . ? N4 Ti3 2.0254(15) . ? N5 Ti1 1.9071(17) . ? N6 Ti2 1.9044(15) . ? N7 Ti2 1.9030(16) . ? N8 Ti3 1.8976(15) . ? N9 Ti3 2.2407(16) . ? N9 H9A 0.93 . ? Ti1 Ti3 2.8786(7) . ? Ti1 Ti2 2.9796(7) . ? Ti2 Ti3 3.0850(9) . ? 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 C6 C1 C2 118.17(18) . . ? C6 C1 N1 120.18(17) . . ? C2 C1 N1 121.56(17) . . ? C3 C2 C1 120.3(2) . . ? C3 C2 H2 119.8 . . ? C1 C2 H2 119.8 . . ? C4 C3 C2 120.8(2) . . ? C4 C3 H3 119.6 . . ? C2 C3 H3 119.6 . . ? C5 C4 C3 119.4(2) . . ? C5 C4 H4 120.3 . . ? C3 C4 H4 120.3 . . ? C4 C5 C6 120.7(2) . . ? C4 C5 H5 119.7 . . ? C6 C5 H5 119.7 . . ? C5 C6 C1 120.5(2) . . ? C5 C6 H6 119.7 . . ? C1 C6 H6 119.7 . . ? C12 C7 C8 117.81(18) . . ? C12 C7 N2 121.68(18) . . ? C8 C7 N2 120.48(18) . . ? C9 C8 C7 121.0(2) . . ? C9 C8 H8 119.5 . . ? C7 C8 H8 119.5 . . ? C10 C9 C8 120.3(2) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C11 C10 C9 119.2(2) . . ? C11 C10 H10 120.4 . . ? C9 C10 H10 120.4 . . ? C10 C11 C12 121.0(2) . . ? C10 C11 H11 119.5 . . ? C12 C11 H11 119.5 . . ? C7 C12 C11 120.6(2) . . ? C7 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C14 C13 C18 117.23(16) . . ? C14 C13 N3 122.04(15) . . ? C18 C13 N3 120.72(16) . . ? C15 C14 C13 121.18(18) . . ? C15 C14 H14 119.4 . . ? C13 C14 H14 119.4 . . ? C16 C15 C14 120.5(2) . . ? C16 C15 H15 119.7 . . ? C14 C15 H15 119.7 . . ? C17 C16 C15 119.23(18) . . ? C17 C16 H16 120.4 . . ? C15 C16 H16 120.4 . . ? C16 C17 C18 120.71(18) . . ? C16 C17 H17 119.6 . . ? C18 C17 H17 119.6 . . ? C17 C18 C13 121.06(18) . . ? C17 C18 H18 119.5 . . ? C13 C18 H18 119.5 . . ? N4 C19 C20 120.11(17) . . ? N4 C19 C24 122.35(17) . . ? C20 C19 C24 117.54(18) . . ? C21 C20 C19 120.8(2) . . ? C21 C20 H20 119.6 . . ? C19 C20 H20 119.6 . . ? C22 C21 C20 120.9(2) . . ? C22 C21 H21 119.6 . . ? C20 C21 H21 119.6 . . ? C21 C22 C23 119.3(2) . . ? C21 C22 H22 120.4 . . ? C23 C22 H22 120.4 . . ? C22 C23 C24 120.6(2) . . ? C22 C23 H23 119.7 . . ? C24 C23 H23 119.7 . . ? C23 C24 C19 120.9(2) . . ? C23 C24 H24 119.6 . . ? C19 C24 H24 119.6 . . ? N5 C25 H25A 109.5 . . ? N5 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? N5 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? N5 C26 H26A 109.5 . . ? N5 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? N5 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? N6 C27 H27A 109.5 . . ? N6 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? N6 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? N6 C28 H28A 109.5 . . ? N6 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? N6 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? N7 C29 H29A 109.5 . . ? N7 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? N7 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? N7 C30 H30A 109.5 . . ? N7 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? N7 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? N8 C31 H31A 109.5 . . ? N8 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? N8 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? N8 C32 H32A 109.5 . . ? N8 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? N8 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? N9 C33 H33A 109.5 . . ? N9 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? N9 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? N9 C34 H34A 109.5 . . ? N9 C34 H34B 109.5 . . ? H34A C34 H34B 109.5 . . ? N9 C34 H34C 109.5 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? C1 N1 Ti1 137.73(12) . . ? C1 N1 Ti3 120.26(11) . . ? Ti1 N1 Ti3 92.92(7) . . ? C1 N1 Ti2 120.19(11) . . ? Ti1 N1 Ti2 85.79(5) . . ? Ti3 N1 Ti2 84.54(5) . . ? C7 N2 Ti1 126.74(12) . . ? C7 N2 Ti2 132.80(13) . . ? Ti1 N2 Ti2 100.31(7) . . ? C13 N3 Ti3 139.14(12) . . ? C13 N3 Ti2 117.99(11) . . ? Ti3 N3 Ti2 102.86(7) . . ? C19 N4 Ti1 123.50(12) . . ? C19 N4 Ti3 130.57(11) . . ? Ti1 N4 Ti3 94.42(7) . . ? C26 N5 C25 112.5(3) . . ? C26 N5 Ti1 121.7(2) . . ? C25 N5 Ti1 125.67(19) . . ? C28 N6 C27 110.22(16) . . ? C28 N6 Ti2 121.00(13) . . ? C27 N6 Ti2 128.23(13) . . ? C29 N7 C30 111.38(16) . . ? C29 N7 Ti2 121.82(13) . . ? C30 N7 Ti2 126.76(13) . . ? C31 N8 C32 112.41(16) . . ? C31 N8 Ti3 122.30(12) . . ? C32 N8 Ti3 125.04(13) . . ? C34 N9 C33 109.58(15) . . ? C34 N9 Ti3 113.93(12) . . ? C33 N9 Ti3 110.59(12) . . ? C34 N9 H9A 107.5 . . ? C33 N9 H9A 107.5 . . ? Ti3 N9 H9A 107.5 . . ? N1 Ti1 N4 90.04(7) . . ? N1 Ti1 N5 118.22(7) . . ? N4 Ti1 N5 118.28(8) . . ? N1 Ti1 N2 93.75(6) . . ? N4 Ti1 N2 109.83(7) . . ? N5 Ti1 N2 120.35(8) . . ? N1 Ti1 Ti3 46.84(5) . . ? N4 Ti1 Ti3 44.55(5) . . ? N5 Ti1 Ti3 140.83(6) . . ? N2 Ti1 Ti3 98.22(5) . . ? N1 Ti1 Ti2 55.66(4) . . ? N4 Ti1 Ti2 95.31(4) . . ? N5 Ti1 Ti2 146.35(6) . . ? N2 Ti1 Ti2 40.15(4) . . ? Ti3 Ti1 Ti2 63.528(18) . . ? N7 Ti2 N6 101.00(7) . . ? N7 Ti2 N2 115.95(7) . . ? N6 Ti2 N2 99.65(7) . . ? N7 Ti2 N3 119.01(6) . . ? N6 Ti2 N3 96.66(7) . . ? N2 Ti2 N3 117.69(6) . . ? N7 Ti2 N1 90.18(6) . . ? N6 Ti2 N1 168.71(6) . . ? N2 Ti2 N1 76.53(6) . . ? N3 Ti2 N1 76.25(5) . . ? N7 Ti2 Ti1 113.95(5) . . ? N6 Ti2 Ti1 134.56(5) . . ? N2 Ti2 Ti1 39.54(5) . . ? N3 Ti2 Ti1 91.08(4) . . ? N1 Ti2 Ti1 38.56(3) . . ? N7 Ti2 Ti3 119.53(5) . . ? N6 Ti2 Ti3 127.77(5) . . ? N2 Ti2 Ti3 91.24(5) . . ? N3 Ti2 Ti3 36.23(4) . . ? N1 Ti2 Ti3 42.72(4) . . ? Ti1 Ti2 Ti3 56.641(10) . . ? N3 Ti3 N8 116.25(6) . . ? N3 Ti3 N4 114.35(6) . . ? N8 Ti3 N4 129.17(6) . . ? N3 Ti3 N1 90.23(6) . . ? N8 Ti3 N1 94.97(7) . . ? N4 Ti3 N1 80.15(6) . . ? N3 Ti3 N9 102.03(6) . . ? N8 Ti3 N9 90.81(7) . . ? N4 Ti3 N9 83.37(6) . . ? N1 Ti3 N9 162.47(6) . . ? N3 Ti3 Ti1 98.66(5) . . ? N8 Ti3 Ti1 124.21(5) . . ? N4 Ti3 Ti1 41.03(4) . . ? N1 Ti3 Ti1 40.25(4) . . ? N9 Ti3 Ti1 124.20(4) . . ? N3 Ti3 Ti2 40.91(4) . . ? N8 Ti3 Ti2 127.17(5) . . ? N4 Ti3 Ti2 89.53(5) . . ? N1 Ti3 Ti2 52.75(4) . . ? N9 Ti3 Ti2 133.36(4) . . ? Ti1 Ti3 Ti2 59.831(19) . . ? _database_code_depnum_ccdc_archive 'CCDC 931099' ####################################################################### # # 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_[V(N-2,6-Cl2-C6H3)(NMe2)(NH-2,6-Cl2-C6H3)]2 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C14 H12 Cl4 N3 V1' _chemical_formula_sum 'C14 H14 Cl4 N3 V' _chemical_formula_weight 417.02 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'F d d 2' _symmetry_space_group_name_Hall 'F 2 -2d' _symmetry_Int_Tables_number 43 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/4, y+1/4, z+1/4' 'x+1/4, -y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x+1/4, y+3/4, z+3/4' 'x+1/4, -y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+3/4, y+1/4, z+3/4' 'x+3/4, -y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+3/4, y+3/4, z+1/4' 'x+3/4, -y+3/4, z+1/4' _cell_length_a 23.961(5) _cell_length_b 32.093(6) _cell_length_c 8.9451(18) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 6879(2) _cell_formula_units_Z 16 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 4788 _cell_measurement_theta_min 2.5446 _cell_measurement_theta_max 32.0956 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description losange _exptl_crystal_colour black _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.236 _exptl_crystal_size_min 0.099 _exptl_crystal_density_diffrn 1.611 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3360 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 1.196 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.7926 _exptl_absorpt_correction_T_max 0.8912 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(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 'Oxford-Diffraction XCALIBUR' _diffrn_measurement_method \w-\f _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_orient_matrix_ub_11 -0.0600051941 _diffrn_orient_matrix_ub_12 0.0183516362 _diffrn_orient_matrix_ub_13 -0.0045592516 _diffrn_orient_matrix_ub_21 0.0517871912 _diffrn_orient_matrix_ub_22 0.0215761865 _diffrn_orient_matrix_ub_23 -0.0045264792 _diffrn_orient_matrix_ub_31 0.0018702122 _diffrn_orient_matrix_ub_32 -0.0085871932 _diffrn_orient_matrix_ub_33 -0.0211137574 _diffrn_reflns_av_R_equivalents 0.0404 _diffrn_reflns_av_unetI/netI 0.0748 _diffrn_reflns_number 17470 _diffrn_reflns_limit_h_min -34 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -47 _diffrn_reflns_limit_k_max 34 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.06 _diffrn_reflns_theta_max 32.17 _diffrn_reflns_theta_full 25 _diffrn_measured_fraction_theta_full 0.998 _diffrn_measured_fraction_theta_max 0.962 _reflns_number_total 5691 _reflns_number_gt 3938 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'CrysAlis CCD, Oxford Diffraction Ltd.' _computing_cell_refinement 'CrysAlis RED, Oxford Diffraction Ltd.' _computing_data_reduction 'CrysAlis RED, Oxford Diffraction Ltd.' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0401P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 5691 _refine_ls_number_parameters 201 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0549 _refine_ls_R_factor_gt 0.0347 _refine_ls_wR_factor_ref 0.0833 _refine_ls_wR_factor_gt 0.0789 _refine_ls_goodness_of_fit_ref 0.884 _refine_ls_restrained_S_all 0.884 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.02(2) _refine_diff_density_max 0.373 _refine_diff_density_min -0.512 _refine_diff_density_rms 0.105 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N2 N 1.19474(8) 0.24004(6) 1.2685(2) 0.0215(5) Uani 1 1 d . . . C2 C 1.14047(10) 0.23221(7) 1.2214(3) 0.0238(5) Uani 1 1 d . . . C3 C 1.12756(12) 0.22004(9) 1.0741(3) 0.0313(7) Uani 1 1 d . . . C4 C 1.07383(13) 0.20988(9) 1.0299(4) 0.0397(7) Uani 1 1 d . . . H4 H 1.0668 0.2009 0.9305 0.048 Uiso 1 1 calc R . . C5 C 1.03070(13) 0.21289(10) 1.1314(5) 0.0444(8) Uani 1 1 d . . . H5 H 0.994 0.2051 1.1026 0.053 Uiso 1 1 calc R . . C6 C 1.04043(11) 0.22703(9) 1.2730(4) 0.0377(8) Uani 1 1 d . . . H6 H 1.0103 0.2306 1.341 0.045 Uiso 1 1 calc R . . C7 C 1.09467(11) 0.23623(8) 1.3170(3) 0.0291(6) Uani 1 1 d . . . N3 N 1.19539(9) 0.31543(7) 1.1314(3) 0.0270(5) Uani 1 1 d . . . H3A H 1.1904 0.295 1.0606 0.032 Uiso 1 1 calc R . . H3B H 1.1608 0.3197 1.1736 0.032 Uiso 1 1 calc R . . C9 C 1.20556(11) 0.35073(8) 1.0512(3) 0.0268(6) Uani 1 1 d . . . C10 C 1.17214(13) 0.36580(9) 0.9350(3) 0.0336(7) Uani 1 1 d . . . C11 C 1.18436(15) 0.40179(9) 0.8561(4) 0.0421(8) Uani 1 1 d . . . H11 H 1.1601 0.4114 0.7794 0.05 Uiso 1 1 calc R . . C12 C 1.23272(15) 0.42361(10) 0.8911(4) 0.0443(8) Uani 1 1 d . . . H12 H 1.2418 0.4481 0.8369 0.053 Uiso 1 1 calc R . . C13 C 1.26735(13) 0.41017(8) 1.0026(4) 0.0358(7) Uani 1 1 d . . . H13 H 1.3006 0.4249 1.0256 0.043 Uiso 1 1 calc R . . C14 C 1.25308(11) 0.37484(8) 1.0809(3) 0.0298(6) Uani 1 1 d . . . Cl4 Cl 1.11153(3) 0.33822(3) 0.88873(10) 0.0491(2) Uani 1 1 d . . . C16 C 1.26099(15) 0.30417(13) 1.6104(4) 0.0546(10) Uani 1 1 d . . . H16A H 1.2355 0.2954 1.6902 0.082 Uiso 1 1 calc R . . H16B H 1.2801 0.3298 1.6403 0.082 Uiso 1 1 calc R . . H16C H 1.2886 0.2822 1.5924 0.082 Uiso 1 1 calc R . . C17 C 1.18921(15) 0.34566(10) 1.4940(4) 0.0514(9) Uani 1 1 d . . . H17A H 1.2088 0.3711 1.5248 0.077 Uiso 1 1 calc R . . H17B H 1.1618 0.338 1.5706 0.077 Uiso 1 1 calc R . . H17C H 1.17 0.3506 1.3989 0.077 Uiso 1 1 calc R . . N1 N 1.22974(9) 0.31157(7) 1.4757(3) 0.0290(5) Uani 1 1 d . . . Cl1 Cl 1.18067(4) 0.21639(3) 0.94339(8) 0.0454(2) Uani 1 1 d . . . Cl2 Cl 1.10712(3) 0.25442(2) 1.49768(9) 0.03995(19) Uani 1 1 d . . . Cl3 Cl 1.29506(3) 0.35696(2) 1.22540(9) 0.03504(17) Uani 1 1 d . . . V1 V 1.239038(18) 0.289063(13) 1.28765(5) 0.02056(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 N2 0.0203(10) 0.0198(10) 0.0243(12) 0.0008(9) 0.0004(9) -0.0012(8) C2 0.0205(12) 0.0161(11) 0.0346(15) 0.0019(12) 0.0002(12) -0.0002(10) C3 0.0258(14) 0.0285(14) 0.0395(17) 0.0018(13) -0.0065(12) 0.0013(11) C4 0.0358(16) 0.0353(16) 0.0481(19) 0.0038(15) -0.0209(16) -0.0045(13) C5 0.0238(15) 0.0367(17) 0.073(2) 0.0096(17) -0.0159(17) -0.0033(13) C6 0.0203(13) 0.0329(16) 0.060(2) 0.0127(16) 0.0036(15) 0.0006(11) C7 0.0240(14) 0.0220(13) 0.0414(17) 0.0037(12) 0.0028(12) 0.0010(11) N3 0.0254(12) 0.0263(12) 0.0294(12) 0.0026(10) -0.0007(11) 0.0010(9) C9 0.0277(13) 0.0253(13) 0.0273(14) 0.0025(12) 0.0060(12) 0.0053(11) C10 0.0382(17) 0.0297(15) 0.0329(16) 0.0038(13) 0.0034(13) 0.0056(13) C11 0.057(2) 0.0346(17) 0.0345(17) 0.0083(14) -0.0001(16) 0.0096(16) C12 0.066(2) 0.0258(16) 0.0416(18) 0.0082(14) 0.0097(18) 0.0018(16) C13 0.0420(17) 0.0253(15) 0.0400(18) 0.0023(13) 0.0097(15) -0.0007(12) C14 0.0324(15) 0.0226(13) 0.0346(15) 0.0044(12) 0.0049(13) 0.0037(12) Cl4 0.0415(5) 0.0567(5) 0.0493(5) 0.0157(4) -0.0148(4) -0.0031(4) C16 0.058(2) 0.074(3) 0.0317(18) -0.0121(18) -0.0081(18) 0.0136(19) C17 0.065(2) 0.0418(19) 0.047(2) -0.0148(16) 0.0068(19) 0.0155(18) N1 0.0313(12) 0.0241(12) 0.0316(12) -0.0032(10) -0.0004(11) -0.0017(10) Cl1 0.0451(5) 0.0617(5) 0.0292(4) -0.0079(4) -0.0019(3) -0.0002(4) Cl2 0.0325(4) 0.0459(4) 0.0415(4) -0.0030(3) 0.0131(3) -0.0002(3) Cl3 0.0306(4) 0.0279(3) 0.0466(4) 0.0058(3) -0.0051(3) -0.0054(3) V1 0.01937(19) 0.02018(19) 0.0221(2) 0.00005(19) -0.00023(18) -0.00009(17) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 N2 C2 1.390(3) . ? N2 V1 1.849(2) 14_755 ? N2 V1 1.905(2) . ? C2 C7 1.397(4) . ? C2 C3 1.408(4) . ? C3 C4 1.386(4) . ? C3 Cl1 1.732(3) . ? C4 C5 1.379(5) . ? C4 H4 0.95 . ? C5 C6 1.366(5) . ? C5 H5 0.95 . ? C6 C7 1.390(4) . ? C6 H6 0.95 . ? C7 Cl2 1.744(3) . ? N3 C9 1.363(3) . ? N3 V1 1.940(2) . ? N3 H3A 0.92 . ? N3 H3B 0.92 . ? C9 C10 1.398(4) . ? C9 C14 1.402(4) . ? C10 C11 1.385(4) . ? C10 Cl4 1.750(3) . ? C11 C12 1.390(5) . ? C11 H11 0.95 . ? C12 C13 1.368(5) . ? C12 H12 0.95 . ? C13 C14 1.376(4) . ? C13 H13 0.95 . ? C14 Cl3 1.735(3) . ? C16 N1 1.439(4) . ? C16 H16A 0.98 . ? C16 H16B 0.98 . ? C16 H16C 0.98 . ? C17 N1 1.472(4) . ? C17 H17A 0.98 . ? C17 H17B 0.98 . ? C17 H17C 0.98 . ? N1 V1 1.844(2) . ? Cl3 V1 2.6192(9) . ? V1 N2 1.849(2) 14_755 ? V1 V1 2.5617(10) 14_755 ? 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 C2 N2 V1 137.69(17) . 14_755 ? C2 N2 V1 134.24(17) . . ? V1 N2 V1 86.04(9) 14_755 . ? N2 C2 C7 122.2(3) . . ? N2 C2 C3 122.6(2) . . ? C7 C2 C3 115.2(2) . . ? C4 C3 C2 122.4(3) . . ? C4 C3 Cl1 118.3(2) . . ? C2 C3 Cl1 119.3(2) . . ? C5 C4 C3 119.5(3) . . ? C5 C4 H4 120.3 . . ? C3 C4 H4 120.3 . . ? C6 C5 C4 120.4(3) . . ? C6 C5 H5 119.8 . . ? C4 C5 H5 119.8 . . ? C5 C6 C7 119.5(3) . . ? C5 C6 H6 120.2 . . ? C7 C6 H6 120.2 . . ? C6 C7 C2 122.8(3) . . ? C6 C7 Cl2 119.6(2) . . ? C2 C7 Cl2 117.6(2) . . ? C9 N3 V1 130.21(19) . . ? C9 N3 H3A 104.7 . . ? V1 N3 H3A 104.7 . . ? C9 N3 H3B 104.7 . . ? V1 N3 H3B 104.7 . . ? H3A N3 H3B 105.7 . . ? N3 C9 C10 125.2(3) . . ? N3 C9 C14 120.3(3) . . ? C10 C9 C14 114.5(3) . . ? C11 C10 C9 123.1(3) . . ? C11 C10 Cl4 118.5(2) . . ? C9 C10 Cl4 118.4(2) . . ? C10 C11 C12 118.8(3) . . ? C10 C11 H11 120.6 . . ? C12 C11 H11 120.6 . . ? C13 C12 C11 120.8(3) . . ? C13 C12 H12 119.6 . . ? C11 C12 H12 119.6 . . ? C12 C13 C14 118.7(3) . . ? C12 C13 H13 120.6 . . ? C14 C13 H13 120.6 . . ? C13 C14 C9 124.1(3) . . ? C13 C14 Cl3 120.5(2) . . ? C9 C14 Cl3 115.4(2) . . ? N1 C16 H16A 109.5 . . ? N1 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? N1 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? N1 C17 H17A 109.5 . . ? N1 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? N1 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C16 N1 C17 111.9(3) . . ? C16 N1 V1 129.5(2) . . ? C17 N1 V1 118.2(2) . . ? C14 Cl3 V1 97.84(10) . . ? N1 V1 N2 112.70(10) . 14_755 ? N1 V1 N2 109.75(10) . . ? N2 V1 N2 93.01(9) 14_755 . ? N1 V1 N3 114.90(10) . . ? N2 V1 N3 128.05(10) 14_755 . ? N2 V1 N3 89.73(9) . . ? N1 V1 V1 114.10(7) . 14_755 ? N2 V1 V1 47.91(6) 14_755 14_755 ? N2 V1 V1 46.06(6) . 14_755 ? N3 V1 V1 122.52(7) . 14_755 ? N1 V1 Cl3 85.98(8) . . ? N2 V1 Cl3 87.76(7) 14_755 . ? N2 V1 Cl3 162.42(7) . . ? N3 V1 Cl3 76.12(7) . . ? V1 V1 Cl3 135.17(3) 14_755 . ? _database_code_depnum_ccdc_archive 'CCDC 931100' ####################################################################### # # 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_7 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C32 H58 N6 Ti2' _chemical_formula_sum 'C32 H58 N6 Ti2' _chemical_formula_weight 622.64 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.7228(3) _cell_length_b 10.4433(3) _cell_length_c 18.5184(5) _cell_angle_alpha 77.236(2) _cell_angle_beta 75.656(2) _cell_angle_gamma 79.334(2) _cell_volume 1759.70(9) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 9977 _cell_measurement_theta_min 2.24 _cell_measurement_theta_max 31.95 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.08 _exptl_crystal_density_diffrn 1.175 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 672 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.482 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.858 _exptl_absorpt_correction_T_max 0.993 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180 _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_unetI/netI 0.0332 _diffrn_reflns_number 50964 _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 -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.15 _diffrn_reflns_theta_max 32.12 _diffrn_reflns_theta_full 32.12 _diffrn_measured_fraction_theta_full 0.989 _diffrn_measured_fraction_theta_max 0.989 _reflns_number_total 12229 _reflns_number_gt 9259 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0462P)^2^+0.4758P] 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_number_reflns 12229 _refine_ls_number_parameters 377 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0571 _refine_ls_R_factor_gt 0.0368 _refine_ls_wR_factor_ref 0.1032 _refine_ls_wR_factor_gt 0.0918 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.405 _refine_diff_density_min -0.273 _refine_diff_density_rms 0.054 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.09854(12) 0.09367(12) 0.19687(6) 0.0196(2) Uani 1 1 d . . . C2 C 0.13976(13) 0.10813(13) 0.11674(7) 0.0232(2) Uani 1 1 d . . . C3 C 0.09688(15) 0.02220(14) 0.08140(7) 0.0295(3) Uani 1 1 d . . . H3 H 0.1252 0.0307 0.0278 0.035 Uiso 1 1 calc R . . C4 C 0.01425(15) -0.07501(14) 0.12209(8) 0.0317(3) Uani 1 1 d . . . H4 H -0.0106 -0.1346 0.0969 0.038 Uiso 1 1 calc R . . C5 C -0.03190(14) -0.08478(13) 0.19972(8) 0.0277(3) Uani 1 1 d . . . H5 H -0.0908 -0.1502 0.2274 0.033 Uiso 1 1 calc R . . C6 C 0.00592(12) -0.00104(12) 0.23832(7) 0.0213(2) Uani 1 1 d . . . C7 C 0.22961(14) 0.21328(15) 0.06797(7) 0.0290(3) Uani 1 1 d . . . H7 H 0.2403 0.2725 0.1013 0.035 Uiso 1 1 calc R . . C8 C 0.15648(19) 0.29880(18) 0.00543(9) 0.0456(4) Uani 1 1 d . . . H8A H 0.1554 0.2449 -0.0315 0.068 Uiso 1 1 calc R . . H8B H 0.2095 0.3733 -0.0201 0.068 Uiso 1 1 calc R . . H8C H 0.0579 0.3327 0.028 0.068 Uiso 1 1 calc R . . C9 C 0.37929(16) 0.15184(19) 0.03216(9) 0.0424(4) Uani 1 1 d . . . H9A H 0.431 0.1078 0.0721 0.064 Uiso 1 1 calc R . . H9B H 0.4317 0.2215 -0.0017 0.064 Uiso 1 1 calc R . . H9C H 0.3712 0.0868 0.0031 0.064 Uiso 1 1 calc R . . C10 C -0.05675(13) -0.00412(13) 0.32197(7) 0.0254(2) Uani 1 1 d . . . H10 H 0.0125 0.0289 0.343 0.031 Uiso 1 1 calc R . . C11 C -0.19630(18) 0.0917(2) 0.33200(10) 0.0493(4) Uani 1 1 d . . . H11A H -0.2678 0.0603 0.3135 0.074 Uiso 1 1 calc R . . H11B H -0.1787 0.18 0.3031 0.074 Uiso 1 1 calc R . . H11C H -0.232 0.0963 0.3858 0.074 Uiso 1 1 calc R . . C12 C -0.0800(2) -0.14209(18) 0.36724(10) 0.0536(5) Uani 1 1 d . . . H12A H -0.1555 -0.1732 0.3518 0.08 Uiso 1 1 calc R . . H12B H -0.1086 -0.1386 0.4214 0.08 Uiso 1 1 calc R . . H12C H 0.0093 -0.2032 0.3576 0.08 Uiso 1 1 calc R . . C13 C 0.46642(13) 0.31874(12) 0.27902(7) 0.0222(2) Uani 1 1 d . . . C14 C 0.57010(13) 0.35775(14) 0.21253(7) 0.0271(3) Uani 1 1 d . . . C15 C 0.65400(17) 0.45239(17) 0.21282(9) 0.0411(4) Uani 1 1 d . . . H15 H 0.7218 0.4806 0.168 0.049 Uiso 1 1 calc R . . C16 C 0.6415(2) 0.50605(19) 0.27597(11) 0.0501(4) Uani 1 1 d . . . H16 H 0.6985 0.5718 0.2743 0.06 Uiso 1 1 calc R . . C17 C 0.54525(19) 0.46351(17) 0.34186(10) 0.0422(4) Uani 1 1 d . . . H17 H 0.5387 0.499 0.3858 0.051 Uiso 1 1 calc R . . C18 C 0.45775(14) 0.37003(13) 0.34531(8) 0.0277(3) Uani 1 1 d . . . C19 C 0.59451(14) 0.30014(15) 0.14142(7) 0.0307(3) Uani 1 1 d . . . H19 H 0.5396 0.2232 0.1539 0.037 Uiso 1 1 calc R . . C20 C 0.54067(18) 0.40025(17) 0.07745(8) 0.0402(4) Uani 1 1 d . . . H20A H 0.4361 0.4209 0.0916 0.06 Uiso 1 1 calc R . . H20B H 0.5674 0.3626 0.0311 0.06 Uiso 1 1 calc R . . H20C H 0.5839 0.4815 0.0686 0.06 Uiso 1 1 calc R . . C21 C 0.75333(18) 0.2493(2) 0.11339(10) 0.0512(4) Uani 1 1 d . . . H21A H 0.808 0.3245 0.0954 0.077 Uiso 1 1 calc R . . H21B H 0.7633 0.2021 0.0717 0.077 Uiso 1 1 calc R . . H21C H 0.7901 0.1888 0.1551 0.077 Uiso 1 1 calc R . . C22 C 0.36283(15) 0.31655(15) 0.41996(8) 0.0298(3) Uani 1 1 d . . . H22 H 0.2773 0.2912 0.4085 0.036 Uiso 1 1 calc R . . C23 C 0.44509(18) 0.1905(2) 0.45795(9) 0.0483(4) Uani 1 1 d . . . H23A H 0.4715 0.1251 0.4245 0.072 Uiso 1 1 calc R . . H23B H 0.3844 0.1538 0.506 0.072 Uiso 1 1 calc R . . H23C H 0.532 0.2119 0.4677 0.072 Uiso 1 1 calc R . . C24 C 0.3092(2) 0.4144(2) 0.47389(12) 0.0614(6) Uani 1 1 d . . . H24A H 0.39 0.4318 0.4914 0.092 Uiso 1 1 calc R . . H24B H 0.2388 0.377 0.5176 0.092 Uiso 1 1 calc R . . H24C H 0.2643 0.4974 0.4475 0.092 Uiso 1 1 calc R . . C25 C 0.40768(17) -0.13967(16) 0.17760(10) 0.0395(3) Uani 1 1 d . . . H25A H 0.4328 -0.1219 0.1221 0.059 Uiso 1 1 calc R . . H25B H 0.3034 -0.1348 0.1948 0.059 Uiso 1 1 calc R . . H25C H 0.4532 -0.2284 0.1967 0.059 Uiso 1 1 calc R . . C26 C 0.61246(19) -0.0566(2) 0.18956(15) 0.0621(6) Uani 1 1 d . . . H26A H 0.6504 -0.1478 0.2093 0.093 Uiso 1 1 calc R . . H26B H 0.6431 0.0047 0.2136 0.093 Uiso 1 1 calc R . . H26C H 0.6488 -0.0365 0.1346 0.093 Uiso 1 1 calc R . . C27 C 0.3296(3) -0.19463(17) 0.37752(11) 0.0570(5) Uani 1 1 d . . . H27A H 0.3941 -0.2212 0.413 0.085 Uiso 1 1 calc R . . H27B H 0.378 -0.2219 0.3291 0.085 Uiso 1 1 calc R . . H27C H 0.2429 -0.2373 0.3988 0.085 Uiso 1 1 calc R . . C28 C 0.21638(19) -0.01074(17) 0.43620(8) 0.0415(4) Uani 1 1 d . . . H28A H 0.1258 -0.0478 0.4545 0.062 Uiso 1 1 calc R . . H28B H 0.1967 0.0862 0.4285 0.062 Uiso 1 1 calc R . . H28C H 0.2764 -0.0432 0.4737 0.062 Uiso 1 1 calc R . . C29 C 0.0627(2) 0.51632(19) 0.14479(13) 0.0575(5) Uani 1 1 d . . . H29A H -0.0042 0.5905 0.1632 0.086 Uiso 1 1 calc R . . H29B H 0.0126 0.439 0.1545 0.086 Uiso 1 1 calc R . . H29C H 0.1004 0.5413 0.0902 0.086 Uiso 1 1 calc R . . C30 C 0.25489(19) 0.59589(16) 0.17477(12) 0.0502(5) Uani 1 1 d . . . H30A H 0.2962 0.6247 0.1209 0.075 Uiso 1 1 calc R . . H30B H 0.3317 0.5695 0.203 0.075 Uiso 1 1 calc R . . H30C H 0.1878 0.669 0.1943 0.075 Uiso 1 1 calc R . . C31 C -0.0379(2) 0.29526(18) 0.40752(9) 0.0450(4) Uani 1 1 d . . . H31A H -0.0127 0.2998 0.4549 0.067 Uiso 1 1 calc R . . H31B H -0.0184 0.2032 0.3999 0.067 Uiso 1 1 calc R . . H31C H -0.1399 0.328 0.4103 0.067 Uiso 1 1 calc R . . C32 C 0.0122(2) 0.51379(19) 0.35475(12) 0.0600(5) Uani 1 1 d . . . H32A H -0.0882 0.5457 0.3524 0.09 Uiso 1 1 calc R . . H32B H 0.0743 0.5681 0.3144 0.09 Uiso 1 1 calc R . . H32C H 0.0273 0.5202 0.4041 0.09 Uiso 1 1 calc R . . N1 N 0.15185(11) 0.16742(10) 0.23643(6) 0.02181(19) Uani 1 1 d . . . N2 N 0.37115(11) 0.23182(11) 0.27936(6) 0.0227(2) Uani 1 1 d . . . N3 N 0.45742(12) -0.04207(12) 0.20602(7) 0.0294(2) Uani 1 1 d . . . N4 N 0.29050(14) -0.05115(12) 0.36521(7) 0.0312(2) Uani 1 1 d . . . N5 N 0.17950(13) 0.48428(11) 0.18372(7) 0.0309(2) Uani 1 1 d . . . N6 N 0.04663(13) 0.37621(12) 0.34476(7) 0.0315(2) Uani 1 1 d . . . Ti1 Ti 0.33121(2) 0.06755(2) 0.269746(12) 0.02123(5) Uani 1 1 d . . . Ti2 Ti 0.18187(2) 0.32607(2) 0.257208(12) 0.02163(5) 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 C1 0.0180(5) 0.0201(5) 0.0215(5) -0.0052(4) -0.0058(4) -0.0011(4) C2 0.0220(5) 0.0266(6) 0.0214(5) -0.0062(4) -0.0046(4) -0.0022(4) C3 0.0336(7) 0.0341(7) 0.0243(6) -0.0105(5) -0.0091(5) -0.0031(5) C4 0.0354(7) 0.0305(7) 0.0362(7) -0.0134(6) -0.0146(6) -0.0038(5) C5 0.0257(6) 0.0237(6) 0.0361(7) -0.0049(5) -0.0098(5) -0.0060(5) C6 0.0191(5) 0.0202(5) 0.0248(5) -0.0041(4) -0.0058(4) -0.0018(4) C7 0.0300(6) 0.0367(7) 0.0203(5) -0.0057(5) -0.0012(5) -0.0096(5) C8 0.0481(9) 0.0500(10) 0.0359(8) 0.0090(7) -0.0118(7) -0.0164(8) C9 0.0323(7) 0.0607(11) 0.0339(8) -0.0159(7) 0.0038(6) -0.0118(7) C10 0.0243(5) 0.0254(6) 0.0250(6) -0.0025(5) -0.0027(4) -0.0058(5) C11 0.0344(8) 0.0729(13) 0.0354(8) -0.0191(8) -0.0050(6) 0.0130(8) C12 0.0861(14) 0.0380(9) 0.0345(8) 0.0031(7) -0.0029(8) -0.0284(9) C13 0.0209(5) 0.0210(5) 0.0256(5) -0.0028(4) -0.0081(4) -0.0031(4) C14 0.0237(6) 0.0296(7) 0.0271(6) 0.0015(5) -0.0079(5) -0.0058(5) C15 0.0359(7) 0.0469(9) 0.0416(8) 0.0037(7) -0.0096(6) -0.0212(7) C16 0.0564(10) 0.0504(10) 0.0547(10) -0.0056(8) -0.0172(8) -0.0331(9) C17 0.0502(9) 0.0442(9) 0.0432(8) -0.0136(7) -0.0165(7) -0.0189(7) C18 0.0293(6) 0.0269(6) 0.0302(6) -0.0071(5) -0.0104(5) -0.0049(5) C19 0.0277(6) 0.0352(7) 0.0248(6) 0.0009(5) -0.0021(5) -0.0056(5) C20 0.0419(8) 0.0467(9) 0.0294(7) 0.0040(6) -0.0103(6) -0.0091(7) C21 0.0356(8) 0.0630(12) 0.0443(9) -0.0062(8) 0.0007(7) 0.0027(8) C22 0.0297(6) 0.0356(7) 0.0274(6) -0.0135(5) -0.0061(5) -0.0034(5) C23 0.0392(8) 0.0635(12) 0.0342(8) 0.0040(8) -0.0090(7) -0.0015(8) C24 0.0670(13) 0.0665(13) 0.0567(11) -0.0413(10) 0.0097(9) -0.0192(10) C25 0.0377(8) 0.0342(8) 0.0526(9) -0.0198(7) -0.0112(7) -0.0038(6) C26 0.0333(8) 0.0447(10) 0.1196(19) -0.0322(11) -0.0295(10) 0.0046(7) C27 0.0905(15) 0.0275(8) 0.0465(10) 0.0020(7) -0.0171(10) 0.0003(9) C28 0.0555(10) 0.0390(9) 0.0265(7) -0.0005(6) -0.0064(6) -0.0077(7) C29 0.0577(11) 0.0438(10) 0.0794(14) -0.0079(9) -0.0401(11) 0.0022(9) C30 0.0428(9) 0.0227(7) 0.0834(14) -0.0028(8) -0.0154(9) -0.0063(6) C31 0.0528(10) 0.0414(9) 0.0363(8) -0.0133(7) 0.0048(7) -0.0078(7) C32 0.0778(14) 0.0371(10) 0.0585(12) -0.0255(9) 0.0120(10) -0.0071(9) N1 0.0243(5) 0.0224(5) 0.0199(4) -0.0035(4) -0.0052(4) -0.0060(4) N2 0.0229(5) 0.0246(5) 0.0220(5) -0.0067(4) -0.0038(4) -0.0057(4) N3 0.0279(5) 0.0286(6) 0.0346(6) -0.0152(5) -0.0075(4) 0.0009(4) N4 0.0412(6) 0.0244(6) 0.0278(5) -0.0013(4) -0.0111(5) -0.0028(5) N5 0.0321(6) 0.0226(5) 0.0373(6) 0.0010(5) -0.0104(5) -0.0054(4) N6 0.0306(6) 0.0278(6) 0.0355(6) -0.0127(5) -0.0027(5) -0.0008(5) Ti1 0.02445(10) 0.01903(10) 0.02118(10) -0.00624(8) -0.00509(8) -0.00211(8) Ti2 0.02320(10) 0.01811(10) 0.02437(11) -0.00469(8) -0.00556(8) -0.00330(8) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 C1 N1 1.4085(15) . ? C1 C2 1.4191(16) . ? C1 C6 1.4248(16) . ? C2 C3 1.3930(18) . ? C2 C7 1.5201(18) . ? C3 C4 1.381(2) . ? C3 H3 0.95 . ? C4 C5 1.382(2) . ? C4 H4 0.95 . ? C5 C6 1.3915(17) . ? C5 H5 0.95 . ? C6 C10 1.5131(17) . ? C7 C9 1.528(2) . ? C7 C8 1.536(2) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C12 1.524(2) . ? C10 C11 1.527(2) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 N2 1.4099(15) . ? C13 C14 1.4190(17) . ? C13 C18 1.4227(18) . ? C14 C15 1.395(2) . ? C14 C19 1.515(2) . ? C15 C16 1.375(2) . ? C15 H15 0.95 . ? C16 C17 1.382(2) . ? C16 H16 0.95 . ? C17 C18 1.3905(19) . ? C17 H17 0.95 . ? C18 C22 1.5140(19) . ? C19 C20 1.5257(19) . ? C19 C21 1.535(2) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C24 1.519(2) . ? C22 C23 1.532(2) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? C25 N3 1.4476(18) . ? C25 H25A 0.98 . ? C25 H25B 0.98 . ? C25 H25C 0.98 . ? C26 N3 1.448(2) . ? C26 H26A 0.98 . ? C26 H26B 0.98 . ? C26 H26C 0.98 . ? C27 N4 1.457(2) . ? C27 H27A 0.98 . ? C27 H27B 0.98 . ? C27 H27C 0.98 . ? C28 N4 1.445(2) . ? C28 H28A 0.98 . ? C28 H28B 0.98 . ? C28 H28C 0.98 . ? C29 N5 1.442(2) . ? C29 H29A 0.98 . ? C29 H29B 0.98 . ? C29 H29C 0.98 . ? C30 N5 1.4472(19) . ? C30 H30A 0.98 . ? C30 H30B 0.98 . ? C30 H30C 0.98 . ? C31 N6 1.446(2) . ? C31 H31A 0.98 . ? C31 H31B 0.98 . ? C31 H31C 0.98 . ? C32 N6 1.456(2) . ? C32 H32A 0.98 . ? C32 H32B 0.98 . ? C32 H32C 0.98 . ? N1 Ti2 1.8694(10) . ? N1 Ti1 2.0211(10) . ? N2 Ti1 1.8818(11) . ? N2 Ti2 2.0123(11) . ? N3 Ti1 1.8890(11) . ? N4 Ti1 1.9197(11) . ? N5 Ti2 1.8948(11) . ? N6 Ti2 1.9224(12) . ? Ti1 Ti2 2.8089(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 C2 121.26(10) . . ? N1 C1 C6 119.36(10) . . ? C2 C1 C6 119.33(11) . . ? C3 C2 C1 118.75(12) . . ? C3 C2 C7 118.69(11) . . ? C1 C2 C7 122.56(11) . . ? C4 C3 C2 121.82(12) . . ? C4 C3 H3 119.1 . . ? C2 C3 H3 119.1 . . ? C3 C4 C5 119.40(12) . . ? C3 C4 H4 120.3 . . ? C5 C4 H4 120.3 . . ? C4 C5 C6 121.56(12) . . ? C4 C5 H5 119.2 . . ? C6 C5 H5 119.2 . . ? C5 C6 C1 118.90(11) . . ? C5 C6 C10 120.91(11) . . ? C1 C6 C10 120.10(11) . . ? C2 C7 C9 111.63(12) . . ? C2 C7 C8 111.47(11) . . ? C9 C7 C8 109.47(12) . . ? C2 C7 H7 108 . . ? C9 C7 H7 108 . . ? C8 C7 H7 108 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C12 113.90(12) . . ? C6 C10 C11 109.47(11) . . ? C12 C10 C11 110.78(14) . . ? C6 C10 H10 107.5 . . ? C12 C10 H10 107.5 . . ? C11 C10 H10 107.5 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 C14 120.62(11) . . ? N2 C13 C18 120.09(11) . . ? C14 C13 C18 119.29(11) . . ? C15 C14 C13 118.63(13) . . ? C15 C14 C19 118.55(12) . . ? C13 C14 C19 122.82(12) . . ? C16 C15 C14 121.98(15) . . ? C16 C15 H15 119 . . ? C14 C15 H15 119 . . ? C15 C16 C17 119.40(14) . . ? C15 C16 H16 120.3 . . ? C17 C16 H16 120.3 . . ? C16 C17 C18 121.55(15) . . ? C16 C17 H17 119.2 . . ? C18 C17 H17 119.2 . . ? C17 C18 C13 119.00(13) . . ? C17 C18 C22 120.28(13) . . ? C13 C18 C22 120.57(11) . . ? C14 C19 C20 111.99(13) . . ? C14 C19 C21 111.80(13) . . ? C20 C19 C21 109.06(12) . . ? C14 C19 H19 107.9 . . ? C20 C19 H19 107.9 . . ? C21 C19 H19 107.9 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C24 114.46(14) . . ? C18 C22 C23 108.50(12) . . ? C24 C22 C23 110.25(14) . . ? C18 C22 H22 107.8 . . ? C24 C22 H22 107.8 . . ? C23 C22 H22 107.8 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? N3 C25 H25A 109.5 . . ? N3 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? N3 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? N3 C26 H26A 109.5 . . ? N3 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? N3 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? N4 C27 H27A 109.5 . . ? N4 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? N4 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? N4 C28 H28A 109.5 . . ? N4 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? N4 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? N5 C29 H29A 109.5 . . ? N5 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? N5 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? N5 C30 H30A 109.5 . . ? N5 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? N5 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? N6 C31 H31A 109.5 . . ? N6 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? N6 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? N6 C32 H32A 109.5 . . ? N6 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? N6 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C1 N1 Ti2 152.99(8) . . ? C1 N1 Ti1 111.28(8) . . ? Ti2 N1 Ti1 92.36(4) . . ? C13 N2 Ti1 152.28(9) . . ? C13 N2 Ti2 113.34(8) . . ? Ti1 N2 Ti2 92.27(4) . . ? C25 N3 C26 111.23(13) . . ? C25 N3 Ti1 121.92(10) . . ? C26 N3 Ti1 126.12(11) . . ? C28 N4 C27 109.64(13) . . ? C28 N4 Ti1 124.73(10) . . ? C27 N4 Ti1 125.62(11) . . ? C29 N5 C30 112.67(13) . . ? C29 N5 Ti2 116.87(11) . . ? C30 N5 Ti2 128.22(11) . . ? C31 N6 C32 109.15(13) . . ? C31 N6 Ti2 129.58(10) . . ? C32 N6 Ti2 121.24(11) . . ? N2 Ti1 N3 123.11(5) . . ? N2 Ti1 N4 112.91(5) . . ? N3 Ti1 N4 103.09(5) . . ? N2 Ti1 N1 87.07(4) . . ? N3 Ti1 N1 118.01(5) . . ? N4 Ti1 N1 112.69(5) . . ? N2 Ti1 Ti2 45.71(3) . . ? N3 Ti1 Ti2 138.42(4) . . ? N4 Ti1 Ti2 118.13(4) . . ? N1 Ti1 Ti2 41.68(3) . . ? N1 Ti2 N5 121.12(5) . . ? N1 Ti2 N6 112.28(5) . . ? N5 Ti2 N6 103.44(5) . . ? N1 Ti2 N2 87.67(4) . . ? N5 Ti2 N2 118.81(5) . . ? N6 Ti2 N2 113.65(5) . . ? N1 Ti2 Ti1 45.96(3) . . ? N5 Ti2 Ti1 137.90(4) . . ? N6 Ti2 Ti1 118.56(4) . . ? N2 Ti2 Ti1 42.02(3) . . ? _database_code_depnum_ccdc_archive 'CCDC 931101' ####################################################################### # # 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_8 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C42 H70 N6 Ti2' _chemical_formula_sum 'C42 H70 N6 Ti2' _chemical_formula_weight 754.84 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' _symmetry_Int_Tables_number 61 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' '-x, -y, -z' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' 'x-1/2, y, -z-1/2' _cell_length_a 11.1946(7) _cell_length_b 20.0122(12) _cell_length_c 38.540(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 8634.0(9) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 9968 _cell_measurement_theta_min 2.58 _cell_measurement_theta_max 27.06 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.02 _exptl_crystal_density_diffrn 1.161 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3264 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.404 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.883 _exptl_absorpt_correction_T_max 0.975 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0524 _diffrn_reflns_av_unetI/netI 0.0361 _diffrn_reflns_number 77764 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -47 _diffrn_reflns_limit_l_max 48 _diffrn_reflns_theta_min 2.62 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _reflns_number_total 8799 _reflns_number_gt 6422 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0456P)^2^+3.8036P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_number_reflns 8799 _refine_ls_number_parameters 473 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0654 _refine_ls_R_factor_gt 0.037 _refine_ls_wR_factor_ref 0.0994 _refine_ls_wR_factor_gt 0.0861 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.296 _refine_diff_density_min -0.312 _refine_diff_density_rms 0.052 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.51786(16) 0.45498(9) 0.12376(5) 0.0227(4) Uani 1 1 d . . . C2 C 0.45128(19) 0.48252(10) 0.09593(5) 0.0290(5) Uani 1 1 d . . . C3 C 0.4898(2) 0.54196(11) 0.08106(6) 0.0381(5) Uani 1 1 d . . . H3 H 0.4472 0.5598 0.0618 0.046 Uiso 1 1 calc R . . C4 C 0.5883(2) 0.57579(11) 0.09347(6) 0.0398(6) Uani 1 1 d . . . H4 H 0.6148 0.6156 0.0824 0.048 Uiso 1 1 calc R . . C5 C 0.6475(2) 0.55128(10) 0.12199(6) 0.0355(5) Uani 1 1 d . . . H5 H 0.7127 0.5759 0.1312 0.043 Uiso 1 1 calc R . . C6 C 0.61460(17) 0.49159(9) 0.13764(5) 0.0263(4) Uani 1 1 d . . . C7 C 0.3383(2) 0.45044(11) 0.08207(6) 0.0369(5) Uani 1 1 d . . . H7 H 0.3156 0.4134 0.0982 0.044 Uiso 1 1 calc R . . C8 C 0.2328(2) 0.50003(14) 0.08054(7) 0.0551(7) Uani 1 1 d . . . H8A H 0.2256 0.5232 0.1029 0.083 Uiso 1 1 calc R . . H8B H 0.1588 0.4756 0.0757 0.083 Uiso 1 1 calc R . . H8C H 0.247 0.5328 0.0621 0.083 Uiso 1 1 calc R . . C9 C 0.3574(2) 0.42046(14) 0.04645(7) 0.0534(7) Uani 1 1 d . . . H9A H 0.3795 0.4558 0.0301 0.08 Uiso 1 1 calc R . . H9B H 0.2835 0.3989 0.0387 0.08 Uiso 1 1 calc R . . H9C H 0.4216 0.3872 0.0476 0.08 Uiso 1 1 calc R . . C10 C 0.67809(19) 0.47026(11) 0.17054(6) 0.0324(5) Uani 1 1 d . . . H10 H 0.6649 0.4212 0.1736 0.039 Uiso 1 1 calc R . . C11 C 0.6233(2) 0.50603(12) 0.20163(6) 0.0488(6) Uani 1 1 d . . . H11A H 0.6328 0.5544 0.1988 0.073 Uiso 1 1 calc R . . H11B H 0.6636 0.4916 0.2229 0.073 Uiso 1 1 calc R . . H11C H 0.5381 0.4951 0.2031 0.073 Uiso 1 1 calc R . . C12 C 0.8137(2) 0.48270(14) 0.16935(7) 0.0534(7) Uani 1 1 d . . . H12A H 0.8463 0.4649 0.1476 0.08 Uiso 1 1 calc R . . H12B H 0.8519 0.4603 0.1891 0.08 Uiso 1 1 calc R . . H12C H 0.8293 0.5308 0.1706 0.08 Uiso 1 1 calc R . . C13 C 0.31027(17) 0.22733(10) 0.15218(5) 0.0259(4) Uani 1 1 d . . . C14 C 0.21680(18) 0.22530(11) 0.12727(6) 0.0322(5) Uani 1 1 d . . . C15 C 0.1146(2) 0.18880(14) 0.13480(7) 0.0540(7) Uani 1 1 d . . . H15 H 0.0513 0.1876 0.1184 0.065 Uiso 1 1 calc R . . C16 C 0.1029(2) 0.15426(17) 0.16548(8) 0.0704(9) Uani 1 1 d . . . H16 H 0.0316 0.1302 0.1702 0.084 Uiso 1 1 calc R . . C17 C 0.1946(2) 0.15464(15) 0.18931(7) 0.0587(8) Uani 1 1 d . . . H17 H 0.1863 0.1297 0.2101 0.07 Uiso 1 1 calc R . . C18 C 0.29888(19) 0.19055(11) 0.18367(6) 0.0348(5) Uani 1 1 d . . . C19 C 0.22555(18) 0.25868(11) 0.09219(5) 0.0329(5) Uani 1 1 d . . . H19 H 0.3023 0.2842 0.0915 0.039 Uiso 1 1 calc R . . C20 C 0.2297(2) 0.20661(13) 0.06342(7) 0.0530(7) Uani 1 1 d . . . H20A H 0.2931 0.1742 0.0684 0.079 Uiso 1 1 calc R . . H20B H 0.246 0.2287 0.0412 0.079 Uiso 1 1 calc R . . H20C H 0.1527 0.1834 0.0622 0.079 Uiso 1 1 calc R . . C21 C 0.1243(2) 0.30806(13) 0.08565(7) 0.0482(6) Uani 1 1 d . . . H21A H 0.0475 0.2847 0.0871 0.072 Uiso 1 1 calc R . . H21B H 0.1333 0.3277 0.0625 0.072 Uiso 1 1 calc R . . H21C H 0.127 0.3436 0.1032 0.072 Uiso 1 1 calc R . . C22 C 0.4001(2) 0.18527(11) 0.20930(6) 0.0363(5) Uani 1 1 d . . . H22 H 0.4613 0.2195 0.2029 0.044 Uiso 1 1 calc R . . C23 C 0.4589(3) 0.11651(12) 0.20682(8) 0.0602(8) Uani 1 1 d . . . H23A H 0.4022 0.0822 0.2144 0.09 Uiso 1 1 calc R . . H23B H 0.5298 0.1154 0.2217 0.09 Uiso 1 1 calc R . . H23C H 0.4823 0.1079 0.1827 0.09 Uiso 1 1 calc R . . C24 C 0.3609(3) 0.19912(15) 0.24661(7) 0.0608(8) Uani 1 1 d . . . H24A H 0.3221 0.243 0.2478 0.091 Uiso 1 1 calc R . . H24B H 0.4309 0.1987 0.2619 0.091 Uiso 1 1 calc R . . H24C H 0.3045 0.1645 0.2541 0.091 Uiso 1 1 calc R . . C25 C 0.65436(17) 0.26477(9) 0.05354(5) 0.0231(4) Uani 1 1 d . . . C26 C 0.66513(17) 0.19795(10) 0.04215(5) 0.0254(4) Uani 1 1 d . . . C27 C 0.77219(18) 0.17796(11) 0.02698(5) 0.0300(5) Uani 1 1 d . . . H27 H 0.7809 0.1329 0.0197 0.036 Uiso 1 1 calc R . . C28 C 0.86576(18) 0.22156(11) 0.02226(5) 0.0328(5) Uani 1 1 d . . . H28 H 0.9388 0.2064 0.0125 0.039 Uiso 1 1 calc R . . C29 C 0.85225(18) 0.28746(11) 0.03186(5) 0.0311(5) Uani 1 1 d . . . H29 H 0.916 0.3178 0.0279 0.037 Uiso 1 1 calc R . . C30 C 0.74784(18) 0.31066(10) 0.04720(5) 0.0270(4) Uani 1 1 d . . . C31 C 0.56244(19) 0.14910(10) 0.04689(5) 0.0310(5) Uani 1 1 d . . . H31 H 0.4868 0.1744 0.0426 0.037 Uiso 1 1 calc R . . C32 C 0.5566(2) 0.12218(12) 0.08419(6) 0.0421(6) Uani 1 1 d . . . H32A H 0.6289 0.0963 0.0892 0.063 Uiso 1 1 calc R . . H32B H 0.4863 0.0934 0.0867 0.063 Uiso 1 1 calc R . . H32C H 0.5508 0.1597 0.1005 0.063 Uiso 1 1 calc R . . C33 C 0.5645(2) 0.09078(11) 0.02154(6) 0.0422(6) Uani 1 1 d . . . H33A H 0.5715 0.1078 -0.0022 0.063 Uiso 1 1 calc R . . H33B H 0.4905 0.065 0.0238 0.063 Uiso 1 1 calc R . . H33C H 0.633 0.0619 0.0267 0.063 Uiso 1 1 calc R . . C34 C 0.7312(2) 0.38487(10) 0.05378(6) 0.0361(5) Uani 1 1 d . . . H34 H 0.6715 0.3902 0.0729 0.043 Uiso 1 1 calc R . . C35 C 0.8460(2) 0.42105(12) 0.06465(7) 0.0485(6) Uani 1 1 d . . . H35A H 0.885 0.396 0.0833 0.073 Uiso 1 1 calc R . . H35B H 0.8262 0.4661 0.0728 0.073 Uiso 1 1 calc R . . H35C H 0.9 0.4242 0.0447 0.073 Uiso 1 1 calc R . . C36 C 0.6797(3) 0.41741(13) 0.02116(7) 0.0577(7) Uani 1 1 d . . . H36A H 0.7372 0.4135 0.0021 0.087 Uiso 1 1 calc R . . H36B H 0.6635 0.4647 0.0257 0.087 Uiso 1 1 calc R . . H36C H 0.6052 0.3949 0.0147 0.087 Uiso 1 1 calc R . . C37 C 0.7927(2) 0.31399(13) 0.13938(8) 0.0507(7) Uani 1 1 d . . . H37A H 0.822 0.3242 0.1627 0.076 Uiso 1 1 calc R . . H37B H 0.7733 0.3557 0.1273 0.076 Uiso 1 1 calc R . . H37C H 0.8545 0.2899 0.1265 0.076 Uiso 1 1 calc R . . C38 C 0.7094(2) 0.21258(12) 0.16145(7) 0.0485(6) Uani 1 1 d . . . H38A H 0.7747 0.1876 0.1505 0.073 Uiso 1 1 calc R . . H38B H 0.6372 0.1848 0.1618 0.073 Uiso 1 1 calc R . . H38C H 0.7318 0.2244 0.1852 0.073 Uiso 1 1 calc R . . C39 C 0.55768(18) 0.33724(11) 0.22358(6) 0.0337(5) Uani 1 1 d . . . H39A H 0.6021 0.3755 0.2328 0.051 Uiso 1 1 calc R . . H39B H 0.598 0.3203 0.2028 0.051 Uiso 1 1 calc R . . H39C H 0.5542 0.3019 0.2412 0.051 Uiso 1 1 calc R . . C40 C 0.3778(2) 0.38801(13) 0.24456(6) 0.0451(6) Uani 1 1 d . . . H40A H 0.3759 0.3557 0.2637 0.068 Uiso 1 1 calc R . . H40B H 0.296 0.4005 0.2383 0.068 Uiso 1 1 calc R . . H40C H 0.422 0.4279 0.2518 0.068 Uiso 1 1 calc R . . C41 C 0.2269(3) 0.46348(14) 0.17472(8) 0.0720(9) Uani 1 1 d . . . H41A H 0.1755 0.4842 0.1572 0.108 Uiso 1 1 calc R . . H41B H 0.3095 0.4783 0.1713 0.108 Uiso 1 1 calc R . . H41C H 0.1999 0.4767 0.1979 0.108 Uiso 1 1 calc R . . C42 C 0.1006(2) 0.36539(18) 0.17547(8) 0.0658(9) Uani 1 1 d . . . H42A H 0.0675 0.3803 0.1977 0.099 Uiso 1 1 calc R . . H42B H 0.103 0.3165 0.1749 0.099 Uiso 1 1 calc R . . H42C H 0.0502 0.3818 0.1565 0.099 Uiso 1 1 calc R . . N1 N 0.48892(13) 0.39092(7) 0.13701(4) 0.0213(3) Uani 1 1 d . . . N2 N 0.41374(14) 0.26556(7) 0.14595(4) 0.0218(3) Uani 1 1 d . . . N3 N 0.55147(16) 0.28618(9) 0.07204(4) 0.0263(4) Uani 1 1 d . . . N4 N 0.68635(14) 0.27278(8) 0.14185(4) 0.0281(4) Uani 1 1 d . . . N5 N 0.43677(15) 0.35806(9) 0.21462(4) 0.0297(4) Uani 1 1 d . . . N6 N 0.22082(15) 0.39162(9) 0.17145(5) 0.0350(4) Uani 1 1 d . . . Ti1 Ti 0.54053(3) 0.301941(16) 0.121720(8) 0.01925(9) Uani 1 1 d . . . Ti2 Ti 0.37435(3) 0.353617(17) 0.168511(9) 0.02189(9) Uani 1 1 d . . . H3A H 0.493(2) 0.2742(13) 0.0648(7) 0.046(8) 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 C1 0.0264(10) 0.0193(9) 0.0223(10) -0.0015(8) 0.0047(8) 0.0025(8) C2 0.0351(11) 0.0248(10) 0.0270(11) -0.0008(9) -0.0006(9) 0.0040(9) C3 0.0529(14) 0.0302(12) 0.0312(12) 0.0060(10) -0.0004(11) 0.0042(11) C4 0.0561(15) 0.0242(11) 0.0393(13) 0.0059(10) 0.0112(11) -0.0036(10) C5 0.0379(12) 0.0282(11) 0.0406(13) -0.0031(10) 0.0042(10) -0.0086(9) C6 0.0267(10) 0.0233(10) 0.0290(11) -0.0037(8) 0.0027(8) 0.0001(8) C7 0.0408(13) 0.0377(12) 0.0322(12) 0.0060(10) -0.0120(10) 0.0006(10) C8 0.0442(15) 0.0609(17) 0.0603(17) 0.0033(14) -0.0067(13) 0.0118(13) C9 0.0609(17) 0.0540(16) 0.0454(15) -0.0088(13) -0.0175(13) 0.0025(13) C10 0.0314(11) 0.0281(11) 0.0377(12) -0.0025(10) -0.0064(9) -0.0049(9) C11 0.0690(18) 0.0429(14) 0.0344(13) -0.0060(11) -0.0097(12) -0.0008(13) C12 0.0368(14) 0.0558(16) 0.0676(18) 0.0052(14) -0.0175(13) -0.0137(12) C13 0.0235(10) 0.0246(10) 0.0296(11) -0.0008(9) 0.0044(8) -0.0037(8) C14 0.0246(10) 0.0362(11) 0.0357(12) 0.0022(10) -0.0010(9) -0.0070(9) C15 0.0336(13) 0.0726(19) 0.0559(17) 0.0151(14) -0.0076(12) -0.0233(13) C16 0.0426(16) 0.093(2) 0.075(2) 0.0273(18) 0.0008(15) -0.0372(16) C17 0.0494(16) 0.074(2) 0.0530(17) 0.0262(15) 0.0026(13) -0.0252(14) C18 0.0356(12) 0.0355(12) 0.0331(12) 0.0051(10) 0.0042(10) -0.0063(10) C19 0.0236(11) 0.0435(13) 0.0317(12) 0.0034(10) -0.0037(9) -0.0102(9) C20 0.0543(16) 0.0576(17) 0.0470(15) -0.0085(13) 0.0115(13) -0.0075(13) C21 0.0380(13) 0.0599(16) 0.0468(15) 0.0068(13) -0.0069(11) 0.0050(12) C22 0.0451(13) 0.0308(12) 0.0330(12) 0.0068(10) 0.0004(10) -0.0067(10) C23 0.0654(19) 0.0375(14) 0.078(2) 0.0069(14) -0.0140(15) 0.0005(13) C24 0.081(2) 0.0663(18) 0.0348(14) 0.0076(14) 0.0049(14) -0.0181(16) C25 0.0253(10) 0.0282(10) 0.0158(9) 0.0018(8) -0.0007(8) 0.0040(8) C26 0.0277(10) 0.0287(10) 0.0199(10) 0.0042(8) -0.0024(8) 0.0034(9) C27 0.0332(12) 0.0294(11) 0.0275(11) -0.0036(9) 0.0008(9) 0.0079(9) C28 0.0252(11) 0.0435(13) 0.0298(12) -0.0036(10) 0.0043(9) 0.0085(9) C29 0.0268(11) 0.0392(12) 0.0274(11) 0.0004(9) 0.0023(9) -0.0023(9) C30 0.0308(11) 0.0298(11) 0.0204(10) -0.0010(9) 0.0020(8) 0.0012(9) C31 0.0305(11) 0.0296(11) 0.0328(12) 0.0016(9) -0.0028(9) 0.0010(9) C32 0.0496(15) 0.0379(13) 0.0389(13) 0.0057(11) 0.0035(11) -0.0078(11) C33 0.0494(15) 0.0338(12) 0.0435(14) -0.0037(11) -0.0077(11) -0.0029(11) C34 0.0407(13) 0.0304(12) 0.0371(13) -0.0035(10) 0.0120(10) -0.0019(10) C35 0.0557(16) 0.0363(13) 0.0535(16) -0.0087(12) 0.0148(13) -0.0140(12) C36 0.0726(19) 0.0377(14) 0.0628(19) 0.0105(13) -0.0002(15) 0.0104(13) C37 0.0272(12) 0.0565(16) 0.0684(18) 0.0027(14) 0.0067(12) -0.0006(11) C38 0.0453(14) 0.0359(13) 0.0643(18) 0.0048(12) -0.0108(12) 0.0139(11) C39 0.0320(12) 0.0393(12) 0.0299(12) 0.0010(10) -0.0040(9) -0.0013(10) C40 0.0430(14) 0.0649(17) 0.0275(12) -0.0112(12) 0.0051(10) 0.0034(12) C41 0.089(2) 0.0524(17) 0.075(2) -0.0052(16) 0.0209(18) 0.0293(17) C42 0.0269(13) 0.110(3) 0.0606(19) -0.0206(18) 0.0128(12) 0.0024(14) N1 0.0220(8) 0.0187(8) 0.0233(8) -0.0014(7) -0.0025(7) -0.0007(6) N2 0.0221(8) 0.0213(8) 0.0221(9) -0.0001(7) 0.0002(7) -0.0022(6) N3 0.0223(9) 0.0325(10) 0.0242(9) -0.0011(7) 0.0025(8) 0.0017(8) N4 0.0241(9) 0.0301(9) 0.0301(9) -0.0028(8) -0.0012(7) 0.0050(7) N5 0.0275(9) 0.0379(10) 0.0238(9) -0.0051(8) 0.0016(7) 0.0026(8) N6 0.0254(9) 0.0447(11) 0.0349(10) -0.0061(9) 0.0015(8) 0.0104(8) Ti1 0.01784(16) 0.01953(17) 0.02038(18) -0.00091(14) 0.00183(13) 0.00039(13) Ti2 0.01777(17) 0.02544(18) 0.02247(18) -0.00313(15) 0.00103(14) 0.00232(14) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 C6 1.413(3) . ? C1 N1 1.418(2) . ? C1 C2 1.418(3) . ? C2 C3 1.389(3) . ? C2 C7 1.516(3) . ? C3 C4 1.379(3) . ? C3 H3 0.95 . ? C4 C5 1.374(3) . ? C4 H4 0.95 . ? C5 C6 1.388(3) . ? C5 H5 0.95 . ? C6 C10 1.515(3) . ? C7 C9 1.513(3) . ? C7 C8 1.543(3) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C11 1.525(3) . ? C10 C12 1.539(3) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 N2 1.409(2) . ? C13 C14 1.421(3) . ? C13 C18 1.425(3) . ? C13 Ti2 2.7014(19) . ? C14 C15 1.388(3) . ? C14 C19 1.511(3) . ? C15 C16 1.376(4) . ? C15 H15 0.95 . ? C16 C17 1.378(4) . ? C16 H16 0.95 . ? C17 C18 1.388(3) . ? C17 H17 0.95 . ? C18 C22 1.507(3) . ? C19 C20 1.522(3) . ? C19 C21 1.525(3) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C23 1.528(3) . ? C22 C24 1.529(3) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? C25 C26 1.413(3) . ? C25 C30 1.414(3) . ? C25 N3 1.421(2) . ? C26 C27 1.392(3) . ? C26 C31 1.520(3) . ? C27 C28 1.375(3) . ? C27 H27 0.95 . ? C28 C29 1.378(3) . ? C28 H28 0.95 . ? C29 C30 1.390(3) . ? C29 H29 0.95 . ? C30 C34 1.518(3) . ? C31 C33 1.522(3) . ? C31 C32 1.537(3) . ? C31 H31 1 . ? C32 H32A 0.98 . ? C32 H32B 0.98 . ? C32 H32C 0.98 . ? C33 H33A 0.98 . ? C33 H33B 0.98 . ? C33 H33C 0.98 . ? C34 C36 1.529(3) . ? C34 C35 1.533(3) . ? C34 H34 1 . ? C35 H35A 0.98 . ? C35 H35B 0.98 . ? C35 H35C 0.98 . ? C36 H36A 0.98 . ? C36 H36B 0.98 . ? C36 H36C 0.98 . ? C37 N4 1.451(3) . ? C37 H37A 0.98 . ? C37 H37B 0.98 . ? C37 H37C 0.98 . ? C38 N4 1.445(3) . ? C38 H38A 0.98 . ? C38 H38B 0.98 . ? C38 H38C 0.98 . ? C39 N5 1.458(3) . ? C39 H39A 0.98 . ? C39 H39B 0.98 . ? C39 H39C 0.98 . ? C40 N5 1.458(3) . ? C40 H40A 0.98 . ? C40 H40B 0.98 . ? C40 H40C 0.98 . ? C41 N6 1.445(3) . ? C41 H41A 0.98 . ? C41 H41B 0.98 . ? C41 H41C 0.98 . ? C42 N6 1.452(3) . ? C42 H42A 0.98 . ? C42 H42B 0.98 . ? C42 H42C 0.98 . ? N1 Ti2 1.9173(16) . ? N1 Ti1 1.9626(15) . ? N2 Ti1 1.8485(15) . ? N2 Ti2 2.0139(15) . ? N3 Ti1 1.9442(17) . ? N3 H3A 0.75(3) . ? N4 Ti1 1.8993(16) . ? N5 Ti2 1.9115(17) . ? N6 Ti2 1.8829(17) . ? Ti1 Ti2 2.7896(5) . ? 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 C6 C1 N1 120.52(17) . . ? C6 C1 C2 119.21(17) . . ? N1 C1 C2 120.27(17) . . ? C3 C2 C1 118.79(19) . . ? C3 C2 C7 118.46(19) . . ? C1 C2 C7 122.73(18) . . ? C4 C3 C2 121.7(2) . . ? C4 C3 H3 119.1 . . ? C2 C3 H3 119.1 . . ? C5 C4 C3 119.2(2) . . ? C5 C4 H4 120.4 . . ? C3 C4 H4 120.4 . . ? C4 C5 C6 121.8(2) . . ? C4 C5 H5 119.1 . . ? C6 C5 H5 119.1 . . ? C5 C6 C1 119.02(19) . . ? C5 C6 C10 118.81(18) . . ? C1 C6 C10 122.03(17) . . ? C9 C7 C2 111.7(2) . . ? C9 C7 C8 109.2(2) . . ? C2 C7 C8 112.31(19) . . ? C9 C7 H7 107.8 . . ? C2 C7 H7 107.8 . . ? C8 C7 H7 107.8 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C11 109.66(18) . . ? C6 C10 C12 113.09(19) . . ? C11 C10 C12 110.2(2) . . ? C6 C10 H10 107.9 . . ? C11 C10 H10 107.9 . . ? C12 C10 H10 107.9 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 C14 120.39(18) . . ? N2 C13 C18 119.96(18) . . ? C14 C13 C18 119.65(18) . . ? N2 C13 Ti2 46.63(8) . . ? C14 C13 Ti2 112.32(14) . . ? C18 C13 Ti2 107.98(14) . . ? C15 C14 C13 118.7(2) . . ? C15 C14 C19 118.2(2) . . ? C13 C14 C19 122.97(18) . . ? C16 C15 C14 121.5(2) . . ? C16 C15 H15 119.2 . . ? C14 C15 H15 119.2 . . ? C15 C16 C17 119.9(2) . . ? C15 C16 H16 120 . . ? C17 C16 H16 120 . . ? C16 C17 C18 121.7(2) . . ? C16 C17 H17 119.2 . . ? C18 C17 H17 119.2 . . ? C17 C18 C13 118.4(2) . . ? C17 C18 C22 119.6(2) . . ? C13 C18 C22 121.81(18) . . ? C14 C19 C20 110.54(19) . . ? C14 C19 C21 112.72(19) . . ? C20 C19 C21 110.24(19) . . ? C14 C19 H19 107.7 . . ? C20 C19 H19 107.7 . . ? C21 C19 H19 107.7 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C23 110.3(2) . . ? C18 C22 C24 112.8(2) . . ? C23 C22 C24 110.2(2) . . ? C18 C22 H22 107.8 . . ? C23 C22 H22 107.8 . . ? C24 C22 H22 107.8 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C26 C25 C30 119.87(17) . . ? C26 C25 N3 120.71(18) . . ? C30 C25 N3 119.41(17) . . ? C27 C26 C25 118.43(18) . . ? C27 C26 C31 121.11(18) . . ? C25 C26 C31 120.45(17) . . ? C28 C27 C26 121.93(19) . . ? C28 C27 H27 119 . . ? C26 C27 H27 119 . . ? C27 C28 C29 119.22(19) . . ? C27 C28 H28 120.4 . . ? C29 C28 H28 120.4 . . ? C28 C29 C30 121.7(2) . . ? C28 C29 H29 119.1 . . ? C30 C29 H29 119.1 . . ? C29 C30 C25 118.63(18) . . ? C29 C30 C34 120.06(18) . . ? C25 C30 C34 121.06(18) . . ? C26 C31 C33 113.84(18) . . ? C26 C31 C32 111.74(17) . . ? C33 C31 C32 109.40(18) . . ? C26 C31 H31 107.2 . . ? C33 C31 H31 107.2 . . ? C32 C31 H31 107.2 . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C31 C33 H33A 109.5 . . ? C31 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? C31 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C30 C34 C36 109.00(19) . . ? C30 C34 C35 113.89(19) . . ? C36 C34 C35 109.9(2) . . ? C30 C34 H34 108 . . ? C36 C34 H34 108 . . ? C35 C34 H34 108 . . ? C34 C35 H35A 109.5 . . ? C34 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? C34 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C34 C36 H36A 109.5 . . ? C34 C36 H36B 109.5 . . ? H36A C36 H36B 109.5 . . ? C34 C36 H36C 109.5 . . ? H36A C36 H36C 109.5 . . ? H36B C36 H36C 109.5 . . ? N4 C37 H37A 109.5 . . ? N4 C37 H37B 109.5 . . ? H37A C37 H37B 109.5 . . ? N4 C37 H37C 109.5 . . ? H37A C37 H37C 109.5 . . ? H37B C37 H37C 109.5 . . ? N4 C38 H38A 109.5 . . ? N4 C38 H38B 109.5 . . ? H38A C38 H38B 109.5 . . ? N4 C38 H38C 109.5 . . ? H38A C38 H38C 109.5 . . ? H38B C38 H38C 109.5 . . ? N5 C39 H39A 109.5 . . ? N5 C39 H39B 109.5 . . ? H39A C39 H39B 109.5 . . ? N5 C39 H39C 109.5 . . ? H39A C39 H39C 109.5 . . ? H39B C39 H39C 109.5 . . ? N5 C40 H40A 109.5 . . ? N5 C40 H40B 109.5 . . ? H40A C40 H40B 109.5 . . ? N5 C40 H40C 109.5 . . ? H40A C40 H40C 109.5 . . ? H40B C40 H40C 109.5 . . ? N6 C41 H41A 109.5 . . ? N6 C41 H41B 109.5 . . ? H41A C41 H41B 109.5 . . ? N6 C41 H41C 109.5 . . ? H41A C41 H41C 109.5 . . ? H41B C41 H41C 109.5 . . ? N6 C42 H42A 109.5 . . ? N6 C42 H42B 109.5 . . ? H42A C42 H42B 109.5 . . ? N6 C42 H42C 109.5 . . ? H42A C42 H42C 109.5 . . ? H42B C42 H42C 109.5 . . ? C1 N1 Ti2 137.15(12) . . ? C1 N1 Ti1 130.17(12) . . ? Ti2 N1 Ti1 91.94(6) . . ? C13 N2 Ti1 158.65(14) . . ? C13 N2 Ti2 102.80(12) . . ? Ti1 N2 Ti2 92.38(6) . . ? C25 N3 Ti1 126.45(14) . . ? C25 N3 H3A 115(2) . . ? Ti1 N3 H3A 111(2) . . ? C38 N4 C37 111.21(18) . . ? C38 N4 Ti1 128.54(15) . . ? C37 N4 Ti1 120.23(15) . . ? C39 N5 C40 110.50(17) . . ? C39 N5 Ti2 123.12(13) . . ? C40 N5 Ti2 126.11(14) . . ? C41 N6 C42 113.2(2) . . ? C41 N6 Ti2 111.34(17) . . ? C42 N6 Ti2 134.92(18) . . ? N2 Ti1 N4 109.42(7) . . ? N2 Ti1 N3 118.81(7) . . ? N4 Ti1 N3 107.35(7) . . ? N2 Ti1 N1 88.83(7) . . ? N4 Ti1 N1 114.15(7) . . ? N3 Ti1 N1 117.48(7) . . ? N2 Ti1 Ti2 46.16(5) . . ? N4 Ti1 Ti2 115.02(5) . . ? N3 Ti1 Ti2 137.62(5) . . ? N1 Ti1 Ti2 43.38(5) . . ? N6 Ti2 N5 105.01(7) . . ? N6 Ti2 N1 119.44(7) . . ? N5 Ti2 N1 109.02(7) . . ? N6 Ti2 N2 125.40(7) . . ? N5 Ti2 N2 111.22(7) . . ? N1 Ti2 N2 85.46(6) . . ? N6 Ti2 C13 98.60(7) . . ? N5 Ti2 C13 110.92(7) . . ? N1 Ti2 C13 113.23(6) . . ? N2 Ti2 C13 30.57(6) . . ? N6 Ti2 Ti1 142.88(6) . . ? N5 Ti2 Ti1 111.98(5) . . ? N1 Ti2 Ti1 44.68(4) . . ? N2 Ti2 Ti1 41.46(4) . . ? C13 Ti2 Ti1 71.32(4) . . ? _database_code_depnum_ccdc_archive 'CCDC 931102' ####################################################################### # # 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_9 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C24 H53 N7 Ti2' _chemical_formula_sum 'C24 H53 N7 Ti2' _chemical_formula_weight 535.53 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' _symmetry_Int_Tables_number 61 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' '-x, -y, -z' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' 'x-1/2, y, -z-1/2' _cell_length_a 17.0404(7) _cell_length_b 16.0775(6) _cell_length_c 23.1921(9) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 6353.9(4) _cell_formula_units_Z 8 _cell_measurement_temperature 180 _cell_measurement_reflns_used 9095 _cell_measurement_theta_min 2.39 _cell_measurement_theta_max 24.54 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description parallelepiped _exptl_crystal_colour yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.03 _exptl_crystal_density_diffrn 1.12 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2320 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.525 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.883 _exptl_absorpt_correction_T_max 0.975 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0714 _diffrn_reflns_av_unetI/netI 0.0385 _diffrn_reflns_number 63139 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 2.84 _diffrn_reflns_theta_max 26.04 _diffrn_reflns_theta_full 26.04 _diffrn_measured_fraction_theta_full 0.998 _diffrn_measured_fraction_theta_max 0.998 _reflns_number_total 6262 _reflns_number_gt 4371 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0449P)^2^+3.4497P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 6262 _refine_ls_number_parameters 314 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0726 _refine_ls_R_factor_gt 0.0402 _refine_ls_wR_factor_ref 0.1052 _refine_ls_wR_factor_gt 0.0908 _refine_ls_goodness_of_fit_ref 1.031 _refine_ls_restrained_S_all 1.031 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.347 _refine_diff_density_min -0.346 _refine_diff_density_rms 0.05 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.00864(13) 0.29185(13) 0.12708(9) 0.0254(5) Uani 1 1 d . . . C2 C -0.05815(14) 0.24153(15) 0.13719(10) 0.0335(5) Uani 1 1 d . . . C3 C -0.13050(16) 0.27893(18) 0.14412(12) 0.0455(7) Uani 1 1 d . . . H3 H -0.1744 0.2459 0.1505 0.055 Uiso 1 1 calc R . . C4 C -0.13903(16) 0.36424(19) 0.14178(13) 0.0504(7) Uani 1 1 d . . . H4 H -0.1883 0.3883 0.1462 0.06 Uiso 1 1 calc R . . C5 C -0.07387(15) 0.41340(16) 0.13281(11) 0.0417(6) Uani 1 1 d . . . H5 H -0.0799 0.4709 0.1314 0.05 Uiso 1 1 calc R . . C6 C 0.00036(14) 0.37971(14) 0.12580(10) 0.0303(5) Uani 1 1 d . . . C7 C -0.05163(16) 0.14711(15) 0.14114(11) 0.0402(6) Uani 1 1 d . . . H7 H 0.0029 0.1325 0.1322 0.048 Uiso 1 1 calc R . . C8 C -0.0687(2) 0.1150(2) 0.20143(13) 0.0693(10) Uani 1 1 d . . . H8A H -0.0349 0.1423 0.2286 0.104 Uiso 1 1 calc R . . H8B H -0.0595 0.0561 0.2027 0.104 Uiso 1 1 calc R . . H8C H -0.1224 0.1261 0.2111 0.104 Uiso 1 1 calc R . . C9 C -0.1029(2) 0.10315(18) 0.09745(13) 0.0613(9) Uani 1 1 d . . . H9A H -0.1571 0.115 0.1055 0.092 Uiso 1 1 calc R . . H9B H -0.0942 0.0443 0.0998 0.092 Uiso 1 1 calc R . . H9C H -0.0901 0.1223 0.0594 0.092 Uiso 1 1 calc R . . C10 C 0.07007(15) 0.43655(14) 0.11720(12) 0.0380(6) Uani 1 1 d . . . H10 H 0.1171 0.4017 0.1143 0.046 Uiso 1 1 calc R . . C11 C 0.0814(2) 0.49552(18) 0.16798(16) 0.0676(10) Uani 1 1 d . . . H11A H 0.0362 0.5309 0.1715 0.101 Uiso 1 1 calc R . . H11B H 0.1272 0.529 0.1617 0.101 Uiso 1 1 calc R . . H11C H 0.0878 0.4638 0.2027 0.101 Uiso 1 1 calc R . . C12 C 0.0625(2) 0.48538(17) 0.06101(15) 0.0627(9) Uani 1 1 d . . . H12A H 0.0588 0.4473 0.0292 0.094 Uiso 1 1 calc R . . H12B H 0.1078 0.5202 0.0561 0.094 Uiso 1 1 calc R . . H12C H 0.0162 0.5193 0.0624 0.094 Uiso 1 1 calc R . . C13 C 0.2356(2) 0.1191(2) -0.0039(2) 0.0937(14) Uani 1 1 d . . . H13A H 0.2715 0.0904 0.021 0.141 Uiso 1 1 calc R . . H13B H 0.2566 0.1726 -0.0136 0.141 Uiso 1 1 calc R . . H13C H 0.2279 0.0873 -0.0385 0.141 Uiso 1 1 calc R . . C14 C 0.1250(2) 0.04922(17) 0.03758(14) 0.0630(9) Uani 1 1 d . . . H14A H 0.117 0.0196 0.0021 0.094 Uiso 1 1 calc R . . H14B H 0.0753 0.0576 0.0563 0.094 Uiso 1 1 calc R . . H14C H 0.1588 0.0175 0.0623 0.094 Uiso 1 1 calc R . . C15 C 0.15201(19) 0.3467(2) -0.05803(13) 0.0623(9) Uani 1 1 d . . . H15A H 0.1499 0.4063 -0.0555 0.093 Uiso 1 1 calc R . . H15B H 0.1041 0.3263 -0.0746 0.093 Uiso 1 1 calc R . . H15C H 0.1955 0.3306 -0.0819 0.093 Uiso 1 1 calc R . . C16 C 0.23127(16) 0.34383(19) 0.02720(13) 0.0516(8) Uani 1 1 d . . . H16A H 0.2765 0.3317 0.004 0.077 Uiso 1 1 calc R . . H16B H 0.2369 0.318 0.0643 0.077 Uiso 1 1 calc R . . H16C H 0.2265 0.4029 0.0319 0.077 Uiso 1 1 calc R . . C17 C -0.04854(16) 0.28020(17) -0.01181(12) 0.0462(7) Uani 1 1 d . . . H17A H -0.0508 0.3048 -0.0495 0.069 Uiso 1 1 calc R . . H17B H -0.0366 0.3223 0.0162 0.069 Uiso 1 1 calc R . . H17C H -0.0983 0.2555 -0.0028 0.069 Uiso 1 1 calc R . . C18 C -0.0033(2) 0.15394(19) -0.05434(13) 0.0617(9) Uani 1 1 d . . . H18A H -0.0521 0.1266 -0.046 0.093 Uiso 1 1 calc R . . H18B H 0.0384 0.1138 -0.0543 0.093 Uiso 1 1 calc R . . H18C H -0.0063 0.1799 -0.0916 0.093 Uiso 1 1 calc R . . C19 C 0.1423(3) 0.1125(3) 0.27817(17) 0.1022(15) Uani 1 1 d . . . H19A H 0.0998 0.0738 0.2825 0.153 Uiso 1 1 calc R . . H19B H 0.1331 0.16 0.3023 0.153 Uiso 1 1 calc R . . H19C H 0.1906 0.0863 0.2892 0.153 Uiso 1 1 calc R . . C20 C 0.1610(3) 0.0707(2) 0.18105(18) 0.0855(13) Uani 1 1 d . . . H20A H 0.2073 0.0415 0.1931 0.128 Uiso 1 1 calc R . . H20B H 0.1682 0.0913 0.1425 0.128 Uiso 1 1 calc R . . H20C H 0.1169 0.0336 0.1819 0.128 Uiso 1 1 calc R . . C21 C 0.02840(19) 0.3207(2) 0.27015(14) 0.0719(10) Uani 1 1 d . . . H21A H 0.0202 0.2916 0.3058 0.108 Uiso 1 1 calc R . . H21B H -0.0051 0.2978 0.2409 0.108 Uiso 1 1 calc R . . H21C H 0.0163 0.3785 0.2754 0.108 Uiso 1 1 calc R . . C22 C 0.1616(2) 0.3469(3) 0.29618(15) 0.0813(12) Uani 1 1 d . . . H22A H 0.1528 0.4057 0.2991 0.122 Uiso 1 1 calc R . . H22B H 0.2152 0.3367 0.2855 0.122 Uiso 1 1 calc R . . H22C H 0.1509 0.3212 0.3327 0.122 Uiso 1 1 calc R . . C23 C 0.27916(18) 0.36002(18) 0.17512(16) 0.0623(9) Uani 1 1 d . . . H23A H 0.3129 0.3698 0.2076 0.093 Uiso 1 1 calc R . . H23B H 0.2346 0.3964 0.1773 0.093 Uiso 1 1 calc R . . H23C H 0.3075 0.3706 0.1401 0.093 Uiso 1 1 calc R . . C24 C 0.3186(2) 0.2187(2) 0.1713(2) 0.0848(13) Uani 1 1 d . . . H24A H 0.3457 0.2287 0.1357 0.127 Uiso 1 1 calc R . . H24B H 0.3004 0.1623 0.1722 0.127 Uiso 1 1 calc R . . H24C H 0.3538 0.2282 0.203 0.127 Uiso 1 1 calc R . . N1 N 0.08355(10) 0.25446(10) 0.11815(8) 0.0257(4) Uani 1 1 d . . . N2 N 0.16094(13) 0.12951(13) 0.02542(10) 0.0446(6) Uani 1 1 d . . . N3 N 0.16186(12) 0.31191(13) -0.00091(9) 0.0378(5) Uani 1 1 d . . . N4 N 0.01196(12) 0.21675(12) -0.01071(9) 0.0357(5) Uani 1 1 d . . . N5 N 0.14702(15) 0.13868(14) 0.21906(10) 0.0490(6) Uani 1 1 d . . . N6 N 0.10976(14) 0.31211(15) 0.25259(10) 0.0507(6) Uani 1 1 d . . . N7 N 0.25278(12) 0.27429(13) 0.17574(10) 0.0415(5) Uani 1 1 d . . . Ti1 Ti 0.10219(2) 0.22869(2) 0.036685(18) 0.02701(11) Uani 1 1 d . . . Ti2 Ti 0.14495(3) 0.24782(3) 0.189063(18) 0.03096(12) 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 C1 0.0257(12) 0.0295(11) 0.0209(11) -0.0042(9) -0.0009(9) -0.0014(9) C2 0.0336(13) 0.0404(13) 0.0264(12) -0.0022(10) 0.0020(10) -0.0068(11) C3 0.0321(14) 0.0571(18) 0.0473(17) -0.0042(14) 0.0073(12) -0.0064(12) C4 0.0283(14) 0.067(2) 0.0556(19) -0.0068(15) 0.0067(13) 0.0116(14) C5 0.0389(15) 0.0385(14) 0.0478(16) -0.0089(12) -0.0001(13) 0.0109(12) C6 0.0334(13) 0.0306(12) 0.0270(12) -0.0059(10) -0.0029(11) 0.0046(10) C7 0.0428(16) 0.0363(14) 0.0414(15) 0.0036(11) 0.0038(13) -0.0124(11) C8 0.098(3) 0.0576(19) 0.052(2) 0.0161(16) -0.0012(19) -0.0232(19) C9 0.078(2) 0.0478(17) 0.058(2) -0.0003(14) -0.0168(18) -0.0190(16) C10 0.0351(14) 0.0227(12) 0.0563(17) -0.0048(11) -0.0025(13) 0.0010(10) C11 0.063(2) 0.0425(16) 0.097(3) -0.0333(17) -0.016(2) -0.0013(15) C12 0.062(2) 0.0388(16) 0.088(2) 0.0188(16) 0.0050(19) -0.0029(14) C13 0.066(3) 0.075(2) 0.141(4) -0.020(3) 0.037(3) 0.017(2) C14 0.086(2) 0.0356(15) 0.067(2) -0.0137(15) 0.0053(19) 0.0084(15) C15 0.053(2) 0.086(2) 0.0473(18) 0.0224(16) 0.0067(15) -0.0085(17) C16 0.0350(16) 0.0623(18) 0.0576(19) 0.0122(15) 0.0032(14) -0.0100(13) C17 0.0477(17) 0.0511(16) 0.0399(15) 0.0016(13) -0.0151(13) 0.0008(13) C18 0.072(2) 0.069(2) 0.0446(18) -0.0197(15) -0.0145(16) 0.0003(17) C19 0.127(4) 0.110(3) 0.069(3) 0.057(2) -0.017(3) -0.006(3) C20 0.111(3) 0.0453(19) 0.100(3) 0.0053(19) -0.030(3) 0.014(2) C21 0.054(2) 0.125(3) 0.0365(17) -0.0214(19) 0.0002(16) 0.000(2) C22 0.065(2) 0.121(3) 0.059(2) -0.039(2) -0.0246(19) 0.014(2) C23 0.0471(18) 0.0580(18) 0.082(2) 0.0063(16) -0.0208(17) -0.0167(15) C24 0.0412(19) 0.075(2) 0.139(4) 0.024(2) 0.013(2) 0.0157(17) N1 0.0261(9) 0.0215(9) 0.0296(10) -0.0010(8) -0.0016(8) 0.0000(7) N2 0.0443(14) 0.0385(12) 0.0510(14) -0.0095(10) 0.0064(11) 0.0084(10) N3 0.0342(12) 0.0426(12) 0.0366(12) 0.0047(9) 0.0037(9) -0.0041(9) N4 0.0366(12) 0.0426(12) 0.0278(10) -0.0034(9) -0.0042(9) -0.0048(9) N5 0.0554(15) 0.0470(13) 0.0446(14) 0.0163(11) -0.0060(12) -0.0018(12) N6 0.0468(14) 0.0706(16) 0.0348(12) -0.0153(11) -0.0099(11) 0.0060(12) N7 0.0309(11) 0.0426(12) 0.0511(13) 0.0069(10) -0.0062(11) 0.0007(9) Ti1 0.0268(2) 0.0265(2) 0.0276(2) -0.00168(17) 0.00007(18) 0.00040(17) Ti2 0.0305(2) 0.0338(2) 0.0286(2) 0.00019(18) -0.00305(18) 0.00141(19) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 C2 1.416(3) . ? C1 C6 1.420(3) . ? C1 N1 1.426(3) . ? C2 C3 1.381(4) . ? C2 C7 1.525(3) . ? C3 C4 1.380(4) . ? C3 H3 0.93 . ? C4 C5 1.379(4) . ? C4 H4 0.93 . ? C5 C6 1.385(3) . ? C5 H5 0.93 . ? C6 C10 1.512(3) . ? C7 C9 1.513(4) . ? C7 C8 1.519(4) . ? C7 H7 0.98 . ? C8 H8A 0.96 . ? C8 H8B 0.96 . ? C8 H8C 0.96 . ? C9 H9A 0.96 . ? C9 H9B 0.96 . ? C9 H9C 0.96 . ? C10 C11 1.524(4) . ? C10 C12 1.527(4) . ? C10 H10 0.98 . ? C11 H11A 0.96 . ? C11 H11B 0.96 . ? C11 H11C 0.96 . ? C12 H12A 0.96 . ? C12 H12B 0.96 . ? C12 H12C 0.96 . ? C13 N2 1.452(4) . ? C13 H13A 0.96 . ? C13 H13B 0.96 . ? C13 H13C 0.96 . ? C14 N2 1.457(4) . ? C14 H14A 0.96 . ? C14 H14B 0.96 . ? C14 H14C 0.96 . ? C15 N3 1.448(3) . ? C15 H15A 0.96 . ? C15 H15B 0.96 . ? C15 H15C 0.96 . ? C16 N3 1.445(3) . ? C16 H16A 0.96 . ? C16 H16B 0.96 . ? C16 H16C 0.96 . ? C17 N4 1.451(3) . ? C17 H17A 0.96 . ? C17 H17B 0.96 . ? C17 H17C 0.96 . ? C18 N4 1.453(3) . ? C18 H18A 0.96 . ? C18 H18B 0.96 . ? C18 H18C 0.96 . ? C19 N5 1.436(4) . ? C19 H19A 0.96 . ? C19 H19B 0.96 . ? C19 H19C 0.96 . ? C20 N5 1.424(4) . ? C20 H20A 0.96 . ? C20 H20B 0.96 . ? C20 H20C 0.96 . ? C21 N6 1.452(4) . ? C21 H21A 0.96 . ? C21 H21B 0.96 . ? C21 H21C 0.96 . ? C22 N6 1.454(4) . ? C22 H22A 0.96 . ? C22 H22B 0.96 . ? C22 H22C 0.96 . ? C23 N7 1.450(3) . ? C23 H23A 0.96 . ? C23 H23B 0.96 . ? C23 H23C 0.96 . ? C24 N7 1.438(4) . ? C24 H24A 0.96 . ? C24 H24B 0.96 . ? C24 H24C 0.96 . ? N1 Ti2 1.9522(18) . ? N1 Ti1 1.9602(19) . ? N2 Ti1 1.901(2) . ? N3 Ti1 1.893(2) . ? N4 Ti1 1.900(2) . ? N5 Ti2 1.888(2) . ? N6 Ti2 1.897(2) . ? N7 Ti2 1.911(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 C2 C1 C6 119.5(2) . . ? C2 C1 N1 120.18(19) . . ? C6 C1 N1 120.34(19) . . ? C3 C2 C1 119.2(2) . . ? C3 C2 C7 119.4(2) . . ? C1 C2 C7 121.3(2) . . ? C4 C3 C2 121.5(2) . . ? C4 C3 H3 119.3 . . ? C2 C3 H3 119.3 . . ? C5 C4 C3 119.4(2) . . ? C5 C4 H4 120.3 . . ? C3 C4 H4 120.3 . . ? C4 C5 C6 121.9(2) . . ? C4 C5 H5 119 . . ? C6 C5 H5 119 . . ? C5 C6 C1 118.5(2) . . ? C5 C6 C10 119.8(2) . . ? C1 C6 C10 121.7(2) . . ? C9 C7 C8 110.3(2) . . ? C9 C7 C2 112.5(2) . . ? C8 C7 C2 112.3(2) . . ? C9 C7 H7 107.1 . . ? C8 C7 H7 107.1 . . ? C2 C7 H7 107.1 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C11 111.9(2) . . ? C6 C10 C12 110.9(2) . . ? C11 C10 C12 110.5(2) . . ? C6 C10 H10 107.8 . . ? C11 C10 H10 107.8 . . ? C12 C10 H10 107.8 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 H13A 109.5 . . ? N2 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? N2 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? N2 C14 H14A 109.5 . . ? N2 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? N2 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? N3 C15 H15A 109.5 . . ? N3 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? N3 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? N3 C16 H16A 109.5 . . ? N3 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? N3 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? N4 C17 H17A 109.5 . . ? N4 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? N4 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? N4 C18 H18A 109.5 . . ? N4 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? N4 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? N5 C19 H19A 109.5 . . ? N5 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? N5 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N5 C20 H20A 109.5 . . ? N5 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? N5 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? N6 C21 H21A 109.5 . . ? N6 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N6 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N6 C22 H22A 109.5 . . ? N6 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N6 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? N7 C23 H23A 109.5 . . ? N7 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? N7 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? N7 C24 H24A 109.5 . . ? N7 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? N7 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C1 N1 Ti2 112.37(14) . . ? C1 N1 Ti1 111.97(14) . . ? Ti2 N1 Ti1 135.53(10) . . ? C13 N2 C14 110.9(2) . . ? C13 N2 Ti1 128.5(2) . . ? C14 N2 Ti1 119.68(19) . . ? C16 N3 C15 111.7(2) . . ? C16 N3 Ti1 118.88(17) . . ? C15 N3 Ti1 129.21(19) . . ? C17 N4 C18 110.4(2) . . ? C17 N4 Ti1 120.95(16) . . ? C18 N4 Ti1 128.18(19) . . ? C20 N5 C19 112.1(3) . . ? C20 N5 Ti2 119.2(2) . . ? C19 N5 Ti2 128.5(2) . . ? C21 N6 C22 110.4(2) . . ? C21 N6 Ti2 124.88(19) . . ? C22 N6 Ti2 123.9(2) . . ? C24 N7 C23 110.3(2) . . ? C24 N7 Ti2 128.6(2) . . ? C23 N7 Ti2 120.76(18) . . ? N3 Ti1 N4 103.87(9) . . ? N3 Ti1 N2 104.28(10) . . ? N4 Ti1 N2 105.19(9) . . ? N3 Ti1 N1 112.43(8) . . ? N4 Ti1 N1 116.61(8) . . ? N2 Ti1 N1 113.27(9) . . ? N5 Ti2 N6 103.07(11) . . ? N5 Ti2 N7 104.40(10) . . ? N6 Ti2 N7 107.95(10) . . ? N5 Ti2 N1 111.79(9) . . ? N6 Ti2 N1 117.07(9) . . ? N7 Ti2 N1 111.52(9) . . ? _database_code_depnum_ccdc_archive 'CCDC 931103' ####################################################################### # # 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_10 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C52 H82 N6 Ti2' _chemical_formula_sum 'C52 H82 N6 Ti2' _chemical_formula_weight 887.04 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 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 11.5158(4) _cell_length_b 22.9429(8) _cell_length_c 19.6453(7) _cell_angle_alpha 90 _cell_angle_beta 98.712(2) _cell_angle_gamma 90 _cell_volume 5130.5(3) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 9534 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 25.16 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description parallelepiped _exptl_crystal_colour red _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.04 _exptl_crystal_density_diffrn 1.148 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1920 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.35 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.9125 _exptl_absorpt_correction_T_max 0.9873 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0592 _diffrn_reflns_av_unetI/netI 0.0478 _diffrn_reflns_number 59919 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.93 _diffrn_reflns_theta_max 25.24 _diffrn_reflns_theta_full 25.24 _diffrn_measured_fraction_theta_full 0.989 _diffrn_measured_fraction_theta_max 0.989 _reflns_number_total 9171 _reflns_number_gt 6513 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0570P)^2^+2.9424P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 9171 _refine_ls_number_parameters 561 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0792 _refine_ls_R_factor_gt 0.0479 _refine_ls_wR_factor_ref 0.1263 _refine_ls_wR_factor_gt 0.11 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.016 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.392 _refine_diff_density_min -0.296 _refine_diff_density_rms 0.052 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.7647(2) 0.03482(11) 0.23510(14) 0.0339(6) Uani 1 1 d . . . C2 C 0.8153(2) -0.00754(12) 0.28331(17) 0.0473(8) Uani 1 1 d . . . C3 C 0.8749(3) -0.05463(14) 0.2586(2) 0.0669(10) Uani 1 1 d . . . H3 H 0.9086 -0.0828 0.2895 0.08 Uiso 1 1 calc R . . C4 C 0.8847(3) -0.06011(15) 0.1906(2) 0.0719(11) Uani 1 1 d . . . H4 H 0.923 -0.0922 0.1756 0.086 Uiso 1 1 calc R . . C5 C 0.8383(3) -0.01855(13) 0.14441(19) 0.0575(9) Uani 1 1 d . . . H5 H 0.8472 -0.0224 0.0984 0.069 Uiso 1 1 calc R . . C6 C 0.7782(2) 0.02930(12) 0.16496(15) 0.0416(7) Uani 1 1 d . . . C7 C 0.8116(3) -0.00208(15) 0.35979(17) 0.0599(9) Uani 1 1 d . . . H7 H 0.7444 0.0229 0.365 0.072 Uiso 1 1 calc R . . C8 C 0.9219(3) 0.02881(19) 0.3964(2) 0.0817(12) Uani 1 1 d . . . H8A H 0.9899 0.0056 0.3924 0.122 Uiso 1 1 calc R . . H8B H 0.9154 0.034 0.4441 0.122 Uiso 1 1 calc R . . H8C H 0.9295 0.0661 0.3754 0.122 Uiso 1 1 calc R . . C9 C 0.7932(4) -0.06016(19) 0.3958(2) 0.1029(16) Uani 1 1 d . . . H9A H 0.7272 -0.0803 0.3706 0.154 Uiso 1 1 calc R . . H9B H 0.7785 -0.0526 0.4418 0.154 Uiso 1 1 calc R . . H9C H 0.8623 -0.0838 0.3975 0.154 Uiso 1 1 calc R . . C10 C 0.7368(3) 0.07568(13) 0.11159(15) 0.0475(7) Uani 1 1 d . . . H10 H 0.6998 0.1065 0.1354 0.057 Uiso 1 1 calc R . . C11 C 0.8400(3) 0.10367(15) 0.08332(17) 0.0610(9) Uani 1 1 d . . . H11A H 0.8915 0.1218 0.1203 0.091 Uiso 1 1 calc R . . H11B H 0.8111 0.1325 0.0496 0.091 Uiso 1 1 calc R . . H11C H 0.8823 0.0743 0.0624 0.091 Uiso 1 1 calc R . . C12 C 0.6451(3) 0.05472(17) 0.05245(17) 0.0672(10) Uani 1 1 d . . . H12A H 0.6267 0.0857 0.0198 0.101 Uiso 1 1 calc R . . H12B H 0.5752 0.0432 0.0701 0.101 Uiso 1 1 calc R . . H12C H 0.6756 0.022 0.0303 0.101 Uiso 1 1 calc R . . C13 C 0.6809(2) 0.22574(10) 0.15347(13) 0.0315(6) Uani 1 1 d . . . C14 C 0.7698(2) 0.23958(11) 0.20843(13) 0.0332(6) Uani 1 1 d . . . C15 C 0.8691(3) 0.26921(13) 0.19400(16) 0.0523(8) Uani 1 1 d . . . H15 H 0.9292 0.2777 0.2298 0.063 Uiso 1 1 calc R . . C16 C 0.8803(3) 0.28597(15) 0.12882(17) 0.0630(10) Uani 1 1 d . . . H16 H 0.9478 0.3053 0.1205 0.076 Uiso 1 1 calc R . . C17 C 0.7916(3) 0.27432(14) 0.07530(16) 0.0551(8) Uani 1 1 d . . . H17 H 0.7991 0.2867 0.0311 0.066 Uiso 1 1 calc R . . C18 C 0.6913(2) 0.24443(11) 0.08607(14) 0.0404(7) Uani 1 1 d . . . C19 C 0.5941(3) 0.23288(14) 0.02595(15) 0.0536(8) Uani 1 1 d . . . H19 H 0.5567 0.1961 0.0356 0.064 Uiso 1 1 calc R . . C20 C 0.6353(3) 0.22631(16) -0.04327(17) 0.0697(10) Uani 1 1 d . . . H20A H 0.6669 0.2627 -0.0562 0.105 Uiso 1 1 calc R . . H20B H 0.5702 0.2153 -0.0773 0.105 Uiso 1 1 calc R . . H20C H 0.6949 0.1968 -0.0402 0.105 Uiso 1 1 calc R . . C21 C 0.5006(4) 0.28003(18) 0.0220(2) 0.0857(13) Uani 1 1 d . . . H21A H 0.5334 0.3166 0.0108 0.129 Uiso 1 1 calc R . . H21B H 0.4733 0.2832 0.0657 0.129 Uiso 1 1 calc R . . H21C H 0.4359 0.2701 -0.0129 0.129 Uiso 1 1 calc R . . C22 C 0.7612(2) 0.22632(11) 0.28313(13) 0.0355(6) Uani 1 1 d . . . H22 H 0.6941 0.2002 0.2837 0.043 Uiso 1 1 calc R . . C23 C 0.8703(3) 0.19488(14) 0.31910(15) 0.0511(8) Uani 1 1 d . . . H23A H 0.8832 0.1602 0.2939 0.077 Uiso 1 1 calc R . . H23B H 0.8591 0.1845 0.365 0.077 Uiso 1 1 calc R . . H23C H 0.9373 0.2201 0.321 0.077 Uiso 1 1 calc R . . C24 C 0.7373(3) 0.28184(13) 0.32184(17) 0.0605(9) Uani 1 1 d . . . H24A H 0.8023 0.3081 0.3227 0.091 Uiso 1 1 calc R . . H24B H 0.7274 0.2721 0.3681 0.091 Uiso 1 1 calc R . . H24C H 0.6671 0.3001 0.2989 0.091 Uiso 1 1 calc R . . C25 C 0.3500(2) 0.04040(11) 0.14496(12) 0.0302(6) Uani 1 1 d . . . C26 C 0.3445(2) -0.02128(12) 0.15358(14) 0.0427(7) Uani 1 1 d . . . C27 C 0.2440(3) -0.04998(15) 0.12177(17) 0.0615(9) Uani 1 1 d . . . H27 H 0.2375 -0.09 0.1277 0.074 Uiso 1 1 calc R . . C28 C 0.1545(3) -0.02078(19) 0.08204(19) 0.0705(11) Uani 1 1 d . . . H28 H 0.0863 -0.0406 0.064 0.085 Uiso 1 1 calc R . . C29 C 0.1648(3) 0.03731(18) 0.06871(16) 0.0596(9) Uani 1 1 d . . . H29 H 0.1059 0.0559 0.0389 0.071 Uiso 1 1 calc R . . C30 C 0.2613(2) 0.06906(13) 0.09880(14) 0.0409(7) Uani 1 1 d . . . C31 C 0.4477(3) -0.05499(12) 0.18938(17) 0.0567(9) Uani 1 1 d . . . H31 H 0.4947 -0.0286 0.2218 0.068 Uiso 1 1 calc R . . C32 C 0.5252(3) -0.07561(16) 0.1371(2) 0.0762(11) Uani 1 1 d . . . H32A H 0.4822 -0.1028 0.1058 0.114 Uiso 1 1 calc R . . H32B H 0.5944 -0.0942 0.1609 0.114 Uiso 1 1 calc R . . H32C H 0.5476 -0.0427 0.1118 0.114 Uiso 1 1 calc R . . C33 C 0.4133(5) -0.10718(16) 0.2299(2) 0.0989(15) Uani 1 1 d . . . H33A H 0.3586 -0.095 0.2595 0.148 Uiso 1 1 calc R . . H33B H 0.4821 -0.1231 0.2573 0.148 Uiso 1 1 calc R . . H33C H 0.3774 -0.1364 0.1985 0.148 Uiso 1 1 calc R . . C34 C 0.2754(3) 0.13155(14) 0.07854(16) 0.0555(9) Uani 1 1 d . . . H34 H 0.3363 0.1487 0.113 0.067 Uiso 1 1 calc R . . C35 C 0.3183(4) 0.1353(2) 0.0106(2) 0.1028(15) Uani 1 1 d . . . H35A H 0.3911 0.1144 0.0129 0.154 Uiso 1 1 calc R . . H35B H 0.3304 0.1754 -0.0004 0.154 Uiso 1 1 calc R . . H35C H 0.261 0.1184 -0.0245 0.154 Uiso 1 1 calc R . . C36 C 0.1655(5) 0.1676(2) 0.0781(4) 0.174(3) Uani 1 1 d . . . H36A H 0.1048 0.1531 0.0433 0.261 Uiso 1 1 calc R . . H36B H 0.1819 0.2075 0.0684 0.261 Uiso 1 1 calc R . . H36C H 0.14 0.1651 0.1223 0.261 Uiso 1 1 calc R . . C37 C 0.4641(2) 0.19130(13) 0.33600(15) 0.0422(7) Uani 1 1 d . . . C38 C 0.5128(3) 0.18723(14) 0.40615(16) 0.0524(8) Uani 1 1 d . . . C39 C 0.5043(4) 0.2358(2) 0.4481(2) 0.0802(13) Uani 1 1 d . . . H39 H 0.5348 0.2335 0.4946 0.096 Uiso 1 1 calc R . . C40 C 0.4523(4) 0.2869(2) 0.4229(3) 0.0999(17) Uani 1 1 d . . . H40 H 0.4484 0.3188 0.4517 0.12 Uiso 1 1 calc R . . C41 C 0.4068(3) 0.28988(17) 0.3553(3) 0.0819(13) Uani 1 1 d . . . H41 H 0.3717 0.3245 0.3384 0.098 Uiso 1 1 calc R . . C42 C 0.4099(3) 0.24379(14) 0.31001(19) 0.0553(9) Uani 1 1 d . . . C43 C 0.5690(3) 0.13195(16) 0.43674(15) 0.0573(9) Uani 1 1 d . . . H43 H 0.5749 0.1051 0.3986 0.069 Uiso 1 1 calc R . . C44 C 0.6929(3) 0.1406(2) 0.4762(2) 0.0930(14) Uani 1 1 d . . . H44A H 0.7403 0.1607 0.4475 0.14 Uiso 1 1 calc R . . H44B H 0.7273 0.1033 0.489 0.14 Uiso 1 1 calc R . . H44C H 0.689 0.1631 0.5169 0.14 Uiso 1 1 calc R . . C45 C 0.4913(4) 0.10272(19) 0.48383(18) 0.0802(12) Uani 1 1 d . . . H45A H 0.5253 0.0661 0.4998 0.12 Uiso 1 1 calc R . . H45B H 0.4142 0.0963 0.4586 0.12 Uiso 1 1 calc R . . H45C H 0.4858 0.1275 0.5226 0.12 Uiso 1 1 calc R . . C46 C 0.3533(3) 0.25227(14) 0.2358(2) 0.0674(10) Uani 1 1 d . . . H46 H 0.3724 0.218 0.2099 0.081 Uiso 1 1 calc R . . C47 C 0.4008(4) 0.30551(15) 0.2027(2) 0.0833(12) Uani 1 1 d . . . H47A H 0.3848 0.3399 0.2275 0.125 Uiso 1 1 calc R . . H47B H 0.3635 0.3087 0.1557 0.125 Uiso 1 1 calc R . . H47C H 0.4841 0.3015 0.204 0.125 Uiso 1 1 calc R . . C48 C 0.2175(3) 0.2552(2) 0.2299(3) 0.124(2) Uani 1 1 d . . . H48A H 0.1961 0.2856 0.2591 0.186 Uiso 1 1 calc R . . H48B H 0.1884 0.2185 0.2438 0.186 Uiso 1 1 calc R . . H48C H 0.1841 0.2631 0.183 0.186 Uiso 1 1 calc R . . C49 C 0.4955(3) -0.00448(14) 0.35479(16) 0.0546(8) Uani 1 1 d . . . H49A H 0.5147 0.0043 0.403 0.082 Uiso 1 1 calc R . . H49B H 0.5521 0.0135 0.3302 0.082 Uiso 1 1 calc R . . H49C H 0.4968 -0.0459 0.3483 0.082 Uiso 1 1 calc R . . C50 C 0.2899(3) -0.01158(18) 0.3630(2) 0.0816(12) Uani 1 1 d . . . H50A H 0.3004 -0.053 0.3611 0.122 Uiso 1 1 calc R . . H50B H 0.2131 -0.0014 0.34 0.122 Uiso 1 1 calc R . . H50C H 0.298 0.0006 0.4103 0.122 Uiso 1 1 calc R . . C51 C 0.1892(3) 0.12597(18) 0.33554(17) 0.0688(11) Uani 1 1 d . . . H51A H 0.1448 0.1552 0.308 0.103 Uiso 1 1 calc R . . H51B H 0.2272 0.1431 0.3777 0.103 Uiso 1 1 calc R . . H51C H 0.1374 0.0955 0.3458 0.103 Uiso 1 1 calc R . . C52 C 0.0795(3) 0.08889(19) 0.22908(18) 0.0742(12) Uani 1 1 d . . . H52A H 0.0358 0.0639 0.2551 0.111 Uiso 1 1 calc R . . H52B H 0.0875 0.0705 0.1862 0.111 Uiso 1 1 calc R . . H52C H 0.0386 0.1252 0.2203 0.111 Uiso 1 1 calc R . . N1 N 0.70206(16) 0.08276(8) 0.25589(10) 0.0298(5) Uani 1 1 d . . . H1 H 0.7363 0.0978 0.2938 0.036 Uiso 1 1 calc R . . N2 N 0.58319(18) 0.19260(9) 0.16627(11) 0.0343(5) Uani 1 1 d . . . H2 H 0.5183 0.2064 0.1449 0.041 Uiso 1 1 calc R . . N3 N 0.44157(17) 0.07248(8) 0.18289(10) 0.0284(5) Uani 1 1 d . . . N4 N 0.46914(17) 0.14208(9) 0.29214(11) 0.0325(5) Uani 1 1 d . . . N5 N 0.3794(2) 0.01773(11) 0.32898(12) 0.0494(6) Uani 1 1 d . . . N6 N 0.19547(19) 0.09959(12) 0.26805(13) 0.0501(6) Uani 1 1 d . . . Ti1 Ti 0.55721(3) 0.123340(18) 0.21998(2) 0.02355(12) Uani 1 1 d . . . Ti2 Ti 0.35290(4) 0.08104(2) 0.26551(2) 0.03459(14) 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 C1 0.0200(12) 0.0276(14) 0.0525(17) 0.0009(12) 0.0009(12) -0.0018(11) C2 0.0296(15) 0.0396(17) 0.072(2) 0.0165(15) 0.0041(14) 0.0007(13) C3 0.049(2) 0.0401(19) 0.111(3) 0.025(2) 0.008(2) 0.0142(15) C4 0.065(2) 0.0397(19) 0.114(3) -0.008(2) 0.022(2) 0.0150(17) C5 0.054(2) 0.0443(19) 0.074(2) -0.0148(17) 0.0115(17) 0.0086(15) C6 0.0350(15) 0.0353(16) 0.0537(19) -0.0105(13) 0.0041(13) 0.0008(12) C7 0.0392(17) 0.069(2) 0.070(2) 0.0370(18) 0.0026(16) 0.0060(16) C8 0.052(2) 0.116(3) 0.072(3) 0.023(2) -0.0049(19) -0.001(2) C9 0.091(3) 0.097(3) 0.122(4) 0.072(3) 0.019(3) 0.006(3) C10 0.0516(18) 0.0506(18) 0.0399(17) -0.0084(14) 0.0059(14) 0.0143(15) C11 0.065(2) 0.059(2) 0.057(2) -0.0011(17) 0.0017(17) -0.0046(17) C12 0.057(2) 0.089(3) 0.053(2) 0.0010(19) 0.0002(17) -0.0019(19) C13 0.0294(14) 0.0228(13) 0.0414(16) 0.0038(11) 0.0028(12) -0.0010(11) C14 0.0332(14) 0.0266(13) 0.0396(15) -0.0018(11) 0.0046(12) -0.0049(11) C15 0.0451(18) 0.060(2) 0.0497(19) 0.0023(15) 0.0009(14) -0.0229(15) C16 0.053(2) 0.077(2) 0.059(2) 0.0129(18) 0.0089(17) -0.0345(18) C17 0.060(2) 0.060(2) 0.0461(19) 0.0148(15) 0.0097(16) -0.0188(16) C18 0.0427(16) 0.0330(15) 0.0439(17) 0.0084(12) 0.0016(13) -0.0049(12) C19 0.058(2) 0.0504(19) 0.0475(19) 0.0159(15) -0.0076(15) -0.0093(15) C20 0.089(3) 0.070(2) 0.046(2) 0.0097(17) -0.0062(18) -0.010(2) C21 0.080(3) 0.094(3) 0.075(3) 0.015(2) -0.017(2) 0.020(2) C22 0.0330(15) 0.0350(15) 0.0388(15) -0.0071(12) 0.0064(12) -0.0081(12) C23 0.0434(17) 0.065(2) 0.0431(18) 0.0031(15) -0.0010(14) -0.0045(15) C24 0.074(2) 0.0465(19) 0.064(2) -0.0214(16) 0.0217(18) -0.0100(17) C25 0.0241(13) 0.0384(15) 0.0290(14) -0.0084(11) 0.0068(11) -0.0069(11) C26 0.0488(17) 0.0405(17) 0.0394(16) -0.0057(13) 0.0081(13) -0.0165(14) C27 0.065(2) 0.057(2) 0.064(2) -0.0180(17) 0.0148(19) -0.0365(18) C28 0.0373(19) 0.104(3) 0.070(2) -0.042(2) 0.0086(18) -0.029(2) C29 0.0348(17) 0.093(3) 0.0471(19) -0.0286(19) -0.0047(14) 0.0041(18) C30 0.0279(14) 0.0586(19) 0.0354(15) -0.0152(13) 0.0017(12) 0.0034(13) C31 0.074(2) 0.0289(16) 0.063(2) 0.0032(14) -0.0041(18) -0.0085(15) C32 0.070(2) 0.056(2) 0.100(3) -0.011(2) 0.003(2) 0.0112(19) C33 0.148(4) 0.046(2) 0.100(3) 0.016(2) 0.008(3) -0.018(2) C34 0.055(2) 0.058(2) 0.0467(19) -0.0008(15) -0.0170(15) 0.0137(16) C35 0.123(4) 0.097(3) 0.098(3) -0.006(3) 0.044(3) -0.045(3) C36 0.135(5) 0.125(5) 0.281(9) 0.103(5) 0.099(5) 0.085(4) C37 0.0269(14) 0.0514(18) 0.0526(19) -0.0227(14) 0.0193(13) -0.0106(13) C38 0.0482(18) 0.067(2) 0.0471(19) -0.0237(16) 0.0243(15) -0.0242(16) C39 0.096(3) 0.092(3) 0.062(2) -0.044(2) 0.040(2) -0.040(3) C40 0.122(4) 0.076(3) 0.117(4) -0.059(3) 0.068(3) -0.019(3) C41 0.073(3) 0.060(2) 0.124(4) -0.039(2) 0.050(3) 0.0016(19) C42 0.0353(16) 0.0482(19) 0.087(3) -0.0247(17) 0.0240(17) 0.0025(14) C43 0.057(2) 0.084(3) 0.0326(17) -0.0153(16) 0.0127(15) -0.0245(18) C44 0.068(3) 0.139(4) 0.071(3) -0.006(3) 0.007(2) -0.032(3) C45 0.086(3) 0.108(3) 0.051(2) 0.000(2) 0.024(2) -0.029(2) C46 0.0421(19) 0.0447(19) 0.111(3) -0.0157(19) -0.0030(19) 0.0156(15) C47 0.082(3) 0.048(2) 0.117(3) -0.004(2) 0.003(2) 0.015(2) C48 0.046(2) 0.085(3) 0.232(7) -0.004(4) -0.007(3) 0.019(2) C49 0.053(2) 0.061(2) 0.0480(19) 0.0156(16) 0.0032(15) -0.0109(16) C50 0.066(2) 0.095(3) 0.091(3) 0.025(2) 0.034(2) -0.024(2) C51 0.0365(18) 0.116(3) 0.054(2) -0.032(2) 0.0057(15) -0.0150(19) C52 0.0304(17) 0.130(3) 0.063(2) -0.039(2) 0.0090(16) -0.0156(19) N1 0.0222(10) 0.0337(12) 0.0314(12) -0.0015(9) -0.0021(9) -0.0016(9) N2 0.0247(11) 0.0297(11) 0.0461(13) 0.0092(10) -0.0021(10) -0.0002(9) N3 0.0252(11) 0.0258(11) 0.0337(12) -0.0013(9) 0.0026(9) -0.0014(9) N4 0.0255(11) 0.0366(12) 0.0358(12) -0.0080(10) 0.0059(9) -0.0030(9) N5 0.0381(14) 0.0613(16) 0.0508(15) 0.0099(12) 0.0136(12) -0.0145(12) N6 0.0256(12) 0.0744(17) 0.0525(15) -0.0206(13) 0.0129(11) -0.0065(12) Ti1 0.0190(2) 0.0235(2) 0.0279(2) -0.00004(18) 0.00286(17) -0.00147(17) Ti2 0.0229(2) 0.0431(3) 0.0392(3) -0.0057(2) 0.0093(2) -0.0078(2) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 N1 1.409(3) . ? C1 C6 1.416(4) . ? C1 C2 1.419(4) . ? C2 C3 1.405(5) . ? C2 C7 1.515(5) . ? C3 C4 1.363(5) . ? C4 C5 1.368(5) . ? C5 C6 1.390(4) . ? C6 C10 1.519(4) . ? C7 C8 1.535(5) . ? C7 C9 1.538(5) . ? C10 C12 1.525(4) . ? C10 C11 1.527(4) . ? C13 C14 1.407(4) . ? C13 N2 1.411(3) . ? C13 C18 1.414(4) . ? C14 C15 1.396(4) . ? C14 C22 1.516(4) . ? C15 C16 1.362(4) . ? C16 C17 1.377(4) . ? C17 C18 1.386(4) . ? C18 C19 1.522(4) . ? C19 C20 1.514(5) . ? C19 C21 1.520(5) . ? C22 C23 1.526(4) . ? C22 C24 1.530(4) . ? C25 N3 1.404(3) . ? C25 C30 1.420(4) . ? C25 C26 1.428(4) . ? C25 Ti2 2.541(2) . ? C26 C27 1.395(4) . ? C26 C31 1.500(4) . ? C27 C28 1.369(5) . ? C28 C29 1.367(5) . ? C29 C30 1.384(4) . ? C30 C34 1.503(4) . ? C31 C33 1.523(5) . ? C31 C32 1.535(5) . ? C34 C35 1.495(5) . ? C34 C36 1.511(5) . ? C37 C38 1.410(4) . ? C37 C42 1.415(4) . ? C37 N4 1.427(3) . ? C38 C39 1.399(5) . ? C38 C43 1.507(5) . ? C39 C40 1.374(6) . ? C40 C41 1.353(6) . ? C41 C42 1.386(5) . ? C42 C46 1.516(5) . ? C43 C44 1.531(5) . ? C43 C45 1.535(4) . ? C46 C47 1.524(5) . ? C46 C48 1.552(5) . ? C49 N5 1.449(4) . ? C50 N5 1.473(4) . ? C51 Ti2 2.701(3) . ? C52 N6 1.457(4) . ? N1 Ti1 1.9469(19) . ? N2 Ti1 1.955(2) . ? N3 Ti1 1.8362(19) . ? N3 Ti2 2.054(2) . ? N4 Ti1 1.913(2) . ? N4 Ti2 1.953(2) . ? N5 Ti2 1.909(2) . ? N6 Ti2 1.870(2) . ? Ti1 Ti2 2.8134(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 N1 C1 C6 119.2(2) . . ? N1 C1 C2 121.2(3) . . ? C6 C1 C2 119.6(2) . . ? C3 C2 C1 118.0(3) . . ? C3 C2 C7 119.6(3) . . ? C1 C2 C7 122.3(3) . . ? C4 C3 C2 121.7(3) . . ? C3 C4 C5 120.3(3) . . ? C4 C5 C6 121.3(3) . . ? C5 C6 C1 119.1(3) . . ? C5 C6 C10 118.1(3) . . ? C1 C6 C10 122.7(2) . . ? C2 C7 C8 110.9(3) . . ? C2 C7 C9 114.3(3) . . ? C8 C7 C9 110.3(3) . . ? C6 C10 C12 114.4(3) . . ? C6 C10 C11 111.4(2) . . ? C12 C10 C11 110.1(3) . . ? C14 C13 N2 119.5(2) . . ? C14 C13 C18 119.6(2) . . ? N2 C13 C18 120.9(2) . . ? C15 C14 C13 118.5(2) . . ? C15 C14 C22 118.0(2) . . ? C13 C14 C22 123.4(2) . . ? C16 C15 C14 121.7(3) . . ? C15 C16 C17 119.9(3) . . ? C16 C17 C18 121.2(3) . . ? C17 C18 C13 118.9(3) . . ? C17 C18 C19 120.0(3) . . ? C13 C18 C19 121.1(2) . . ? C20 C19 C21 110.0(3) . . ? C20 C19 C18 114.9(3) . . ? C21 C19 C18 110.3(3) . . ? C14 C22 C23 111.9(2) . . ? C14 C22 C24 110.9(2) . . ? C23 C22 C24 111.2(2) . . ? N3 C25 C30 120.4(2) . . ? N3 C25 C26 120.0(2) . . ? C30 C25 C26 119.7(2) . . ? N3 C25 Ti2 53.85(11) . . ? C30 C25 Ti2 109.41(16) . . ? C26 C25 Ti2 104.35(17) . . ? C27 C26 C25 117.6(3) . . ? C27 C26 C31 120.8(3) . . ? C25 C26 C31 121.4(2) . . ? C28 C27 C26 121.8(3) . . ? C29 C28 C27 120.4(3) . . ? C28 C29 C30 121.2(3) . . ? C29 C30 C25 118.8(3) . . ? C29 C30 C34 120.0(3) . . ? C25 C30 C34 121.0(2) . . ? C26 C31 C33 113.6(3) . . ? C26 C31 C32 110.2(3) . . ? C33 C31 C32 109.4(3) . . ? C35 C34 C30 110.7(3) . . ? C35 C34 C36 110.7(4) . . ? C30 C34 C36 113.6(3) . . ? C38 C37 C42 119.8(3) . . ? C38 C37 N4 119.4(3) . . ? C42 C37 N4 120.8(3) . . ? C39 C38 C37 118.0(4) . . ? C39 C38 C43 120.0(3) . . ? C37 C38 C43 121.9(3) . . ? C40 C39 C38 122.2(4) . . ? C41 C40 C39 118.6(4) . . ? C40 C41 C42 123.2(4) . . ? C41 C42 C37 118.1(4) . . ? C41 C42 C46 118.0(3) . . ? C37 C42 C46 123.9(3) . . ? C38 C43 C44 113.9(3) . . ? C38 C43 C45 110.7(3) . . ? C44 C43 C45 109.6(3) . . ? C42 C46 C47 112.6(3) . . ? C42 C46 C48 111.0(4) . . ? C47 C46 C48 110.9(3) . . ? C1 N1 Ti1 135.74(17) . . ? C13 N2 Ti1 136.48(16) . . ? C25 N3 Ti1 170.07(18) . . ? C25 N3 Ti2 92.63(14) . . ? Ti1 N3 Ti2 92.48(9) . . ? C37 N4 Ti1 134.43(17) . . ? C37 N4 Ti2 129.81(16) . . ? Ti1 N4 Ti2 93.39(9) . . ? C49 N5 C50 110.6(3) . . ? C49 N5 Ti2 122.95(18) . . ? C50 N5 Ti2 126.2(2) . . ? C52 N6 Ti2 139.8(2) . . ? N3 Ti1 N4 90.16(9) . . ? N3 Ti1 N1 111.71(9) . . ? N4 Ti1 N1 111.12(9) . . ? N3 Ti1 N2 117.60(9) . . ? N4 Ti1 N2 111.03(9) . . ? N1 Ti1 N2 113.05(8) . . ? N3 Ti1 Ti2 46.82(6) . . ? N4 Ti1 Ti2 43.87(6) . . ? N1 Ti1 Ti2 115.57(6) . . ? N2 Ti1 Ti2 130.96(6) . . ? N6 Ti2 N5 102.44(11) . . ? N6 Ti2 N4 117.22(10) . . ? N5 Ti2 N4 109.60(10) . . ? N6 Ti2 N3 130.01(10) . . ? N5 Ti2 N3 113.22(10) . . ? N4 Ti2 N3 82.97(8) . . ? N6 Ti2 C25 103.43(9) . . ? N5 Ti2 C25 107.94(10) . . ? N4 Ti2 C25 115.13(8) . . ? N3 Ti2 C25 33.52(7) . . ? N6 Ti2 C51 31.27(10) . . ? N5 Ti2 C51 90.71(12) . . ? N4 Ti2 C51 95.33(9) . . ? N3 Ti2 C51 155.23(10) . . ? C25 Ti2 C51 134.67(9) . . ? N6 Ti2 Ti1 142.25(9) . . ? N5 Ti2 Ti1 114.31(7) . . ? N4 Ti2 Ti1 42.74(6) . . ? N3 Ti2 Ti1 40.70(5) . . ? C25 Ti2 Ti1 73.98(5) . . ? C51 Ti2 Ti1 135.41(8) . . ? _database_code_depnum_ccdc_archive 'CCDC 931104' ####################################################################### # # 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_11 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C42 H70 N6 Ti2, 2(C6 H6)' _chemical_formula_sum 'C54 H82 N6 Ti2 ' _chemical_formula_weight 911 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/m' _symmetry_space_group_name_Hall '-P 2yb' _symmetry_Int_Tables_number 11 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 11.1210(8) _cell_length_b 24.3670(9) _cell_length_c 11.1710(7) _cell_angle_alpha 90 _cell_angle_beta 119.258(9) _cell_angle_gamma 90 _cell_volume 2641.0(3) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 9020 _cell_measurement_theta_min 3.2584 _cell_measurement_theta_max 31.4737 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.05 _exptl_crystal_density_diffrn 1.146 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 984 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.341 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.971 _exptl_absorpt_correction_T_max 0.998 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(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 Xcalibur _diffrn_measurement_method '\w scans' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_detector_area_resol_mean 8.2632 _diffrn_orient_matrix_ub_11 0.0585516 _diffrn_orient_matrix_ub_12 -0.0124877 _diffrn_orient_matrix_ub_13 0.002024 _diffrn_orient_matrix_ub_21 -0.0086432 _diffrn_orient_matrix_ub_22 0.0165401 _diffrn_orient_matrix_ub_23 -0.0559041 _diffrn_orient_matrix_ub_31 0.0428748 _diffrn_orient_matrix_ub_32 0.0204372 _diffrn_orient_matrix_ub_33 0.0465768 _diffrn_reflns_av_R_equivalents 0.0337 _diffrn_reflns_av_unetI/netI 0.0343 _diffrn_reflns_number 17960 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 29 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.26 _diffrn_reflns_theta_max 25.03 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 4775 _reflns_number_gt 3884 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0413P)^2^+11.5437P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 4775 _refine_ls_number_parameters 305 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0992 _refine_ls_R_factor_gt 0.084 _refine_ls_wR_factor_ref 0.2081 _refine_ls_wR_factor_gt 0.2023 _refine_ls_goodness_of_fit_ref 1.172 _refine_ls_restrained_S_all 1.172 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.503 _refine_diff_density_min -1.441 _refine_diff_density_rms 0.083 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.9883(5) 0.13920(19) 0.7967(5) 0.0302(11) Uani 1 1 d . . . C2 C 1.1205(6) 0.1219(2) 0.8238(6) 0.0383(12) Uani 1 1 d . . . C3 C 1.1573(6) 0.0674(2) 0.8546(6) 0.0474(14) Uani 1 1 d . . . H3 H 1.2465 0.0558 0.8737 0.057 Uiso 1 1 calc R . . C4 C 1.0677(7) 0.0299(2) 0.8581(7) 0.0509(15) Uani 1 1 d . . . H4 H 1.0949 -0.0074 0.8797 0.061 Uiso 1 1 calc R . . C5 C 0.9391(6) 0.0460(2) 0.8305(6) 0.0432(13) Uani 1 1 d . . . H5 H 0.878 0.0195 0.8338 0.052 Uiso 1 1 calc R . . C6 C 0.8952(5) 0.1000(2) 0.7977(5) 0.0335(11) Uani 1 1 d . . . C7 C 0.7503(5) 0.1147(2) 0.7641(6) 0.0376(12) Uani 1 1 d . . . H7 H 0.7367 0.1545 0.7398 0.045 Uiso 1 1 calc R . . C8 C 0.6435(7) 0.0831(3) 0.6406(7) 0.0585(17) Uani 1 1 d . . . H8A H 0.66 0.0885 0.5629 0.088 Uiso 1 1 calc R . . H8B H 0.5512 0.0963 0.6162 0.088 Uiso 1 1 calc R . . H8C H 0.6504 0.0439 0.663 0.088 Uiso 1 1 calc R . . C9 C 0.7272(7) 0.1065(3) 0.8872(6) 0.0528(15) Uani 1 1 d . . . H9A H 0.737 0.0676 0.9119 0.079 Uiso 1 1 calc R . . H9B H 0.6343 0.119 0.8633 0.079 Uiso 1 1 calc R . . H9C H 0.7955 0.1279 0.9652 0.079 Uiso 1 1 calc R . . C10 C 1.2264(7) 0.1615(2) 0.8233(7) 0.0522(16) Uani 1 1 d . . . H10 H 1.1772 0.196 0.7763 0.063 Uiso 1 1 calc R . . C11 C 1.2956(8) 0.1379(3) 0.7433(9) 0.072(2) Uani 1 1 d . . . H11A H 1.3451 0.1672 0.7255 0.109 Uiso 1 1 calc R . . H11B H 1.2249 0.1225 0.6559 0.109 Uiso 1 1 calc R . . H11C H 1.3607 0.1089 0.7977 0.109 Uiso 1 1 calc R . . C12 C 1.3331(7) 0.1760(3) 0.9652(8) 0.068(2) Uani 1 1 d . . . H12A H 1.2893 0.1941 1.0124 0.102 Uiso 1 1 calc R . . H12B H 1.4005 0.2009 0.9617 0.102 Uiso 1 1 calc R . . H12C H 1.3799 0.1426 1.015 0.102 Uiso 1 1 calc R . . C13 C 1.2018(6) 0.25 1.2119(7) 0.0251(14) Uani 1 2 d S . . C14 C 1.2515(5) 0.19951(19) 1.2856(5) 0.0284(10) Uani 1 1 d . . . C15 C 1.3382(5) 0.2010(2) 1.4252(5) 0.0363(12) Uani 1 1 d . . . H15 H 1.3699 0.1675 1.4743 0.044 Uiso 1 1 calc R . . C16 C 1.3802(7) 0.25 1.4955(8) 0.0400(18) Uani 1 2 d S . . H16 H 1.4379 0.25 1.5923 0.048 Uiso 1 2 calc SR . . C17 C 1.2015(5) 0.1460(2) 1.2104(5) 0.0343(11) Uani 1 1 d . . . H17 H 1.1721 0.1533 1.1118 0.041 Uiso 1 1 calc R . . C18 C 1.3108(6) 0.1012(2) 1.2592(7) 0.0502(15) Uani 1 1 d . . . H18A H 1.392 0.1148 1.2558 0.075 Uiso 1 1 calc R . . H18B H 1.2738 0.069 1.1996 0.075 Uiso 1 1 calc R . . H18C H 1.3371 0.091 1.3537 0.075 Uiso 1 1 calc R . . C19 C 1.0750(6) 0.1254(3) 1.2165(7) 0.0536(16) Uani 1 1 d . . . H19A H 1.1015 0.1153 1.3111 0.08 Uiso 1 1 calc R . . H19B H 1.0372 0.0932 1.157 0.08 Uiso 1 1 calc R . . H19C H 1.0052 0.1544 1.1852 0.08 Uiso 1 1 calc R . . C20 C 1.0094(8) 0.2994(3) 0.4651(7) 0.0598(18) Uani 1 1 d . . . H20A H 1.1043 0.2984 0.4813 0.09 Uiso 1 1 calc R . . H20B H 0.9974 0.3315 0.5108 0.09 Uiso 1 1 calc R . . H20C H 0.9454 0.3016 0.3663 0.09 Uiso 1 1 calc R . . C21 C 0.6567(9) 0.2007(3) 0.4022(10) 0.086(3) Uani 1 1 d . . . H21A H 0.5646 0.2054 0.3229 0.128 Uiso 1 1 calc R . . H21B H 0.6565 0.1693 0.4568 0.128 Uiso 1 1 calc R . . H21C H 0.7234 0.1942 0.3702 0.128 Uiso 1 1 calc R . . C22 C 0.6682(7) 0.25 0.8373(8) 0.0368(17) Uani 1 2 d S . . H22A H 0.6179 0.2191 0.8481 0.055 Uiso 0.5 1 calc PR . . H22B H 0.6686 0.2464 0.7501 0.055 Uiso 0.5 1 calc PR . . H22C H 0.6232 0.2845 0.8378 0.055 Uiso 0.5 1 calc PR . . C23 C 0.8104(8) 0.25 1.0793(8) 0.0401(18) Uani 1 2 d S . . H23A H 0.9051 0.2452 1.154 0.06 Uiso 0.5 1 calc PR . . H23B H 0.7529 0.2199 1.0809 0.06 Uiso 0.5 1 calc PR . . H23C H 0.774 0.285 1.091 0.06 Uiso 0.5 1 calc PR . . C25 C 0.8445(12) 0.0574(5) 0.3771(15) 0.103(4) Uani 1 1 d . . . H25 H 0.9379 0.069 0.4268 0.123 Uiso 1 1 calc R . . C26 C 0.7931(16) 0.0220(5) 0.4369(11) 0.117(4) Uani 1 1 d . . . H26 H 0.8481 0.0105 0.5294 0.14 Uiso 1 1 calc R . . C27 C 0.6600(18) 0.0036(4) 0.3594(18) 0.114(4) Uani 1 1 d . . . H27 H 0.6221 -0.0213 0.3976 0.136 Uiso 1 1 calc R . . C28 C 0.5852(10) 0.0208(5) 0.2321(17) 0.110(4) Uani 1 1 d . . . H28 H 0.4936 0.0076 0.1781 0.133 Uiso 1 1 calc R . . C29 C 0.6371(14) 0.0567(5) 0.1776(11) 0.104(3) Uani 1 1 d . . . H29 H 0.5821 0.0691 0.0858 0.124 Uiso 1 1 calc R . . C30 C 0.7661(15) 0.0749(4) 0.2530(17) 0.104(4) Uani 1 1 d . . . H30 H 0.8011 0.1012 0.2151 0.125 Uiso 1 1 calc R . . N1 N 0.9488(4) 0.19478(15) 0.7684(4) 0.0302(9) Uani 1 1 d . . . N2 N 1.1067(6) 0.25 1.0759(6) 0.0297(13) Uani 1 2 d S . . N3 N 0.9817(8) 0.25 0.5198(7) 0.0496(18) Uani 1 2 d S . . N4 N 0.6950(9) 0.25 0.4861(7) 0.057(2) Uani 1 2 d S . . H4A H 0.6442 0.25 0.532 0.069 Uiso 1 2 calc SR . . N5 N 0.8093(6) 0.25 0.9499(5) 0.0282(12) Uani 1 2 d S . . Ti1 Ti 0.96240(12) 0.25 0.91573(12) 0.0230(3) Uani 1 2 d S . . Ti2 Ti 0.91244(16) 0.25 0.64277(14) 0.0367(4) Uani 1 2 d S . . 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 C1 0.046(3) 0.022(2) 0.032(3) -0.001(2) 0.027(2) 0.000(2) C2 0.050(3) 0.025(3) 0.055(3) 0.000(2) 0.037(3) 0.002(2) C3 0.053(4) 0.032(3) 0.067(4) 0.007(3) 0.037(3) 0.007(3) C4 0.067(4) 0.021(3) 0.071(4) 0.010(3) 0.038(4) 0.008(3) C5 0.049(3) 0.026(3) 0.056(4) 0.007(2) 0.027(3) -0.004(2) C6 0.040(3) 0.024(2) 0.035(3) 0.000(2) 0.018(2) -0.004(2) C7 0.043(3) 0.024(3) 0.047(3) 0.005(2) 0.023(3) -0.003(2) C8 0.051(4) 0.048(4) 0.055(4) 0.005(3) 0.009(3) -0.004(3) C9 0.054(4) 0.054(4) 0.060(4) 0.007(3) 0.036(3) 0.000(3) C10 0.055(4) 0.031(3) 0.092(5) 0.010(3) 0.053(4) 0.006(3) C11 0.079(5) 0.067(5) 0.110(6) 0.015(4) 0.076(5) 0.008(4) C12 0.065(5) 0.046(4) 0.116(6) -0.002(4) 0.062(5) -0.005(3) C13 0.016(3) 0.027(3) 0.032(4) 0 0.012(3) 0 C14 0.023(2) 0.029(3) 0.034(3) 0.002(2) 0.015(2) 0.0036(19) C15 0.030(3) 0.039(3) 0.034(3) 0.010(2) 0.011(2) 0.008(2) C16 0.021(4) 0.056(5) 0.029(4) 0 0.001(3) 0 C17 0.036(3) 0.026(3) 0.038(3) 0.004(2) 0.016(2) 0.002(2) C18 0.046(3) 0.034(3) 0.066(4) 0.000(3) 0.024(3) 0.006(3) C19 0.044(3) 0.044(3) 0.075(4) -0.012(3) 0.031(3) -0.010(3) C20 0.090(5) 0.052(4) 0.056(4) 0.007(3) 0.050(4) -0.010(4) C21 0.107(7) 0.068(5) 0.121(7) -0.024(5) 0.085(6) -0.024(5) C22 0.022(4) 0.039(4) 0.046(4) 0 0.013(3) 0 C23 0.045(5) 0.050(5) 0.037(4) 0 0.029(4) 0 C25 0.090(7) 0.075(7) 0.151(11) -0.051(7) 0.065(8) -0.019(6) C26 0.164(12) 0.104(9) 0.091(8) 0.001(6) 0.070(8) 0.049(9) C27 0.160(13) 0.074(7) 0.180(13) -0.026(8) 0.140(12) -0.029(8) C28 0.061(6) 0.115(9) 0.175(12) -0.066(9) 0.073(8) -0.020(6) C29 0.112(9) 0.109(8) 0.100(8) 0.004(6) 0.059(7) 0.055(7) C30 0.123(10) 0.063(6) 0.183(13) 0.011(7) 0.119(10) 0.009(6) N1 0.043(2) 0.0220(19) 0.038(2) -0.0014(17) 0.029(2) -0.0007(18) N2 0.030(3) 0.027(3) 0.034(3) 0 0.017(3) 0 N3 0.085(5) 0.037(4) 0.054(4) 0 0.056(4) 0 N4 0.092(6) 0.051(4) 0.036(4) 0 0.036(4) 0 N5 0.026(3) 0.032(3) 0.025(3) 0 0.012(2) 0 Ti1 0.0259(6) 0.0217(6) 0.0234(6) 0 0.0137(5) 0 Ti2 0.0700(10) 0.0208(6) 0.0386(8) 0 0.0416(8) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 N1 1.411(6) . ? C1 C6 1.412(7) . ? C1 C2 1.413(7) . ? C2 C3 1.384(7) . ? C2 C10 1.524(7) . ? C3 C4 1.367(8) . ? C3 H3 0.95 . ? C4 C5 1.365(8) . ? C4 H4 0.95 . ? C5 C6 1.390(7) . ? C5 H5 0.95 . ? C6 C7 1.508(7) . ? C7 C8 1.518(8) . ? C7 C9 1.531(8) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C12 1.485(10) . ? C10 C11 1.548(8) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 N2 1.362(8) . ? C13 C14 1.433(6) 4_565 ? C13 C14 1.433(6) . ? C14 C15 1.377(7) . ? C14 C17 1.502(7) . ? C15 C16 1.379(6) . ? C15 H15 0.95 . ? C16 C15 1.379(6) 4_565 ? C16 H16 0.95 . ? C17 C18 1.523(7) . ? C17 C19 1.526(7) . ? C17 H17 1 . ? C18 H18A 0.98 . ? C18 H18B 0.98 . ? C18 H18C 0.98 . ? C19 H19A 0.98 . ? C19 H19B 0.98 . ? C19 H19C 0.98 . ? C20 N3 1.449(6) . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 N4 1.454(8) . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 N5 1.454(9) . ? C22 H22A 0.98 . ? C22 H22B 0.98 . ? C22 H22C 0.98 . ? C23 N5 1.439(9) . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C25 C30 1.297(15) . ? C25 C26 1.376(15) . ? C25 H25 0.95 . ? C26 C27 1.374(16) . ? C26 H26 0.95 . ? C27 C28 1.317(16) . ? C27 H27 0.95 . ? C28 C29 1.347(16) . ? C28 H28 0.95 . ? C29 C30 1.336(15) . ? C29 H29 0.95 . ? C30 H30 0.95 . ? N1 Ti2 1.841(4) . ? N1 Ti1 2.074(4) . ? N2 Ti1 1.723(6) . ? N3 C20 1.449(6) 4_565 ? N3 Ti2 1.875(6) . ? N4 C21 1.454(8) 4_565 ? N4 Ti2 2.185(8) . ? N4 H4A 0.93 . ? N5 Ti1 1.918(6) . ? Ti1 N1 2.074(4) 4_565 ? Ti1 Ti2 2.8198(17) . ? Ti2 N1 1.841(4) 4_565 ? 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 C1 C6 120.1(4) . . ? N1 C1 C2 120.7(4) . . ? C6 C1 C2 119.1(4) . . ? C3 C2 C1 119.3(5) . . ? C3 C2 C10 118.3(5) . . ? C1 C2 C10 122.4(5) . . ? C4 C3 C2 121.2(5) . . ? C4 C3 H3 119.4 . . ? C2 C3 H3 119.4 . . ? C5 C4 C3 119.9(5) . . ? C5 C4 H4 120 . . ? C3 C4 H4 120 . . ? C4 C5 C6 121.7(5) . . ? C4 C5 H5 119.1 . . ? C6 C5 H5 119.1 . . ? C5 C6 C1 118.6(5) . . ? C5 C6 C7 119.0(5) . . ? C1 C6 C7 122.4(4) . . ? C6 C7 C8 111.9(5) . . ? C6 C7 C9 112.0(5) . . ? C8 C7 C9 110.5(5) . . ? C6 C7 H7 107.4 . . ? C8 C7 H7 107.4 . . ? C9 C7 H7 107.4 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C12 C10 C2 111.3(5) . . ? C12 C10 C11 110.0(6) . . ? C2 C10 C11 111.7(5) . . ? C12 C10 H10 107.9 . . ? C2 C10 H10 107.9 . . ? C11 C10 H10 107.9 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 C14 120.8(3) . 4_565 ? N2 C13 C14 120.8(3) . . ? C14 C13 C14 118.4(6) 4_565 . ? C15 C14 C13 119.2(5) . . ? C15 C14 C17 121.3(4) . . ? C13 C14 C17 119.4(4) . . ? C14 C15 C16 121.5(5) . . ? C14 C15 H15 119.2 . . ? C16 C15 H15 119.2 . . ? C15 C16 C15 120.0(7) 4_565 . ? C15 C16 H16 120 4_565 . ? C15 C16 H16 120 . . ? C14 C17 C18 114.2(4) . . ? C14 C17 C19 111.0(4) . . ? C18 C17 C19 109.9(5) . . ? C14 C17 H17 107.2 . . ? C18 C17 H17 107.2 . . ? C19 C17 H17 107.2 . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C17 C19 H19A 109.5 . . ? C17 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C17 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N3 C20 H20A 109.5 . . ? N3 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? N3 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? N4 C21 H21A 109.5 . . ? N4 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N4 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N5 C22 H22A 109.5 . . ? N5 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N5 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? N5 C23 H23A 109.5 . . ? N5 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? N5 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C30 C25 C26 120.2(11) . . ? C30 C25 H25 119.9 . . ? C26 C25 H25 119.9 . . ? C27 C26 C25 118.3(11) . . ? C27 C26 H26 120.9 . . ? C25 C26 H26 120.9 . . ? C28 C27 C26 119.7(11) . . ? C28 C27 H27 120.2 . . ? C26 C27 H27 120.2 . . ? C27 C28 C29 120.7(11) . . ? C27 C28 H28 119.6 . . ? C29 C28 H28 119.6 . . ? C30 C29 C28 119.7(11) . . ? C30 C29 H29 120.1 . . ? C28 C29 H29 120.1 . . ? C25 C30 C29 121.3(11) . . ? C25 C30 H30 119.4 . . ? C29 C30 H30 119.4 . . ? C1 N1 Ti2 143.2(3) . . ? C1 N1 Ti1 123.4(3) . . ? Ti2 N1 Ti1 91.97(16) . . ? C13 N2 Ti1 168.2(5) . . ? C20 N3 C20 112.3(6) . 4_565 ? C20 N3 Ti2 123.9(3) . . ? C20 N3 Ti2 123.9(3) 4_565 . ? C21 N4 C21 111.5(9) 4_565 . ? C21 N4 Ti2 112.2(5) 4_565 . ? C21 N4 Ti2 112.2(5) . . ? C21 N4 H4A 106.9 4_565 . ? C21 N4 H4A 106.9 . . ? Ti2 N4 H4A 106.9 . . ? C23 N5 C22 110.2(6) . . ? C23 N5 Ti1 128.8(5) . . ? C22 N5 Ti1 121.0(4) . . ? N2 Ti1 N5 105.1(3) . . ? N2 Ti1 N1 119.57(18) . 4_565 ? N5 Ti1 N1 115.52(16) . 4_565 ? N2 Ti1 N1 119.57(18) . . ? N5 Ti1 N1 115.52(16) . . ? N1 Ti1 N1 80.9(2) 4_565 . ? N2 Ti1 Ti2 135.5(2) . . ? N5 Ti1 Ti2 119.36(17) . . ? N1 Ti1 Ti2 40.72(11) 4_565 . ? N1 Ti1 Ti2 40.72(11) . . ? N1 Ti2 N1 93.9(2) 4_565 . ? N1 Ti2 N3 122.85(18) 4_565 . ? N1 Ti2 N3 122.85(18) . . ? N1 Ti2 N4 110.83(18) 4_565 . ? N1 Ti2 N4 110.83(19) . . ? N3 Ti2 N4 95.9(3) . . ? N1 Ti2 Ti1 47.31(12) 4_565 . ? N1 Ti2 Ti1 47.31(12) . . ? N3 Ti2 Ti1 149.1(3) . . ? N4 Ti2 Ti1 115.0(2) . . ? _database_code_depnum_ccdc_archive 'CCDC 931105' ####################################################################### # # 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_12 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C48 H76 N4 Ti' _chemical_formula_sum 'C48 H76 N4 Ti' _chemical_formula_weight 757.03 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 2/c 1' _symmetry_space_group_name_Hall '-C 2yc' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 19.1831(6) _cell_length_b 13.1110(4) _cell_length_c 18.5082(6) _cell_angle_alpha 90 _cell_angle_beta 91.513(3) _cell_angle_gamma 90 _cell_volume 4653.4(3) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 5290 _cell_measurement_theta_min 3.2903 _cell_measurement_theta_max 29.1994 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.04 _exptl_crystal_density_diffrn 1.081 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1656 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.218 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.922 _exptl_absorpt_correction_T_max 0.978 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector_area_resol_mean 16.1978 _diffrn_orient_matrix_ub_11 0.0085583 _diffrn_orient_matrix_ub_12 0.0097815 _diffrn_orient_matrix_ub_13 0.0368599 _diffrn_orient_matrix_ub_21 0.0308949 _diffrn_orient_matrix_ub_22 0.0252735 _diffrn_orient_matrix_ub_23 -0.0102957 _diffrn_orient_matrix_ub_31 -0.0184474 _diffrn_orient_matrix_ub_32 0.0468337 _diffrn_orient_matrix_ub_33 -0.0021467 _diffrn_measurement_device_type 'Xcalibur, Eos, Gemini ultra' _diffrn_measurement_method '\w scans' _diffrn_reflns_av_R_equivalents 0.0532 _diffrn_reflns_av_unetI/netI 0.0818 _diffrn_reflns_number 19596 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 3.3 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.998 _diffrn_measured_fraction_theta_max 0.998 _reflns_number_total 4756 _reflns_number_gt 2943 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; ? ; _computing_cell_refinement ; ? ; _computing_data_reduction ; ? ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0676P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 4756 _refine_ls_number_parameters 248 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0874 _refine_ls_R_factor_gt 0.0497 _refine_ls_wR_factor_ref 0.1243 _refine_ls_wR_factor_gt 0.117 _refine_ls_goodness_of_fit_ref 0.917 _refine_ls_restrained_S_all 0.917 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.322 _refine_diff_density_min -0.546 _refine_diff_density_rms 0.045 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 1.09866(11) 0.27360(16) 0.64463(11) 0.0318(5) Uani 1 1 d . . . C2 C 1.09163(12) 0.37227(16) 0.61482(12) 0.0365(6) Uani 1 1 d . . . C3 C 1.11720(13) 0.3887(2) 0.54601(14) 0.0480(7) Uani 1 1 d . . . H3 H 1.1119 0.454 0.5243 0.058 Uiso 1 1 calc R . . C4 C 1.15001(14) 0.3122(2) 0.50881(13) 0.0564(8) Uani 1 1 d . . . H4 H 1.1677 0.3251 0.4622 0.068 Uiso 1 1 calc R . . C5 C 1.15704(14) 0.2174(2) 0.53927(15) 0.0537(7) Uani 1 1 d . . . H5 H 1.1799 0.1653 0.5133 0.064 Uiso 1 1 calc R . . C6 C 1.13167(12) 0.19550(18) 0.60699(13) 0.0416(6) Uani 1 1 d . . . C7 C 1.05762(14) 0.45654(17) 0.65713(14) 0.0467(7) Uani 1 1 d . . . H7 H 1.0178 0.4255 0.6832 0.056 Uiso 1 1 calc R . . C8 C 1.02786(18) 0.5437(2) 0.61054(18) 0.0789(10) Uani 1 1 d . . . H8A H 1.0662 0.5821 0.5895 0.118 Uiso 1 1 calc R . . H8B H 1.0004 0.5893 0.6406 0.118 Uiso 1 1 calc R . . H8C H 0.998 0.5155 0.5717 0.118 Uiso 1 1 calc R . . C9 C 1.10820(16) 0.5011(2) 0.71468(15) 0.0626(8) Uani 1 1 d . . . H9A H 1.1258 0.4462 0.7461 0.094 Uiso 1 1 calc R . . H9B H 1.0837 0.5515 0.7437 0.094 Uiso 1 1 calc R . . H9C H 1.1473 0.534 0.6909 0.094 Uiso 1 1 calc R . . C10 C 1.14200(13) 0.08961(17) 0.63903(15) 0.0478(7) Uani 1 1 d . . . H10 H 1.1126 0.0853 0.6828 0.057 Uiso 1 1 calc R . . C11 C 1.1171(2) 0.0055(2) 0.58683(19) 0.0964(13) Uani 1 1 d . . . H11A H 1.0689 0.0193 0.5708 0.145 Uiso 1 1 calc R . . H11B H 1.1193 -0.0606 0.6115 0.145 Uiso 1 1 calc R . . H11C H 1.1471 0.0041 0.5448 0.145 Uiso 1 1 calc R . . C12 C 1.21758(17) 0.0743(3) 0.6643(3) 0.1082(16) Uani 1 1 d . . . H12A H 1.248 0.0778 0.6226 0.162 Uiso 1 1 calc R . . H12B H 1.2226 0.0074 0.6874 0.162 Uiso 1 1 calc R . . H12C H 1.2308 0.1278 0.699 0.162 Uiso 1 1 calc R . . C13 C 0.89352(11) 0.06551(16) 0.64474(11) 0.0323(5) Uani 1 1 d . . . C14 C 0.86420(12) 0.14752(17) 0.60590(12) 0.0367(5) Uani 1 1 d . . . C15 C 0.79814(14) 0.1356(2) 0.57503(15) 0.0535(7) Uani 1 1 d . . . H15 H 0.777 0.191 0.5496 0.064 Uiso 1 1 calc R . . C16 C 0.76251(14) 0.0449(2) 0.58046(16) 0.0600(8) Uani 1 1 d . . . H16 H 0.7178 0.0377 0.5578 0.072 Uiso 1 1 calc R . . C17 C 0.79143(14) -0.0348(2) 0.61838(14) 0.0508(7) Uani 1 1 d . . . H17 H 0.7661 -0.0967 0.6222 0.061 Uiso 1 1 calc R . . C18 C 0.85726(13) -0.02704(17) 0.65160(13) 0.0398(6) Uani 1 1 d . . . C19 C 0.90443(13) 0.24503(17) 0.59267(13) 0.0447(6) Uani 1 1 d . . . H19 H 0.9407 0.2509 0.6323 0.054 Uiso 1 1 calc R . . C20 C 0.94275(18) 0.2361(2) 0.52176(15) 0.0730(10) Uani 1 1 d . . . H20A H 0.9719 0.1747 0.5228 0.109 Uiso 1 1 calc R . . H20B H 0.9722 0.2963 0.5155 0.109 Uiso 1 1 calc R . . H20C H 0.9087 0.2315 0.4814 0.109 Uiso 1 1 calc R . . C21 C 0.85966(18) 0.3406(2) 0.5954(2) 0.0857(12) Uani 1 1 d . . . H21A H 0.8287 0.3433 0.5525 0.129 Uiso 1 1 calc R . . H21B H 0.8898 0.401 0.5965 0.129 Uiso 1 1 calc R . . H21C H 0.8317 0.3392 0.6389 0.129 Uiso 1 1 calc R . . C22 C 0.88978(15) -0.11447(18) 0.69467(15) 0.0536(7) Uani 1 1 d . . . H22 H 0.9145 -0.0838 0.7377 0.064 Uiso 1 1 calc R . . C23 C 0.94470(17) -0.1707(2) 0.65100(18) 0.0734(10) Uani 1 1 d . . . H23A H 0.9217 -0.2071 0.6107 0.11 Uiso 1 1 calc R . . H23B H 0.9696 -0.2196 0.6823 0.11 Uiso 1 1 calc R . . H23C H 0.9779 -0.1213 0.632 0.11 Uiso 1 1 calc R . . C24 C 0.8360(2) -0.1900(2) 0.7233(2) 0.0913(12) Uani 1 1 d . . . H24A H 0.7993 -0.1524 0.7478 0.137 Uiso 1 1 calc R . . H24B H 0.859 -0.2371 0.7574 0.137 Uiso 1 1 calc R . . H24C H 0.8153 -0.2286 0.6828 0.137 Uiso 1 1 calc R . . N1 N 1.06943(9) 0.25292(13) 0.71241(9) 0.0312(4) Uani 1 1 d . . . H1A H 1.0553 0.3164 0.7274 0.037 Uiso 1 1 calc R . . H1B H 1.108 0.2379 0.741 0.037 Uiso 1 1 calc R . . N2 N 0.95972(9) 0.07784(12) 0.67872(10) 0.0331(4) Uani 1 1 d . . . H2A H 0.9888 0.0855 0.6404 0.04 Uiso 1 1 calc R . . H2B H 0.9693 0.0138 0.6968 0.04 Uiso 1 1 calc R . . Ti1 Ti 1 0.16549(4) 0.75 0.02499(17) Uani 1 2 d S . . 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 C1 0.0303(13) 0.0347(13) 0.0302(12) -0.0021(10) -0.0020(10) -0.0133(10) C2 0.0340(13) 0.0411(13) 0.0340(12) 0.0020(11) -0.0047(10) -0.0170(11) C3 0.0461(16) 0.0561(16) 0.0414(15) 0.0104(13) -0.0070(12) -0.0275(13) C4 0.0554(18) 0.084(2) 0.0305(13) -0.0034(14) 0.0074(13) -0.0313(15) C5 0.0483(17) 0.0645(18) 0.0489(16) -0.0185(14) 0.0152(13) -0.0198(14) C6 0.0335(13) 0.0501(15) 0.0414(14) -0.0116(11) 0.0057(11) -0.0158(11) C7 0.0540(17) 0.0341(13) 0.0520(16) 0.0058(11) 0.0012(13) -0.0073(12) C8 0.097(3) 0.0527(18) 0.087(2) 0.0235(17) 0.000(2) 0.0084(17) C9 0.083(2) 0.0464(15) 0.0588(18) -0.0124(14) 0.0078(16) -0.0232(15) C10 0.0415(16) 0.0382(14) 0.0646(18) -0.0124(12) 0.0153(13) -0.0070(12) C11 0.148(4) 0.0546(18) 0.088(3) -0.0328(18) 0.039(3) -0.028(2) C12 0.050(2) 0.072(2) 0.203(5) 0.053(3) 0.007(3) 0.0011(17) C13 0.0308(13) 0.0367(13) 0.0292(12) -0.0080(10) -0.0012(10) -0.0075(10) C14 0.0340(13) 0.0439(14) 0.0317(12) -0.0016(10) -0.0067(10) -0.0084(11) C15 0.0441(16) 0.0591(17) 0.0563(17) 0.0066(13) -0.0190(14) -0.0076(13) C16 0.0361(16) 0.076(2) 0.067(2) 0.0067(16) -0.0164(14) -0.0155(15) C17 0.0449(16) 0.0538(16) 0.0539(16) -0.0075(13) 0.0039(13) -0.0236(13) C18 0.0435(15) 0.0383(14) 0.0375(13) -0.0079(10) 0.0021(11) -0.0101(11) C19 0.0537(16) 0.0402(14) 0.0391(14) 0.0068(11) -0.0188(12) -0.0102(12) C20 0.097(3) 0.077(2) 0.0452(17) 0.0104(15) -0.0043(17) -0.0477(18) C21 0.090(3) 0.0453(17) 0.119(3) 0.0034(18) -0.048(2) -0.0005(17) C22 0.071(2) 0.0330(14) 0.0566(17) -0.0035(12) -0.0086(15) -0.0106(13) C23 0.083(2) 0.0451(16) 0.091(2) -0.0228(16) -0.0201(19) 0.0054(16) C24 0.122(3) 0.0539(19) 0.097(3) 0.0184(18) -0.006(2) -0.0347(19) N1 0.0323(10) 0.0289(9) 0.0320(10) -0.0012(8) -0.0045(8) 0.0000(8) N2 0.0343(11) 0.0312(10) 0.0338(10) 0.0002(8) -0.0016(8) -0.0026(8) Ti1 0.0277(3) 0.0222(3) 0.0249(3) 0 -0.0035(2) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 C6 1.399(3) . ? C1 C2 1.412(3) . ? C1 N1 1.414(3) . ? C2 C3 1.394(3) . ? C2 C7 1.512(3) . ? C3 C4 1.378(4) . ? C3 H3 0.95 . ? C4 C5 1.370(4) . ? C4 H4 0.95 . ? C5 C6 1.386(3) . ? C5 H5 0.95 . ? C6 C10 1.521(3) . ? C7 C8 1.533(3) . ? C7 C9 1.537(4) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C12 1.525(4) . ? C10 C11 1.534(4) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 C14 1.403(3) . ? C13 C18 1.406(3) . ? C13 N2 1.412(3) . ? C14 C15 1.385(3) . ? C14 C19 1.517(3) . ? C15 C16 1.376(4) . ? C15 H15 0.95 . ? C16 C17 1.368(4) . ? C16 H16 0.95 . ? C17 C18 1.394(3) . ? C17 H17 0.95 . ? C18 C22 1.521(3) . ? C19 C21 1.521(4) . ? C19 C20 1.526(4) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C23 1.533(4) . ? C22 C24 1.534(4) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? N1 Ti1 1.9028(17) . ? N1 H1A 0.92 . ? N1 H1B 0.92 . ? N2 Ti1 1.8984(17) . ? N2 H2A 0.92 . ? N2 H2B 0.92 . ? Ti1 N2 1.8984(17) 2_756 ? Ti1 N1 1.9028(17) 2_756 ? 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 C6 C1 C2 121.1(2) . . ? C6 C1 N1 119.79(19) . . ? C2 C1 N1 119.1(2) . . ? C3 C2 C1 117.8(2) . . ? C3 C2 C7 121.8(2) . . ? C1 C2 C7 120.4(2) . . ? C4 C3 C2 121.4(2) . . ? C4 C3 H3 119.3 . . ? C2 C3 H3 119.3 . . ? C5 C4 C3 119.7(2) . . ? C5 C4 H4 120.1 . . ? C3 C4 H4 120.1 . . ? C4 C5 C6 121.8(3) . . ? C4 C5 H5 119.1 . . ? C6 C5 H5 119.1 . . ? C5 C6 C1 118.2(2) . . ? C5 C6 C10 119.8(2) . . ? C1 C6 C10 122.0(2) . . ? C2 C7 C8 114.4(2) . . ? C2 C7 C9 111.3(2) . . ? C8 C7 C9 109.0(2) . . ? C2 C7 H7 107.3 . . ? C8 C7 H7 107.3 . . ? C9 C7 H7 107.3 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C12 110.7(2) . . ? C6 C10 C11 112.0(2) . . ? C12 C10 C11 112.1(3) . . ? C6 C10 H10 107.2 . . ? C12 C10 H10 107.2 . . ? C11 C10 H10 107.2 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C14 C13 C18 121.0(2) . . ? C14 C13 N2 118.97(18) . . ? C18 C13 N2 120.0(2) . . ? C15 C14 C13 118.3(2) . . ? C15 C14 C19 119.5(2) . . ? C13 C14 C19 122.0(2) . . ? C16 C15 C14 121.2(2) . . ? C16 C15 H15 119.4 . . ? C14 C15 H15 119.4 . . ? C17 C16 C15 120.1(2) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C16 C17 C18 121.4(2) . . ? C16 C17 H17 119.3 . . ? C18 C17 H17 119.3 . . ? C17 C18 C13 117.9(2) . . ? C17 C18 C22 122.1(2) . . ? C13 C18 C22 120.1(2) . . ? C14 C19 C21 113.5(2) . . ? C14 C19 C20 109.5(2) . . ? C21 C19 C20 112.1(2) . . ? C14 C19 H19 107.1 . . ? C21 C19 H19 107.1 . . ? C20 C19 H19 107.1 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C23 111.3(2) . . ? C18 C22 C24 113.4(3) . . ? C23 C22 C24 110.5(2) . . ? C18 C22 H22 107.1 . . ? C23 C22 H22 107.1 . . ? C24 C22 H22 107.1 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C1 N1 Ti1 137.54(14) . . ? C1 N1 H1A 102.7 . . ? Ti1 N1 H1A 102.7 . . ? C1 N1 H1B 102.7 . . ? Ti1 N1 H1B 102.7 . . ? H1A N1 H1B 105 . . ? C13 N2 Ti1 136.37(14) . . ? C13 N2 H2A 103.1 . . ? Ti1 N2 H2A 103.1 . . ? C13 N2 H2B 103.1 . . ? Ti1 N2 H2B 103.1 . . ? H2A N2 H2B 105.1 . . ? N2 Ti1 N2 105.49(11) . 2_756 ? N2 Ti1 N1 112.74(8) . . ? N2 Ti1 N1 110.04(8) 2_756 . ? N2 Ti1 N1 110.04(8) . 2_756 ? N2 Ti1 N1 112.74(8) 2_756 2_756 ? N1 Ti1 N1 105.92(11) . 2_756 ? _database_code_depnum_ccdc_archive 'CCDC 931106' ####################################################################### # # 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_15 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C50 H73 N7 Ti2' _chemical_formula_sum 'C50 H73 N7 Ti2' _chemical_formula_weight 867.95 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 12.6101(6) _cell_length_b 22.6800(14) _cell_length_c 21.3541(10) _cell_angle_alpha 90 _cell_angle_beta 99.489(5) _cell_angle_gamma 90 _cell_volume 6023.6(5) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 4143 _cell_measurement_theta_min 3.37 _cell_measurement_theta_max 29.1325 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description needle _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.04 _exptl_crystal_density_diffrn 0.957 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1864 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.297 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.9359 _exptl_absorpt_correction_T_max 0.9987 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_measurement_device_type 'Xcalibur, Eos, Gemini ultra' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.1978 _diffrn_orient_matrix_ub_11 0.0437128 _diffrn_orient_matrix_ub_12 0.0053357 _diffrn_orient_matrix_ub_13 0.0248155 _diffrn_orient_matrix_ub_21 0.0240423 _diffrn_orient_matrix_ub_22 -0.0269218 _diffrn_orient_matrix_ub_23 -0.0071386 _diffrn_orient_matrix_ub_31 0.0276221 _diffrn_orient_matrix_ub_32 0.0150007 _diffrn_orient_matrix_ub_33 -0.0216148 _diffrn_reflns_av_R_equivalents 0.1365 _diffrn_reflns_av_unetI/netI 0.179 _diffrn_reflns_number 50674 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 3.38 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 12293 _reflns_number_gt 6025 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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. ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.500 0.200 0.210 1650 341 ' ' _platon_squeeze_details ; ; _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^)+(0.0650P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 12293 _refine_ls_number_parameters 548 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1516 _refine_ls_R_factor_gt 0.0742 _refine_ls_wR_factor_ref 0.1816 _refine_ls_wR_factor_gt 0.1545 _refine_ls_goodness_of_fit_ref 0.918 _refine_ls_restrained_S_all 0.918 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.374 _refine_diff_density_min -0.337 _refine_diff_density_rms 0.073 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.2648(3) 0.12523(17) 0.66723(17) 0.0229(9) Uani 1 1 d . . . C2 C 0.3313(3) 0.15618(19) 0.71685(17) 0.0271(10) Uani 1 1 d . . . C3 C 0.4348(3) 0.1349(2) 0.73904(19) 0.0331(11) Uani 1 1 d . . . H3 H 0.4794 0.1552 0.7723 0.04 Uiso 1 1 calc R . . C4 C 0.4730(3) 0.0855(2) 0.7140(2) 0.0373(11) Uani 1 1 d . . . H4 H 0.5424 0.0708 0.7308 0.045 Uiso 1 1 calc R . . C5 C 0.4112(3) 0.0572(2) 0.66454(19) 0.0365(11) Uani 1 1 d . . . H5 H 0.4399 0.0235 0.6468 0.044 Uiso 1 1 calc R . . C6 C 0.3077(3) 0.07569(19) 0.63907(18) 0.0296(10) Uani 1 1 d . . . C7 C 0.2949(3) 0.2112(2) 0.74594(19) 0.0343(11) Uani 1 1 d . . . H7 H 0.2186 0.219 0.7262 0.041 Uiso 1 1 calc R . . C8 C 0.3631(3) 0.2650(2) 0.7333(2) 0.0431(12) Uani 1 1 d . . . H8A H 0.4368 0.26 0.7559 0.065 Uiso 1 1 calc R . . H8B H 0.332 0.3008 0.7484 0.065 Uiso 1 1 calc R . . H8C H 0.3639 0.2684 0.6877 0.065 Uiso 1 1 calc R . . C9 C 0.2991(4) 0.2040(2) 0.8176(2) 0.0575(15) Uani 1 1 d . . . H9A H 0.2494 0.1727 0.8256 0.086 Uiso 1 1 calc R . . H9B H 0.2782 0.2411 0.8356 0.086 Uiso 1 1 calc R . . H9C H 0.3723 0.1935 0.8374 0.086 Uiso 1 1 calc R . . C10 C 0.2469(3) 0.0446(2) 0.58127(19) 0.0344(11) Uani 1 1 d . . . H10 H 0.1735 0.0624 0.5714 0.041 Uiso 1 1 calc R . . C11 C 0.3036(4) 0.0543(2) 0.5237(2) 0.0509(14) Uani 1 1 d . . . H11A H 0.3177 0.0965 0.5193 0.076 Uiso 1 1 calc R . . H11B H 0.2575 0.0401 0.4853 0.076 Uiso 1 1 calc R . . H11C H 0.3717 0.0326 0.5299 0.076 Uiso 1 1 calc R . . C12 C 0.2338(4) -0.0212(2) 0.5936(2) 0.0492(13) Uani 1 1 d . . . H12A H 0.3046 -0.0402 0.6005 0.074 Uiso 1 1 calc R . . H12B H 0.1884 -0.0392 0.5569 0.074 Uiso 1 1 calc R . . H12C H 0.2 -0.0264 0.6314 0.074 Uiso 1 1 calc R . . C13 C -0.1307(3) 0.19847(18) 0.68195(18) 0.0267(9) Uani 1 1 d . . . C14 C -0.1189(3) 0.23980(19) 0.73225(19) 0.0320(10) Uani 1 1 d . . . C15 C -0.2096(3) 0.2565(2) 0.7570(2) 0.0429(12) Uani 1 1 d . . . H15 H -0.2024 0.2848 0.7902 0.051 Uiso 1 1 calc R . . C16 C -0.3091(4) 0.2334(2) 0.7349(2) 0.0516(14) Uani 1 1 d . . . H16 H -0.3695 0.2448 0.7535 0.062 Uiso 1 1 calc R . . C17 C -0.3208(3) 0.1935(2) 0.6857(2) 0.0436(12) Uani 1 1 d . . . H17 H -0.3901 0.178 0.6699 0.052 Uiso 1 1 calc R . . C18 C -0.2333(3) 0.17555(19) 0.65857(19) 0.0317(10) Uani 1 1 d . . . C19 C -0.0117(3) 0.26529(19) 0.76324(19) 0.0322(10) Uani 1 1 d . . . H19 H 0.0424 0.2567 0.7351 0.039 Uiso 1 1 calc R . . C20 C -0.0159(4) 0.3317(2) 0.7721(2) 0.0487(13) Uani 1 1 d . . . H20A H -0.0639 0.341 0.8024 0.073 Uiso 1 1 calc R . . H20B H -0.0428 0.3505 0.7312 0.073 Uiso 1 1 calc R . . H20C H 0.0565 0.3465 0.7884 0.073 Uiso 1 1 calc R . . C21 C 0.0277(4) 0.2372(2) 0.8279(2) 0.0481(13) Uani 1 1 d . . . H21A H 0.0932 0.2573 0.8484 0.072 Uiso 1 1 calc R . . H21B H 0.0433 0.1954 0.8223 0.072 Uiso 1 1 calc R . . H21C H -0.028 0.2409 0.8547 0.072 Uiso 1 1 calc R . . C22 C -0.2514(3) 0.1290(2) 0.60648(19) 0.0355(11) Uani 1 1 d . . . H22 H -0.184 0.1252 0.5878 0.043 Uiso 1 1 calc R . . C23 C -0.3434(4) 0.1450(3) 0.5532(2) 0.0583(15) Uani 1 1 d . . . H23A H -0.412 0.1416 0.5688 0.087 Uiso 1 1 calc R . . H23B H -0.3431 0.1181 0.5173 0.087 Uiso 1 1 calc R . . H23C H -0.334 0.1856 0.5394 0.087 Uiso 1 1 calc R . . C24 C -0.2769(4) 0.0681(2) 0.6336(2) 0.0533(14) Uani 1 1 d . . . H24A H -0.219 0.0571 0.668 0.08 Uiso 1 1 calc R . . H24B H -0.2829 0.0384 0.5998 0.08 Uiso 1 1 calc R . . H24C H -0.3449 0.0704 0.6499 0.08 Uiso 1 1 calc R . . C25 C 0.1680(3) 0.28391(19) 0.50952(18) 0.0317(10) Uani 1 1 d . . . H25 H 0.0948 0.2958 0.5014 0.038 Uiso 1 1 calc R . . C26 C 0.2370(4) 0.3082(2) 0.47305(19) 0.0372(11) Uani 1 1 d . . . H26 H 0.2122 0.337 0.4417 0.045 Uiso 1 1 calc R . . C27 C 0.3409(4) 0.2905(2) 0.4827(2) 0.0442(13) Uani 1 1 d . . . H27 H 0.3901 0.3065 0.458 0.053 Uiso 1 1 calc R . . C28 C 0.3745(4) 0.2487(2) 0.52912(19) 0.0394(12) Uani 1 1 d . . . H28 H 0.4468 0.2352 0.5365 0.047 Uiso 1 1 calc R . . C29 C 0.3006(3) 0.2272(2) 0.56425(18) 0.0323(10) Uani 1 1 d . . . H29 H 0.3237 0.1986 0.5961 0.039 Uiso 1 1 calc R . . C30 C -0.0605(3) 0.3206(2) 0.59812(19) 0.0334(11) Uani 1 1 d . . . H30 H -0.1186 0.2949 0.5832 0.04 Uiso 1 1 calc R . . C31 C -0.0806(4) 0.3801(2) 0.5990(2) 0.0406(12) Uani 1 1 d . . . H31 H -0.1501 0.3951 0.583 0.049 Uiso 1 1 calc R . . C32 C 0.0020(4) 0.4174(2) 0.6234(2) 0.0431(12) Uani 1 1 d . . . H32 H -0.0097 0.4588 0.625 0.052 Uiso 1 1 calc R . . C33 C 0.1014(4) 0.3940(2) 0.6454(2) 0.0382(11) Uani 1 1 d . . . H33 H 0.1593 0.4188 0.6633 0.046 Uiso 1 1 calc R . . C34 C 0.1161(3) 0.3345(2) 0.64118(19) 0.0339(11) Uani 1 1 d . . . H34 H 0.1857 0.3189 0.6559 0.041 Uiso 1 1 calc R . . C35 C 0.0778(3) 0.07429(17) 0.83501(17) 0.0259(9) Uani 1 1 d . . . C36 C 0.1771(3) 0.04832(18) 0.86255(17) 0.0278(10) Uani 1 1 d . . . C37 C 0.1933(4) 0.03305(19) 0.92639(18) 0.0352(11) Uani 1 1 d . . . H37 H 0.2593 0.0152 0.9447 0.042 Uiso 1 1 calc R . . C38 C 0.1158(4) 0.0433(2) 0.96386(19) 0.0395(12) Uani 1 1 d . . . H38 H 0.129 0.0333 1.0077 0.047 Uiso 1 1 calc R . . C39 C 0.0188(4) 0.0681(2) 0.93700(19) 0.0389(12) Uani 1 1 d . . . H39 H -0.0347 0.0747 0.9628 0.047 Uiso 1 1 calc R . . C40 C -0.0025(3) 0.08362(19) 0.87372(18) 0.0301(10) Uani 1 1 d . . . C41 C 0.2624(3) 0.0346(2) 0.82172(19) 0.0354(11) Uani 1 1 d . . . H41 H 0.2554 0.0651 0.7874 0.042 Uiso 1 1 calc R . . C42 C 0.3777(3) 0.0379(2) 0.8574(2) 0.0536(14) Uani 1 1 d . . . H42A H 0.3914 0.0774 0.8757 0.08 Uiso 1 1 calc R . . H42B H 0.4279 0.0299 0.828 0.08 Uiso 1 1 calc R . . H42C H 0.3877 0.0085 0.8915 0.08 Uiso 1 1 calc R . . C43 C 0.2415(4) -0.0254(2) 0.7893(2) 0.0562(15) Uani 1 1 d . . . H43A H 0.2536 -0.0567 0.8213 0.084 Uiso 1 1 calc R . . H43B H 0.2905 -0.0308 0.7586 0.084 Uiso 1 1 calc R . . H43C H 0.167 -0.0271 0.7672 0.084 Uiso 1 1 calc R . . C44 C -0.1130(4) 0.1054(2) 0.8439(2) 0.0399(12) Uani 1 1 d . . . H44 H -0.1036 0.1323 0.8081 0.048 Uiso 1 1 calc R . . C45 C -0.1836(4) 0.0544(3) 0.8162(2) 0.0577(15) Uani 1 1 d . . . H45A H -0.1471 0.0323 0.7865 0.087 Uiso 1 1 calc R . . H45B H -0.2521 0.0697 0.7938 0.087 Uiso 1 1 calc R . . H45C H -0.1971 0.0282 0.8506 0.087 Uiso 1 1 calc R . . C46 C -0.1709(4) 0.1402(3) 0.8895(2) 0.0677(17) Uani 1 1 d . . . H46A H -0.1892 0.1137 0.9224 0.102 Uiso 1 1 calc R . . H46B H -0.2368 0.1575 0.866 0.102 Uiso 1 1 calc R . . H46C H -0.1238 0.1717 0.9094 0.102 Uiso 1 1 calc R . . C47 C -0.0380(3) 0.0319(2) 0.57911(18) 0.0374(11) Uani 1 1 d . . . H47A H 0.007 0.0023 0.5628 0.056 Uiso 1 1 calc R . . H47B H -0.0254 0.0705 0.5612 0.056 Uiso 1 1 calc R . . H47C H -0.1139 0.0212 0.567 0.056 Uiso 1 1 calc R . . C48 C -0.0318(4) -0.0222(2) 0.6753(2) 0.0450(12) Uani 1 1 d . . . H48A H -0.1076 -0.0326 0.662 0.067 Uiso 1 1 calc R . . H48B H -0.0158 -0.02 0.7217 0.067 Uiso 1 1 calc R . . H48C H 0.0137 -0.0523 0.6602 0.067 Uiso 1 1 calc R . . C49 C -0.1126(3) 0.1882(2) 0.4913(2) 0.0461(13) Uani 1 1 d . . . H49A H -0.119 0.2127 0.453 0.069 Uiso 1 1 calc R . . H49B H -0.1507 0.2071 0.5224 0.069 Uiso 1 1 calc R . . H49C H -0.1442 0.1493 0.4802 0.069 Uiso 1 1 calc R . . C50 C 0.0572(4) 0.1514(2) 0.47360(19) 0.0452(13) Uani 1 1 d . . . H50A H 0.0271 0.1119 0.4649 0.068 Uiso 1 1 calc R . . H50B H 0.1336 0.1482 0.4918 0.068 Uiso 1 1 calc R . . H50C H 0.0493 0.1739 0.434 0.068 Uiso 1 1 calc R . . N1 N 0.1591(2) 0.14474(15) 0.64539(14) 0.0259(8) Uani 1 1 d . . . N2 N -0.0388(2) 0.18095(14) 0.65599(14) 0.0227(8) Uani 1 1 d . . . N3 N 0.1978(3) 0.24454(15) 0.55566(14) 0.0281(8) Uani 1 1 d . . . N4 N 0.0375(2) 0.29689(15) 0.61738(14) 0.0257(8) Uani 1 1 d . . . N5 N 0.0608(2) 0.09115(14) 0.77195(14) 0.0258(8) Uani 1 1 d . . . N6 N -0.0107(2) 0.03448(15) 0.64850(14) 0.0279(8) Uani 1 1 d . . . N7 N 0.0003(3) 0.18140(15) 0.51844(14) 0.0303(8) Uani 1 1 d . . . Ti1 Ti 0.04284(5) 0.10625(3) 0.69015(3) 0.02304(19) Uani 1 1 d . . . Ti2 Ti 0.06311(5) 0.20021(3) 0.60447(3) 0.02267(19) 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 C1 0.027(2) 0.019(2) 0.024(2) 0.0049(17) 0.0083(17) -0.0016(19) C2 0.029(2) 0.031(3) 0.021(2) 0.0001(18) 0.0040(17) -0.005(2) C3 0.025(2) 0.040(3) 0.032(2) 0.000(2) -0.0007(19) -0.005(2) C4 0.026(2) 0.047(3) 0.038(3) 0.006(2) 0.001(2) 0.006(2) C5 0.034(2) 0.037(3) 0.040(3) 0.003(2) 0.011(2) 0.014(2) C6 0.034(2) 0.022(3) 0.033(2) 0.0038(19) 0.0066(19) -0.001(2) C7 0.027(2) 0.037(3) 0.038(3) -0.010(2) 0.0019(19) -0.006(2) C8 0.045(3) 0.035(3) 0.047(3) -0.003(2) 0.002(2) 0.000(2) C9 0.079(4) 0.053(4) 0.047(3) -0.020(3) 0.031(3) -0.010(3) C10 0.036(2) 0.027(3) 0.041(3) -0.011(2) 0.008(2) 0.002(2) C11 0.063(3) 0.056(4) 0.034(3) -0.010(2) 0.008(2) -0.002(3) C12 0.056(3) 0.033(3) 0.056(3) -0.009(2) -0.001(2) -0.001(3) C13 0.034(2) 0.017(2) 0.032(2) 0.0052(18) 0.0115(18) 0.003(2) C14 0.043(3) 0.020(3) 0.036(2) -0.0005(19) 0.014(2) 0.000(2) C15 0.038(3) 0.045(3) 0.049(3) -0.011(2) 0.019(2) -0.002(3) C16 0.043(3) 0.051(4) 0.066(3) -0.007(3) 0.026(3) 0.010(3) C17 0.029(2) 0.046(3) 0.057(3) -0.002(3) 0.009(2) -0.001(2) C18 0.034(2) 0.029(3) 0.033(2) 0.003(2) 0.010(2) 0.001(2) C19 0.036(2) 0.029(3) 0.034(2) -0.004(2) 0.0123(19) 0.000(2) C20 0.072(3) 0.032(3) 0.045(3) -0.011(2) 0.020(3) -0.008(3) C21 0.057(3) 0.044(3) 0.042(3) -0.005(2) 0.004(2) -0.002(3) C22 0.033(2) 0.037(3) 0.036(2) -0.002(2) 0.007(2) 0.003(2) C23 0.040(3) 0.080(5) 0.052(3) -0.006(3) -0.002(2) 0.002(3) C24 0.061(3) 0.034(3) 0.070(3) -0.006(3) 0.026(3) -0.014(3) C25 0.035(2) 0.027(3) 0.034(2) 0.006(2) 0.009(2) 0.006(2) C26 0.055(3) 0.027(3) 0.032(2) 0.007(2) 0.014(2) -0.002(2) C27 0.052(3) 0.050(4) 0.034(3) -0.001(2) 0.020(2) -0.021(3) C28 0.039(3) 0.048(3) 0.033(3) 0.003(2) 0.011(2) -0.009(2) C29 0.041(3) 0.031(3) 0.025(2) -0.0018(19) 0.0054(19) -0.004(2) C30 0.035(2) 0.028(3) 0.038(3) -0.003(2) 0.006(2) -0.004(2) C31 0.036(3) 0.033(3) 0.050(3) 0.001(2) 0.002(2) 0.008(2) C32 0.059(3) 0.022(3) 0.050(3) 0.003(2) 0.014(2) 0.009(3) C33 0.048(3) 0.023(3) 0.045(3) -0.008(2) 0.011(2) -0.004(2) C34 0.028(2) 0.033(3) 0.041(3) 0.000(2) 0.007(2) 0.001(2) C35 0.039(2) 0.018(2) 0.021(2) 0.0009(17) 0.0053(18) -0.005(2) C36 0.039(2) 0.021(2) 0.023(2) -0.0012(17) 0.0030(18) -0.005(2) C37 0.045(3) 0.032(3) 0.027(2) 0.0035(19) 0.000(2) -0.010(2) C38 0.067(3) 0.034(3) 0.018(2) -0.0008(19) 0.007(2) -0.014(3) C39 0.057(3) 0.035(3) 0.027(2) -0.004(2) 0.017(2) -0.006(3) C40 0.044(3) 0.025(3) 0.024(2) 0.0013(18) 0.0118(19) -0.001(2) C41 0.041(3) 0.034(3) 0.032(2) 0.011(2) 0.007(2) 0.002(2) C42 0.040(3) 0.071(4) 0.049(3) 0.023(3) 0.003(2) 0.001(3) C43 0.067(3) 0.054(4) 0.051(3) -0.006(3) 0.021(3) 0.009(3) C44 0.054(3) 0.032(3) 0.039(3) 0.009(2) 0.025(2) 0.008(3) C45 0.041(3) 0.065(4) 0.064(3) 0.000(3) 0.004(3) 0.003(3) C46 0.082(4) 0.066(4) 0.068(4) 0.015(3) 0.048(3) 0.034(3) C47 0.042(3) 0.035(3) 0.032(2) -0.010(2) -0.004(2) -0.006(2) C48 0.060(3) 0.028(3) 0.047(3) 0.004(2) 0.009(2) -0.008(3) C49 0.046(3) 0.047(3) 0.040(3) 0.013(2) -0.010(2) -0.003(3) C50 0.071(3) 0.041(3) 0.024(2) -0.001(2) 0.007(2) -0.004(3) N1 0.0277(18) 0.027(2) 0.0215(17) 0.0005(15) 0.0005(14) 0.0013(17) N2 0.0231(17) 0.0184(19) 0.0263(17) -0.0015(14) 0.0036(14) -0.0001(15) N3 0.033(2) 0.024(2) 0.0292(19) 0.0043(15) 0.0091(15) 0.0037(17) N4 0.0229(17) 0.025(2) 0.0294(18) 0.0053(15) 0.0056(14) 0.0052(17) N5 0.0366(19) 0.019(2) 0.0209(17) 0.0057(14) 0.0026(14) -0.0012(16) N6 0.0345(19) 0.022(2) 0.0279(19) 0.0001(15) 0.0059(15) -0.0033(17) N7 0.038(2) 0.028(2) 0.0236(18) 0.0074(15) 0.0011(15) 0.0019(18) Ti1 0.0309(4) 0.0185(4) 0.0196(4) 0.0015(3) 0.0040(3) -0.0007(4) Ti2 0.0275(4) 0.0184(4) 0.0219(4) 0.0013(3) 0.0037(3) -0.0005(4) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 N1 1.409(5) . ? C1 C6 1.423(6) . ? C1 C2 1.423(5) . ? C2 C3 1.400(5) . ? C2 C7 1.499(6) . ? C3 C4 1.363(6) . ? C3 H3 0.95 . ? C4 C5 1.365(6) . ? C4 H4 0.95 . ? C5 C6 1.393(5) . ? C5 H5 0.95 . ? C6 C10 1.516(5) . ? C7 C9 1.531(6) . ? C7 C8 1.542(6) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C12 1.529(6) . ? C10 C11 1.536(6) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 C18 1.407(5) . ? C13 C14 1.415(5) . ? C13 N2 1.422(5) . ? C14 C15 1.390(5) . ? C14 C19 1.518(6) . ? C15 C16 1.370(6) . ? C15 H15 0.95 . ? C16 C17 1.378(6) . ? C16 H16 0.95 . ? C17 C18 1.389(6) . ? C17 H17 0.95 . ? C18 C22 1.524(6) . ? C19 C20 1.521(6) . ? C19 C21 1.528(6) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C23 1.528(6) . ? C22 C24 1.550(6) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? C25 N3 1.337(5) . ? C25 C26 1.375(5) . ? C25 H25 0.95 . ? C26 C27 1.353(6) . ? C26 H26 0.95 . ? C27 C28 1.387(6) . ? C27 H27 0.95 . ? C28 C29 1.379(5) . ? C28 H28 0.95 . ? C29 N3 1.338(5) . ? C29 H29 0.95 . ? C30 N4 1.348(5) . ? C30 C31 1.372(6) . ? C30 H30 0.95 . ? C31 C32 1.377(6) . ? C31 H31 0.95 . ? C32 C33 1.372(6) . ? C32 H32 0.95 . ? C33 C34 1.368(6) . ? C33 H33 0.95 . ? C34 N4 1.342(5) . ? C34 H34 0.95 . ? C35 N5 1.382(4) . ? C35 C36 1.420(5) . ? C35 C40 1.425(5) . ? C36 C37 1.389(5) . ? C36 C41 1.524(5) . ? C37 C38 1.381(6) . ? C37 H37 0.95 . ? C38 C39 1.382(6) . ? C38 H38 0.95 . ? C39 C40 1.379(5) . ? C39 H39 0.95 . ? C40 C44 1.516(6) . ? C41 C42 1.529(6) . ? C41 C43 1.530(6) . ? C41 H41 1 . ? C42 H42A 0.98 . ? C42 H42B 0.98 . ? C42 H42C 0.98 . ? C43 H43A 0.98 . ? C43 H43B 0.98 . ? C43 H43C 0.98 . ? C44 C45 1.520(6) . ? C44 C46 1.529(6) . ? C44 H44 1 . ? C45 H45A 0.98 . ? C45 H45B 0.98 . ? C45 H45C 0.98 . ? C46 H46A 0.98 . ? C46 H46B 0.98 . ? C46 H46C 0.98 . ? C47 N6 1.466(5) . ? C47 H47A 0.98 . ? C47 H47B 0.98 . ? C47 H47C 0.98 . ? C48 N6 1.449(5) . ? C48 H48A 0.98 . ? C48 H48B 0.98 . ? C48 H48C 0.98 . ? C49 N7 1.454(5) . ? C49 H49A 0.98 . ? C49 H49B 0.98 . ? C49 H49C 0.98 . ? C50 N7 1.457(5) . ? C50 H50A 0.98 . ? C50 H50B 0.98 . ? C50 H50C 0.98 . ? N1 Ti2 1.861(3) . ? N1 Ti1 2.070(3) . ? N2 Ti2 1.876(3) . ? N2 Ti1 2.053(3) . ? N3 Ti2 2.359(3) . ? N4 Ti2 2.240(3) . ? N5 Ti1 1.758(3) . ? N6 Ti1 1.923(3) . ? N7 Ti2 1.925(3) . ? Ti1 Ti2 2.8475(10) . ? 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 C1 C6 120.9(3) . . ? N1 C1 C2 120.0(3) . . ? C6 C1 C2 119.1(3) . . ? C3 C2 C1 118.9(4) . . ? C3 C2 C7 118.7(4) . . ? C1 C2 C7 122.4(4) . . ? C4 C3 C2 121.4(4) . . ? C4 C3 H3 119.3 . . ? C2 C3 H3 119.3 . . ? C3 C4 C5 119.8(4) . . ? C3 C4 H4 120.1 . . ? C5 C4 H4 120.1 . . ? C4 C5 C6 122.6(4) . . ? C4 C5 H5 118.7 . . ? C6 C5 H5 118.7 . . ? C5 C6 C1 118.0(4) . . ? C5 C6 C10 119.6(4) . . ? C1 C6 C10 122.4(4) . . ? C2 C7 C9 111.3(4) . . ? C2 C7 C8 111.6(3) . . ? C9 C7 C8 109.3(4) . . ? C2 C7 H7 108.2 . . ? C9 C7 H7 108.2 . . ? C8 C7 H7 108.2 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C12 111.6(4) . . ? C6 C10 C11 110.1(3) . . ? C12 C10 C11 110.9(4) . . ? C6 C10 H10 108 . . ? C12 C10 H10 108 . . ? C11 C10 H10 108 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C18 C13 C14 119.3(4) . . ? C18 C13 N2 121.3(4) . . ? C14 C13 N2 119.4(4) . . ? C15 C14 C13 118.6(4) . . ? C15 C14 C19 117.4(4) . . ? C13 C14 C19 123.9(4) . . ? C16 C15 C14 122.0(4) . . ? C16 C15 H15 119 . . ? C14 C15 H15 119 . . ? C15 C16 C17 119.4(4) . . ? C15 C16 H16 120.3 . . ? C17 C16 H16 120.3 . . ? C16 C17 C18 121.2(4) . . ? C16 C17 H17 119.4 . . ? C18 C17 H17 119.4 . . ? C17 C18 C13 119.4(4) . . ? C17 C18 C22 118.3(4) . . ? C13 C18 C22 122.2(4) . . ? C14 C19 C20 112.6(4) . . ? C14 C19 C21 111.6(4) . . ? C20 C19 C21 108.2(4) . . ? C14 C19 H19 108.1 . . ? C20 C19 H19 108.1 . . ? C21 C19 H19 108.1 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C23 112.5(4) . . ? C18 C22 C24 111.1(4) . . ? C23 C22 C24 108.1(4) . . ? C18 C22 H22 108.3 . . ? C23 C22 H22 108.3 . . ? C24 C22 H22 108.3 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? N3 C25 C26 123.9(4) . . ? N3 C25 H25 118 . . ? C26 C25 H25 118 . . ? C27 C26 C25 118.8(4) . . ? C27 C26 H26 120.6 . . ? C25 C26 H26 120.6 . . ? C26 C27 C28 119.1(4) . . ? C26 C27 H27 120.5 . . ? C28 C27 H27 120.5 . . ? C29 C28 C27 118.5(4) . . ? C29 C28 H28 120.8 . . ? C27 C28 H28 120.8 . . ? N3 C29 C28 123.2(4) . . ? N3 C29 H29 118.4 . . ? C28 C29 H29 118.4 . . ? N4 C30 C31 123.4(4) . . ? N4 C30 H30 118.3 . . ? C31 C30 H30 118.3 . . ? C30 C31 C32 118.7(4) . . ? C30 C31 H31 120.7 . . ? C32 C31 H31 120.7 . . ? C33 C32 C31 118.9(4) . . ? C33 C32 H32 120.6 . . ? C31 C32 H32 120.6 . . ? C34 C33 C32 119.1(4) . . ? C34 C33 H33 120.5 . . ? C32 C33 H33 120.5 . . ? N4 C34 C33 123.5(4) . . ? N4 C34 H34 118.2 . . ? C33 C34 H34 118.2 . . ? N5 C35 C36 120.2(3) . . ? N5 C35 C40 120.9(4) . . ? C36 C35 C40 118.9(3) . . ? C37 C36 C35 119.2(4) . . ? C37 C36 C41 120.5(4) . . ? C35 C36 C41 120.3(3) . . ? C38 C37 C36 121.5(4) . . ? C38 C37 H37 119.2 . . ? C36 C37 H37 119.2 . . ? C37 C38 C39 119.4(4) . . ? C37 C38 H38 120.3 . . ? C39 C38 H38 120.3 . . ? C40 C39 C38 121.8(4) . . ? C40 C39 H39 119.1 . . ? C38 C39 H39 119.1 . . ? C39 C40 C35 119.2(4) . . ? C39 C40 C44 120.7(4) . . ? C35 C40 C44 119.8(3) . . ? C36 C41 C42 114.1(4) . . ? C36 C41 C43 110.8(4) . . ? C42 C41 C43 110.3(4) . . ? C36 C41 H41 107.1 . . ? C42 C41 H41 107.1 . . ? C43 C41 H41 107.1 . . ? C41 C42 H42A 109.5 . . ? C41 C42 H42B 109.5 . . ? H42A C42 H42B 109.5 . . ? C41 C42 H42C 109.5 . . ? H42A C42 H42C 109.5 . . ? H42B C42 H42C 109.5 . . ? C41 C43 H43A 109.5 . . ? C41 C43 H43B 109.5 . . ? H43A C43 H43B 109.5 . . ? C41 C43 H43C 109.5 . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? C40 C44 C45 110.7(4) . . ? C40 C44 C46 113.8(4) . . ? C45 C44 C46 109.3(4) . . ? C40 C44 H44 107.6 . . ? C45 C44 H44 107.6 . . ? C46 C44 H44 107.6 . . ? C44 C45 H45A 109.5 . . ? C44 C45 H45B 109.5 . . ? H45A C45 H45B 109.5 . . ? C44 C45 H45C 109.5 . . ? H45A C45 H45C 109.5 . . ? H45B C45 H45C 109.5 . . ? C44 C46 H46A 109.5 . . ? C44 C46 H46B 109.5 . . ? H46A C46 H46B 109.5 . . ? C44 C46 H46C 109.5 . . ? H46A C46 H46C 109.5 . . ? H46B C46 H46C 109.5 . . ? N6 C47 H47A 109.5 . . ? N6 C47 H47B 109.5 . . ? H47A C47 H47B 109.5 . . ? N6 C47 H47C 109.5 . . ? H47A C47 H47C 109.5 . . ? H47B C47 H47C 109.5 . . ? N6 C48 H48A 109.5 . . ? N6 C48 H48B 109.5 . . ? H48A C48 H48B 109.5 . . ? N6 C48 H48C 109.5 . . ? H48A C48 H48C 109.5 . . ? H48B C48 H48C 109.5 . . ? N7 C49 H49A 109.5 . . ? N7 C49 H49B 109.5 . . ? H49A C49 H49B 109.5 . . ? N7 C49 H49C 109.5 . . ? H49A C49 H49C 109.5 . . ? H49B C49 H49C 109.5 . . ? N7 C50 H50A 109.5 . . ? N7 C50 H50B 109.5 . . ? H50A C50 H50B 109.5 . . ? N7 C50 H50C 109.5 . . ? H50A C50 H50C 109.5 . . ? H50B C50 H50C 109.5 . . ? C1 N1 Ti2 151.0(3) . . ? C1 N1 Ti1 114.7(2) . . ? Ti2 N1 Ti1 92.67(13) . . ? C13 N2 Ti2 147.7(3) . . ? C13 N2 Ti1 119.0(2) . . ? Ti2 N2 Ti1 92.80(13) . . ? C25 N3 C29 116.5(3) . . ? C25 N3 Ti2 118.4(3) . . ? C29 N3 Ti2 124.5(3) . . ? C34 N4 C30 116.4(4) . . ? C34 N4 Ti2 123.8(3) . . ? C30 N4 Ti2 119.8(3) . . ? C35 N5 Ti1 174.9(3) . . ? C48 N6 C47 109.6(3) . . ? C48 N6 Ti1 129.9(3) . . ? C47 N6 Ti1 120.5(3) . . ? C49 N7 C50 110.1(3) . . ? C49 N7 Ti2 125.4(3) . . ? C50 N7 Ti2 124.1(3) . . ? N5 Ti1 N6 105.81(14) . . ? N5 Ti1 N2 119.25(14) . . ? N6 Ti1 N2 114.65(13) . . ? N5 Ti1 N1 123.79(14) . . ? N6 Ti1 N1 111.39(13) . . ? N2 Ti1 N1 80.77(12) . . ? N5 Ti1 Ti2 140.70(11) . . ? N6 Ti1 Ti2 113.47(10) . . ? N2 Ti1 Ti2 41.14(8) . . ? N1 Ti1 Ti2 40.75(9) . . ? N1 Ti2 N2 91.29(13) . . ? N1 Ti2 N7 115.58(14) . . ? N2 Ti2 N7 107.12(14) . . ? N1 Ti2 N4 134.41(13) . . ? N2 Ti2 N4 91.67(13) . . ? N7 Ti2 N4 106.83(13) . . ? N1 Ti2 N3 92.04(13) . . ? N2 Ti2 N3 166.18(13) . . ? N7 Ti2 N3 83.45(13) . . ? N4 Ti2 N3 76.47(11) . . ? N1 Ti2 Ti1 46.58(10) . . ? N2 Ti2 Ti1 46.06(10) . . ? N7 Ti2 Ti1 112.39(11) . . ? N4 Ti2 Ti1 128.57(8) . . ? N3 Ti2 Ti1 138.61(9) . . ? _database_code_depnum_ccdc_archive 'CCDC 931107' ####################################################################### # # 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_16 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C36 H51 N5 Ti, C7 H8' _chemical_formula_sum 'C43 H59 N5 Ti' _chemical_formula_weight 693.85 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration unk #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 c 1' _symmetry_space_group_name_Hall 'C -2yc' _symmetry_Int_Tables_number 9 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, z+1/2' 'x+1/2, y+1/2, z' 'x+1/2, -y+1/2, z+1/2' _cell_length_a 14.4789(10) _cell_length_b 15.7622(10) _cell_length_c 18.8740(10) _cell_angle_alpha 90 _cell_angle_beta 110.076(2) _cell_angle_gamma 90 _cell_volume 4045.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 8402 _cell_measurement_theta_min 2.53 _cell_measurement_theta_max 27.74 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.03 _exptl_crystal_density_diffrn 1.139 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1496 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.246 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.852 _exptl_absorpt_correction_T_max 0.981 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0338 _diffrn_reflns_av_unetI/netI 0.0546 _diffrn_reflns_number 30095 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 30 _diffrn_reflns_theta_full 30 _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _reflns_number_total 11376 _reflns_number_gt 9292 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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^)+(0.0456P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 11376 _refine_ls_number_parameters 454 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0601 _refine_ls_R_factor_gt 0.0407 _refine_ls_wR_factor_ref 0.0907 _refine_ls_wR_factor_gt 0.0836 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.016 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.114(14) _refine_diff_density_max 0.244 _refine_diff_density_min -0.203 _refine_diff_density_rms 0.044 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.75964(12) 0.78281(11) 0.91095(8) 0.0197(3) Uani 1 1 d . . . C2 C 0.78850(13) 0.86428(11) 0.94480(9) 0.0237(4) Uani 1 1 d . . . C3 C 0.76862(15) 0.88508(12) 1.01000(10) 0.0309(4) Uani 1 1 d . . . H3 H 0.7899 0.9385 1.0332 0.037 Uiso 1 1 calc R . . C5 C 0.68752(15) 0.75396(13) 1.00769(10) 0.0311(4) Uani 1 1 d . . . H5 H 0.6524 0.7169 1.029 0.037 Uiso 1 1 calc R . . C6 C 0.70535(13) 0.72880(11) 0.94268(9) 0.0233(4) Uani 1 1 d . . . C7 C 0.84356(16) 0.92726(11) 0.91338(10) 0.0311(4) Uani 1 1 d . . . H7 H 0.8397 0.9071 0.8622 0.037 Uiso 1 1 calc R . . C08 C 0.71926(15) 0.83094(13) 1.04189(10) 0.0339(4) Uani 1 1 d . . . H08 H 0.7073 0.8464 1.0866 0.041 Uiso 1 1 calc R . . C8 C 0.8003(2) 1.01671(13) 0.90486(14) 0.0471(6) Uani 1 1 d . . . H8A H 0.7304 1.0146 0.8738 0.071 Uiso 1 1 calc R . . H8B H 0.8352 1.0533 0.8805 0.071 Uiso 1 1 calc R . . H8C H 0.8074 1.0395 0.9548 0.071 Uiso 1 1 calc R . . C9 C 0.95157(18) 0.92960(18) 0.96308(16) 0.0585(7) Uani 1 1 d . . . H9A H 0.9575 0.9514 1.0131 0.088 Uiso 1 1 calc R . . H9B H 0.9877 0.9667 0.9401 0.088 Uiso 1 1 calc R . . H9C H 0.979 0.8722 0.9681 0.088 Uiso 1 1 calc R . . C10 C 0.66662(15) 0.64363(12) 0.90796(10) 0.0308(4) Uani 1 1 d . . . H10 H 0.6825 0.6387 0.8606 0.037 Uiso 1 1 calc R . . C11 C 0.7168(2) 0.56972(14) 0.95833(13) 0.0530(6) Uani 1 1 d . . . H11A H 0.7882 0.5745 0.9713 0.08 Uiso 1 1 calc R . . H11B H 0.6941 0.5162 0.9316 0.08 Uiso 1 1 calc R . . H11C H 0.7003 0.5708 1.0046 0.08 Uiso 1 1 calc R . . C12 C 0.55473(17) 0.63838(18) 0.88528(14) 0.0532(7) Uani 1 1 d . . . H12A H 0.5313 0.5861 0.8567 0.08 Uiso 1 1 calc R . . H12B H 0.5247 0.6874 0.8539 0.08 Uiso 1 1 calc R . . H12C H 0.5365 0.6383 0.9307 0.08 Uiso 1 1 calc R . . C13 C 0.87560(12) 0.75804(10) 0.66990(8) 0.0187(3) Uani 1 1 d . . . C14 C 0.94398(13) 0.71209(11) 0.64648(9) 0.0230(4) Uani 1 1 d . . . C15 C 0.99740(14) 0.75410(12) 0.60812(11) 0.0288(4) Uani 1 1 d . . . H15 H 1.0431 0.723 0.5923 0.035 Uiso 1 1 calc R . . C16 C 0.98557(15) 0.83995(12) 0.59253(10) 0.0307(4) Uani 1 1 d . . . H16 H 1.0222 0.8675 0.566 0.037 Uiso 1 1 calc R . . C17 C 0.91932(13) 0.88504(11) 0.61635(9) 0.0251(4) Uani 1 1 d . . . H17 H 0.9111 0.944 0.6057 0.03 Uiso 1 1 calc R . . C18 C 0.86479(13) 0.84694(10) 0.65505(9) 0.0201(3) Uani 1 1 d . . . C19 C 0.95961(14) 0.61725(11) 0.66136(10) 0.0281(4) Uani 1 1 d . . . H19 H 0.9147 0.5982 0.6884 0.034 Uiso 1 1 calc R . . C20 C 0.9324(2) 0.56782(13) 0.58695(13) 0.0484(6) Uani 1 1 d . . . H20A H 0.8632 0.5781 0.5571 0.073 Uiso 1 1 calc R . . H20B H 0.9427 0.507 0.5977 0.073 Uiso 1 1 calc R . . H20C H 0.9739 0.5868 0.5585 0.073 Uiso 1 1 calc R . . C21 C 1.06466(16) 0.59706(14) 0.71146(13) 0.0439(5) Uani 1 1 d . . . H21A H 1.1101 0.6136 0.6856 0.066 Uiso 1 1 calc R . . H21B H 1.0708 0.5361 0.7221 0.066 Uiso 1 1 calc R . . H21C H 1.0806 0.6286 0.7589 0.066 Uiso 1 1 calc R . . C22 C 0.79041(13) 0.89771(11) 0.67779(9) 0.0242(4) Uani 1 1 d . . . H22 H 0.7747 0.8646 0.7174 0.029 Uiso 1 1 calc R . . C23 C 0.82958(17) 0.98452(12) 0.71158(12) 0.0365(5) Uani 1 1 d . . . H23A H 0.8421 1.0198 0.6731 0.055 Uiso 1 1 calc R . . H23B H 0.8909 0.9769 0.7543 0.055 Uiso 1 1 calc R . . H23C H 0.7808 1.0124 0.729 0.055 Uiso 1 1 calc R . . C24 C 0.69522(15) 0.90783(14) 0.61075(12) 0.0371(5) Uani 1 1 d . . . H24A H 0.7079 0.9416 0.5715 0.056 Uiso 1 1 calc R . . H24B H 0.6461 0.9366 0.6272 0.056 Uiso 1 1 calc R . . H24C H 0.6706 0.8518 0.5905 0.056 Uiso 1 1 calc R . . C25 C 0.69960(17) 0.52957(14) 0.64700(14) 0.0466(6) Uani 1 1 d . . . H25A H 0.7135 0.4709 0.6645 0.07 Uiso 1 1 calc R . . H25B H 0.7571 0.5535 0.638 0.07 Uiso 1 1 calc R . . H25C H 0.6429 0.5306 0.6 0.07 Uiso 1 1 calc R . . C26 C 0.58974(17) 0.54744(15) 0.71519(12) 0.0449(6) Uani 1 1 d . . . H26A H 0.5339 0.5517 0.6679 0.067 Uiso 1 1 calc R . . H26B H 0.5763 0.5811 0.7542 0.067 Uiso 1 1 calc R . . H26C H 0.5997 0.488 0.7311 0.067 Uiso 1 1 calc R . . N4 N 0.60673(11) 0.75181(9) 0.70679(8) 0.0246(3) Uani 1 1 d . . . C28 C 0.54771(15) 0.73236(13) 0.63631(11) 0.0341(4) Uani 1 1 d . . . H28 H 0.5688 0.6899 0.6096 0.041 Uiso 1 1 calc R . . C29 C 0.45865(16) 0.77071(14) 0.60106(12) 0.0427(5) Uani 1 1 d . . . H29 H 0.4198 0.7554 0.551 0.051 Uiso 1 1 calc R . . C30 C 0.42626(16) 0.83179(14) 0.63930(14) 0.0430(6) Uani 1 1 d . . . H30 H 0.3639 0.8579 0.6168 0.052 Uiso 1 1 calc R . . C31 C 0.48599(16) 0.85413(14) 0.71061(12) 0.0389(5) Uani 1 1 d . . . H31 H 0.4665 0.8972 0.7377 0.047 Uiso 1 1 calc R . . C32 C 0.57511(14) 0.81280(12) 0.74234(11) 0.0303(4) Uani 1 1 d . . . H32 H 0.6159 0.8285 0.7918 0.036 Uiso 1 1 calc R . . N5 N 0.86757(12) 0.59139(10) 0.82970(8) 0.0256(3) Uani 1 1 d . . . C34 C 0.95831(16) 0.62231(14) 0.86416(12) 0.0403(5) Uani 1 1 d . . . H34 H 0.9695 0.6809 0.8582 0.048 Uiso 1 1 calc R . . C35 C 1.03607(18) 0.57371(16) 0.90760(14) 0.0523(6) Uani 1 1 d . . . H35 H 1.0993 0.5982 0.9304 0.063 Uiso 1 1 calc R . . C36 C 1.0206(2) 0.48892(16) 0.91755(13) 0.0510(6) Uani 1 1 d . . . H36 H 1.0727 0.4538 0.9476 0.061 Uiso 1 1 calc R . . C37 C 0.92833(19) 0.45671(14) 0.88304(13) 0.0466(6) Uani 1 1 d . . . H37 H 0.9155 0.3985 0.889 0.056 Uiso 1 1 calc R . . C38 C 0.85420(16) 0.50874(12) 0.83978(11) 0.0332(4) Uani 1 1 d . . . H38 H 0.7907 0.4851 0.816 0.04 Uiso 1 1 calc R . . C39 C 0.7354(2) 0.72548(15) 1.32285(14) 0.0511(6) Uani 1 1 d . . . C40 C 0.78822(18) 0.74985(15) 1.39612(15) 0.0487(6) Uani 1 1 d . . . H40 H 0.8506 0.7761 1.4067 0.058 Uiso 1 1 calc R . . C41 C 0.7522(2) 0.73686(16) 1.45374(14) 0.0532(6) Uani 1 1 d . . . H41 H 0.7897 0.754 1.5036 0.064 Uiso 1 1 calc R . . C42 C 0.6621(2) 0.69906(18) 1.43930(16) 0.0613(7) Uani 1 1 d . . . H42 H 0.6372 0.6895 1.479 0.074 Uiso 1 1 calc R . . C43 C 0.6082(2) 0.67506(18) 1.36640(16) 0.0600(8) Uani 1 1 d . . . H43 H 0.5457 0.6492 1.3561 0.072 Uiso 1 1 calc R . . C44 C 0.6435(2) 0.68798(15) 1.30912(14) 0.0525(6) Uani 1 1 d . . . H44 H 0.6053 0.6713 1.2593 0.063 Uiso 1 1 calc R . . C45 C 0.7733(3) 0.7402(2) 1.2595(2) 0.0902(12) Uani 1 1 d . . . H45A H 0.81 0.7937 1.2678 0.135 Uiso 1 1 calc R . . H45B H 0.718 0.7431 1.2117 0.135 Uiso 1 1 calc R . . H45C H 0.8169 0.6934 1.2574 0.135 Uiso 1 1 calc R . . N1 N 0.78155(11) 0.75750(9) 0.84852(8) 0.0223(3) Uani 1 1 d . . . H1 H 0.8307 0.7896 0.8474 0.027 Uiso 1 1 calc R . . N2 N 0.81851(11) 0.71861(9) 0.70555(8) 0.0203(3) Uani 1 1 d . . . N3 N 0.67776(12) 0.57941(10) 0.70387(8) 0.0285(3) Uani 1 1 d . . . Ti1 Ti 0.750220(19) 0.678334(17) 0.757440(16) 0.01824(6) 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 C1 0.0177(8) 0.0246(8) 0.0159(7) 0.0008(6) 0.0047(6) 0.0007(7) C2 0.0266(10) 0.0241(9) 0.0209(8) -0.0006(6) 0.0089(7) -0.0001(7) C3 0.0401(12) 0.0289(9) 0.0272(9) -0.0060(7) 0.0160(8) 0.0002(8) C5 0.0324(11) 0.0382(10) 0.0284(9) 0.0003(8) 0.0177(8) -0.0049(8) C6 0.0211(9) 0.0296(9) 0.0204(8) -0.0004(7) 0.0085(7) -0.0035(7) C7 0.0477(12) 0.0223(9) 0.0276(9) -0.0054(7) 0.0184(9) -0.0063(8) C08 0.0402(12) 0.0426(12) 0.0251(9) -0.0043(8) 0.0192(8) 0.0031(9) C8 0.0648(16) 0.0271(11) 0.0526(13) 0.0062(9) 0.0240(12) 0.0020(10) C9 0.0400(14) 0.0614(17) 0.0800(18) 0.0211(14) 0.0280(13) -0.0050(12) C10 0.0382(11) 0.0325(10) 0.0262(9) -0.0046(7) 0.0169(8) -0.0135(8) C11 0.083(2) 0.0297(11) 0.0474(13) 0.0017(9) 0.0241(13) -0.0084(12) C12 0.0417(14) 0.0748(18) 0.0473(13) -0.0150(13) 0.0210(11) -0.0286(13) C13 0.0200(8) 0.0217(8) 0.0143(7) -0.0020(6) 0.0060(6) -0.0036(6) C14 0.0243(9) 0.0222(8) 0.0232(8) -0.0026(7) 0.0089(7) -0.0012(7) C15 0.0267(10) 0.0312(10) 0.0349(9) -0.0026(8) 0.0187(8) -0.0002(8) C16 0.0323(11) 0.0348(11) 0.0316(9) 0.0046(8) 0.0195(8) -0.0055(8) C17 0.0298(10) 0.0209(8) 0.0250(8) 0.0024(7) 0.0100(7) -0.0031(7) C18 0.0216(9) 0.0222(8) 0.0159(7) -0.0012(6) 0.0057(6) -0.0022(6) C19 0.0313(11) 0.0241(9) 0.0329(9) -0.0012(7) 0.0164(8) 0.0013(7) C20 0.0739(18) 0.0285(11) 0.0450(12) -0.0081(9) 0.0232(12) -0.0012(11) C21 0.0406(13) 0.0327(11) 0.0583(14) 0.0089(10) 0.0168(11) 0.0061(9) C22 0.0287(10) 0.0204(8) 0.0272(8) 0.0032(7) 0.0143(8) 0.0001(7) C23 0.0496(13) 0.0248(10) 0.0402(11) -0.0041(8) 0.0220(10) 0.0011(9) C24 0.0273(11) 0.0412(12) 0.0416(11) 0.0084(9) 0.0103(9) 0.0030(9) C25 0.0392(13) 0.0396(12) 0.0590(14) -0.0244(11) 0.0141(11) -0.0063(10) C26 0.0515(14) 0.0432(12) 0.0397(11) -0.0097(9) 0.0154(10) -0.0256(11) N4 0.0238(8) 0.0240(7) 0.0259(7) -0.0012(6) 0.0082(6) -0.0049(6) C28 0.0343(11) 0.0335(11) 0.0288(9) -0.0047(8) 0.0034(8) -0.0029(9) C29 0.0328(12) 0.0413(12) 0.0397(11) -0.0004(9) -0.0060(10) -0.0031(10) C30 0.0253(11) 0.0411(12) 0.0536(14) 0.0073(10) 0.0017(10) 0.0048(9) C31 0.0348(12) 0.0377(11) 0.0458(11) 0.0018(9) 0.0157(10) 0.0079(9) C32 0.0314(11) 0.0315(10) 0.0284(9) 0.0007(8) 0.0107(8) 0.0008(8) N5 0.0271(9) 0.0255(8) 0.0228(7) 0.0002(6) 0.0071(6) -0.0007(6) C34 0.0349(12) 0.0359(11) 0.0415(11) 0.0033(9) 0.0019(9) -0.0047(9) C35 0.0351(14) 0.0611(16) 0.0478(13) 0.0070(12) -0.0022(10) 0.0013(12) C36 0.0484(15) 0.0564(15) 0.0401(12) 0.0161(11) 0.0048(11) 0.0182(12) C37 0.0565(16) 0.0333(11) 0.0461(12) 0.0119(10) 0.0126(11) 0.0070(11) C38 0.0358(11) 0.0294(10) 0.0318(9) 0.0035(8) 0.0083(8) -0.0003(8) C39 0.0602(17) 0.0415(13) 0.0533(14) 0.0101(11) 0.0215(12) 0.0211(12) C40 0.0389(13) 0.0398(13) 0.0606(15) -0.0040(11) 0.0083(11) 0.0013(10) C41 0.0547(16) 0.0514(15) 0.0450(13) -0.0068(11) 0.0063(12) 0.0015(12) C42 0.0643(18) 0.0705(18) 0.0509(14) 0.0048(13) 0.0223(14) -0.0044(15) C43 0.0539(17) 0.0539(16) 0.0605(16) 0.0024(12) 0.0045(14) -0.0117(13) C44 0.0577(17) 0.0389(13) 0.0478(13) -0.0022(10) 0.0010(12) 0.0041(12) C45 0.097(3) 0.115(3) 0.0739(19) 0.023(2) 0.048(2) 0.035(2) N1 0.0237(8) 0.0239(7) 0.0225(7) -0.0037(6) 0.0121(6) -0.0089(6) N2 0.0239(8) 0.0186(7) 0.0204(6) 0.0007(5) 0.0103(6) -0.0007(6) N3 0.0282(9) 0.0235(8) 0.0290(8) -0.0034(6) 0.0035(7) -0.0056(7) Ti1 0.02054(14) 0.01741(12) 0.01775(11) -0.00166(12) 0.00785(10) -0.00433(13) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 N1 1.380(2) . ? C1 C6 1.423(2) . ? C1 C2 1.431(2) . ? C2 C3 1.395(2) . ? C2 C7 1.516(3) . ? C3 C08 1.377(3) . ? C3 H3 0.95 . ? C5 C08 1.377(3) . ? C5 C6 1.395(2) . ? C5 H5 0.95 . ? C6 C10 1.514(3) . ? C7 C9 1.523(3) . ? C7 C8 1.529(3) . ? C7 H7 1 . ? C08 H08 0.95 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C11 1.521(3) . ? C10 C12 1.529(3) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 N2 1.380(2) . ? C13 C14 1.414(2) . ? C13 C18 1.427(2) . ? C14 C15 1.395(2) . ? C14 C19 1.524(3) . ? C15 C16 1.383(3) . ? C15 H15 0.95 . ? C16 C17 1.387(3) . ? C16 H16 0.95 . ? C17 C18 1.383(2) . ? C17 H17 0.95 . ? C18 C22 1.517(2) . ? C19 C21 1.524(3) . ? C19 C20 1.535(3) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C24 1.526(3) . ? C22 C23 1.534(3) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? C25 N3 1.450(3) . ? C25 H25A 0.98 . ? C25 H25B 0.98 . ? C25 H25C 0.98 . ? C26 N3 1.453(3) . ? C26 H26A 0.98 . ? C26 H26B 0.98 . ? C26 H26C 0.98 . ? N4 C32 1.340(2) . ? N4 C28 1.347(2) . ? N4 Ti1 2.2821(16) . ? C28 C29 1.372(3) . ? C28 H28 0.95 . ? C29 C30 1.378(3) . ? C29 H29 0.95 . ? C30 C31 1.373(3) . ? C30 H30 0.95 . ? C31 C32 1.385(3) . ? C31 H31 0.95 . ? C32 H32 0.95 . ? N5 C38 1.340(2) . ? N5 C34 1.342(3) . ? N5 Ti1 2.2437(15) . ? C34 C35 1.376(3) . ? C34 H34 0.95 . ? C35 C36 1.378(4) . ? C35 H35 0.95 . ? C36 C37 1.368(4) . ? C36 H36 0.95 . ? C37 C38 1.375(3) . ? C37 H37 0.95 . ? C38 H38 0.95 . ? C39 C40 1.385(4) . ? C39 C44 1.396(4) . ? C39 C45 1.496(4) . ? C40 C41 1.373(4) . ? C40 H40 0.95 . ? C41 C42 1.374(4) . ? C41 H41 0.95 . ? C42 C43 1.381(4) . ? C42 H42 0.95 . ? C43 C44 1.360(4) . ? C43 H43 0.95 . ? C44 H44 0.95 . ? C45 H45A 0.98 . ? C45 H45B 0.98 . ? C45 H45C 0.98 . ? N1 Ti1 2.0450(13) . ? N1 H1 0.88 . ? N2 Ti1 1.7334(14) . ? N3 Ti1 1.9560(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 N1 C1 C6 120.56(15) . . ? N1 C1 C2 121.55(14) . . ? C6 C1 C2 117.88(14) . . ? C3 C2 C1 119.18(16) . . ? C3 C2 C7 119.11(16) . . ? C1 C2 C7 121.67(14) . . ? C08 C3 C2 122.34(17) . . ? C08 C3 H3 118.8 . . ? C2 C3 H3 118.8 . . ? C08 C5 C6 122.00(17) . . ? C08 C5 H5 119 . . ? C6 C5 H5 119 . . ? C5 C6 C1 119.72(16) . . ? C5 C6 C10 118.66(15) . . ? C1 C6 C10 121.62(14) . . ? C2 C7 C9 109.98(16) . . ? C2 C7 C8 113.17(17) . . ? C9 C7 C8 109.86(19) . . ? C2 C7 H7 107.9 . . ? C9 C7 H7 107.9 . . ? C8 C7 H7 107.9 . . ? C5 C08 C3 118.74(16) . . ? C5 C08 H08 120.6 . . ? C3 C08 H08 120.6 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C6 C10 C11 112.46(16) . . ? C6 C10 C12 111.62(18) . . ? C11 C10 C12 111.46(19) . . ? C6 C10 H10 107 . . ? C11 C10 H10 107 . . ? C12 C10 H10 107 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 C14 121.50(15) . . ? N2 C13 C18 119.63(15) . . ? C14 C13 C18 118.86(14) . . ? C15 C14 C13 119.44(15) . . ? C15 C14 C19 119.20(16) . . ? C13 C14 C19 121.35(15) . . ? C16 C15 C14 121.66(17) . . ? C16 C15 H15 119.2 . . ? C14 C15 H15 119.2 . . ? C15 C16 C17 118.77(16) . . ? C15 C16 H16 120.6 . . ? C17 C16 H16 120.6 . . ? C18 C17 C16 122.17(16) . . ? C18 C17 H17 118.9 . . ? C16 C17 H17 118.9 . . ? C17 C18 C13 119.08(15) . . ? C17 C18 C22 120.64(15) . . ? C13 C18 C22 120.20(14) . . ? C14 C19 C21 111.89(16) . . ? C14 C19 C20 110.74(15) . . ? C21 C19 C20 110.49(17) . . ? C14 C19 H19 107.9 . . ? C21 C19 H19 107.9 . . ? C20 C19 H19 107.9 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C24 110.33(14) . . ? C18 C22 C23 113.03(15) . . ? C24 C22 C23 110.57(16) . . ? C18 C22 H22 107.6 . . ? C24 C22 H22 107.6 . . ? C23 C22 H22 107.6 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? N3 C25 H25A 109.5 . . ? N3 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? N3 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? N3 C26 H26A 109.5 . . ? N3 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? N3 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C32 N4 C28 116.62(16) . . ? C32 N4 Ti1 124.94(12) . . ? C28 N4 Ti1 118.43(13) . . ? N4 C28 C29 123.4(2) . . ? N4 C28 H28 118.3 . . ? C29 C28 H28 118.3 . . ? C28 C29 C30 119.08(19) . . ? C28 C29 H29 120.5 . . ? C30 C29 H29 120.5 . . ? C31 C30 C29 118.6(2) . . ? C31 C30 H30 120.7 . . ? C29 C30 H30 120.7 . . ? C30 C31 C32 118.9(2) . . ? C30 C31 H31 120.5 . . ? C32 C31 H31 120.5 . . ? N4 C32 C31 123.28(18) . . ? N4 C32 H32 118.4 . . ? C31 C32 H32 118.4 . . ? C38 N5 C34 116.71(17) . . ? C38 N5 Ti1 124.32(13) . . ? C34 N5 Ti1 118.95(13) . . ? N5 C34 C35 123.5(2) . . ? N5 C34 H34 118.3 . . ? C35 C34 H34 118.3 . . ? C34 C35 C36 118.9(2) . . ? C34 C35 H35 120.5 . . ? C36 C35 H35 120.5 . . ? C37 C36 C35 118.2(2) . . ? C37 C36 H36 120.9 . . ? C35 C36 H36 120.9 . . ? C36 C37 C38 119.8(2) . . ? C36 C37 H37 120.1 . . ? C38 C37 H37 120.1 . . ? N5 C38 C37 122.9(2) . . ? N5 C38 H38 118.6 . . ? C37 C38 H38 118.6 . . ? C40 C39 C44 117.8(2) . . ? C40 C39 C45 121.8(3) . . ? C44 C39 C45 120.4(3) . . ? C41 C40 C39 121.3(2) . . ? C41 C40 H40 119.3 . . ? C39 C40 H40 119.3 . . ? C40 C41 C42 120.0(2) . . ? C40 C41 H41 120 . . ? C42 C41 H41 120 . . ? C41 C42 C43 119.3(3) . . ? C41 C42 H42 120.3 . . ? C43 C42 H42 120.3 . . ? C44 C43 C42 120.8(3) . . ? C44 C43 H43 119.6 . . ? C42 C43 H43 119.6 . . ? C43 C44 C39 120.6(2) . . ? C43 C44 H44 119.7 . . ? C39 C44 H44 119.7 . . ? C39 C45 H45A 109.5 . . ? C39 C45 H45B 109.5 . . ? H45A C45 H45B 109.5 . . ? C39 C45 H45C 109.5 . . ? H45A C45 H45C 109.5 . . ? H45B C45 H45C 109.5 . . ? C1 N1 Ti1 147.60(12) . . ? C1 N1 H1 106.2 . . ? Ti1 N1 H1 106.2 . . ? C13 N2 Ti1 173.62(12) . . ? C25 N3 C26 110.25(16) . . ? C25 N3 Ti1 126.87(13) . . ? C26 N3 Ti1 122.85(13) . . ? N2 Ti1 N3 107.98(7) . . ? N2 Ti1 N1 104.27(6) . . ? N3 Ti1 N1 147.75(6) . . ? N2 Ti1 N5 96.16(6) . . ? N3 Ti1 N5 89.27(6) . . ? N1 Ti1 N5 87.62(6) . . ? N2 Ti1 N4 101.03(6) . . ? N3 Ti1 N4 86.47(6) . . ? N1 Ti1 N4 87.12(6) . . ? N5 Ti1 N4 162.78(5) . . ? _database_code_depnum_ccdc_archive 'CCDC 931108' ####################################################################### # # 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_17 #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C46 H63 N5 Ti1' _chemical_formula_sum 'C46 H63 N5 Ti' _chemical_formula_weight 733.91 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.6975(5) _cell_length_b 12.1115(6) _cell_length_c 22.0445(10) _cell_angle_alpha 80.776(2) _cell_angle_beta 79.744(2) _cell_angle_gamma 73.268(2) _cell_volume 2423.5(2) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 9909 _cell_measurement_theta_min 2.21 _cell_measurement_theta_max 30.97 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour 'yellow orange' _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.05 _exptl_crystal_density_diffrn 1.006 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.208 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.901 _exptl_absorpt_correction_T_max 0.978 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 180(2) _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Kappa APEX II' _diffrn_measurement_method \w-\f _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_av_R_equivalents 0.0353 _diffrn_reflns_av_unetI/netI 0.025 _diffrn_reflns_number 56608 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 0.95 _diffrn_reflns_theta_max 26.37 _diffrn_reflns_theta_full 26.37 _diffrn_measured_fraction_theta_full 0.998 _diffrn_measured_fraction_theta_max 0.998 _reflns_number_total 9895 _reflns_number_gt 8489 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(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. ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.000 -0.002 0.000 391 126 ' ' _platon_squeeze_details ; ; _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^)+(0.1027P)^2^+1.3448P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_coef 0.0111(14) _refine_ls_number_reflns 9895 _refine_ls_number_parameters 482 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0661 _refine_ls_R_factor_gt 0.0591 _refine_ls_wR_factor_ref 0.1721 _refine_ls_wR_factor_gt 0.1662 _refine_ls_goodness_of_fit_ref 1.082 _refine_ls_restrained_S_all 1.082 _refine_ls_shift/su_max 0.021 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.275 _refine_diff_density_min -0.48 _refine_diff_density_rms 0.098 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 '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' 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 C1 C 0.2842(2) 0.17233(17) 0.17693(9) 0.0225(4) Uani 1 1 d . . . C2 C 0.3139(2) 0.05576(18) 0.20449(9) 0.0275(4) Uani 1 1 d . . . C3 C 0.4064(3) -0.0314(2) 0.17077(11) 0.0369(5) Uani 1 1 d . . . H3 H 0.4252 -0.1096 0.1895 0.044 Uiso 1 1 calc R . . C4 C 0.4713(3) -0.0075(2) 0.11118(11) 0.0386(5) Uani 1 1 d . . . H4 H 0.5334 -0.0684 0.0889 0.046 Uiso 1 1 calc R . . C5 C 0.4449(2) 0.1056(2) 0.08449(10) 0.0345(5) Uani 1 1 d . . . H5 H 0.4907 0.1223 0.0436 0.041 Uiso 1 1 calc R . . C6 C 0.3531(2) 0.19675(19) 0.11551(9) 0.0280(4) Uani 1 1 d . . . C7 C 0.2467(3) 0.02174(19) 0.27001(11) 0.0377(5) Uani 1 1 d . . . H7 H 0.1851 0.0948 0.2868 0.045 Uiso 1 1 calc R . . C8 C 0.1469(4) -0.0558(3) 0.27092(16) 0.0628(9) Uani 1 1 d . . . H8A H 0.0688 -0.015 0.2462 0.094 Uiso 1 1 calc R . . H8B H 0.1046 -0.0748 0.3138 0.094 Uiso 1 1 calc R . . H8C H 0.2031 -0.1275 0.2534 0.094 Uiso 1 1 calc R . . C9 C 0.3621(4) -0.0340(3) 0.31257(14) 0.0710(10) Uani 1 1 d . . . H9A H 0.4197 -0.1093 0.2995 0.106 Uiso 1 1 calc R . . H9B H 0.3149 -0.0452 0.3554 0.106 Uiso 1 1 calc R . . H9C H 0.426 0.0167 0.3102 0.106 Uiso 1 1 calc R . . C10 C 0.3269(3) 0.3212(2) 0.08441(11) 0.0403(6) Uani 1 1 d . . . H10 H 0.2228 0.3603 0.0985 0.048 Uiso 1 1 calc R . . C11 C 0.3427(7) 0.3325(4) 0.01390(17) 0.0986(16) Uani 1 1 d . . . H11A H 0.2937 0.4119 -0.0019 0.148 Uiso 1 1 calc R . . H11B H 0.2986 0.278 0.0014 0.148 Uiso 1 1 calc R . . H11C H 0.4461 0.315 -0.0032 0.148 Uiso 1 1 calc R . . C12 C 0.4133(6) 0.3859(4) 0.1060(2) 0.0865(12) Uani 1 1 d . . . H12A H 0.4116 0.3676 0.151 0.13 Uiso 1 1 calc R . . H12B H 0.3717 0.4694 0.0958 0.13 Uiso 1 1 calc R . . H12C H 0.5139 0.3635 0.0854 0.13 Uiso 1 1 calc R . . C13 C -0.0872(2) 0.56200(17) 0.25445(10) 0.0277(4) Uani 1 1 d . . . C14 C -0.1994(2) 0.6179(2) 0.21760(11) 0.0360(5) Uani 1 1 d . . . C15 C -0.2505(3) 0.7383(2) 0.21311(15) 0.0514(7) Uani 1 1 d . . . H15 H -0.3248 0.7767 0.1882 0.062 Uiso 1 1 calc R . . C16 C -0.1958(4) 0.8032(2) 0.24403(17) 0.0603(8) Uani 1 1 d . . . H16 H -0.2342 0.8852 0.241 0.072 Uiso 1 1 calc R . . C17 C -0.0858(3) 0.7497(2) 0.27918(14) 0.0484(6) Uani 1 1 d . . . H17 H -0.049 0.7953 0.3002 0.058 Uiso 1 1 calc R . . C18 C -0.0275(3) 0.62943(19) 0.28446(11) 0.0337(5) Uani 1 1 d . . . C19 C -0.2587(3) 0.5452(2) 0.18471(12) 0.0435(6) Uani 1 1 d . . . H19 H -0.2633 0.4733 0.2135 0.052 Uiso 1 1 calc R . . C20 C -0.1544(4) 0.5069(3) 0.12649(14) 0.0612(8) Uani 1 1 d . . . H20A H -0.1507 0.575 0.0961 0.092 Uiso 1 1 calc R . . H20B H -0.1888 0.4525 0.1085 0.092 Uiso 1 1 calc R . . H20C H -0.057 0.4688 0.1376 0.092 Uiso 1 1 calc R . . C21 C -0.4133(3) 0.6042(3) 0.16944(19) 0.0697(9) Uani 1 1 d . . . H21A H -0.4761 0.6329 0.2068 0.105 Uiso 1 1 calc R . . H21B H -0.4514 0.5479 0.1549 0.105 Uiso 1 1 calc R . . H21C H -0.4111 0.6693 0.1369 0.105 Uiso 1 1 calc R . . C22 C 0.1024(3) 0.5715(2) 0.31762(11) 0.0366(5) Uani 1 1 d . . . H22 H 0.0938 0.4922 0.3357 0.044 Uiso 1 1 calc R . . C23 C 0.2403(3) 0.5562(3) 0.27025(15) 0.0514(7) Uani 1 1 d . . . H23A H 0.2366 0.5064 0.24 0.077 Uiso 1 1 calc R . . H23B H 0.3255 0.5201 0.2916 0.077 Uiso 1 1 calc R . . H23C H 0.2473 0.6322 0.2488 0.077 Uiso 1 1 calc R . . C24 C 0.1181(4) 0.6329(3) 0.37074(14) 0.0551(7) Uani 1 1 d . . . H24A H 0.1501 0.7026 0.3535 0.083 Uiso 1 1 calc R . . H24B H 0.19 0.5803 0.3956 0.083 Uiso 1 1 calc R . . H24C H 0.024 0.6549 0.3971 0.083 Uiso 1 1 calc R . . C25 C -0.2005(2) 0.23039(17) 0.40625(9) 0.0231(4) Uani 1 1 d . . . C26 C -0.2359(2) 0.12817(18) 0.43872(9) 0.0271(4) Uani 1 1 d . . . C27 C -0.3125(2) 0.1318(2) 0.49843(10) 0.0343(5) Uani 1 1 d . . . H27 H -0.3333 0.0628 0.5202 0.041 Uiso 1 1 calc R . . C28 C -0.3593(3) 0.2318(2) 0.52707(10) 0.0366(5) Uani 1 1 d . . . H28 H -0.4082 0.2315 0.5684 0.044 Uiso 1 1 calc R . . C29 C -0.3333(2) 0.3322(2) 0.49420(10) 0.0317(5) Uani 1 1 d . . . H29 H -0.3685 0.402 0.5132 0.038 Uiso 1 1 calc R . . C30 C -0.2577(2) 0.33571(18) 0.43434(9) 0.0259(4) Uani 1 1 d . . . C31 C -0.1879(3) 0.01326(19) 0.41121(10) 0.0339(5) Uani 1 1 d . . . H31 H -0.158 0.0305 0.3657 0.041 Uiso 1 1 calc R . . C32 C -0.3107(3) -0.0468(3) 0.41912(14) 0.0502(7) Uani 1 1 d . . . H32A H -0.335 -0.0728 0.4632 0.075 Uiso 1 1 calc R . . H32B H -0.2787 -0.1139 0.3955 0.075 Uiso 1 1 calc R . . H32C H -0.3967 0.008 0.4038 0.075 Uiso 1 1 calc R . . C33 C -0.0548(3) -0.0661(2) 0.43836(14) 0.0491(6) Uani 1 1 d . . . H33A H 0.0229 -0.0267 0.4309 0.074 Uiso 1 1 calc R . . H33B H -0.0213 -0.1378 0.4185 0.074 Uiso 1 1 calc R . . H33C H -0.0804 -0.0847 0.4831 0.074 Uiso 1 1 calc R . . C34 C -0.2453(2) 0.45112(19) 0.39873(10) 0.0323(5) Uani 1 1 d . . . H34 H -0.1545 0.4356 0.3681 0.039 Uiso 1 1 calc R . . C35 C -0.2346(3) 0.5391(2) 0.43922(14) 0.0514(7) Uani 1 1 d . . . H35A H -0.3256 0.561 0.4675 0.077 Uiso 1 1 calc R . . H35B H -0.2174 0.6083 0.4127 0.077 Uiso 1 1 calc R . . H35C H -0.1539 0.5043 0.4634 0.077 Uiso 1 1 calc R . . C36 C -0.3736(3) 0.5033(2) 0.36201(12) 0.0441(6) Uani 1 1 d . . . H36A H -0.3731 0.45 0.3328 0.066 Uiso 1 1 calc R . . H36B H -0.365 0.5778 0.339 0.066 Uiso 1 1 calc R . . H36C H -0.4648 0.5154 0.3907 0.066 Uiso 1 1 calc R . . C37 C -0.2477(3) 0.2244(3) 0.23978(15) 0.0589(8) Uani 1 1 d . . . H37 H -0.293 0.2553 0.2776 0.071 Uiso 1 1 calc R . . C38 C -0.3259(4) 0.1770(4) 0.20964(19) 0.0799(12) Uani 1 1 d . . . H38 H -0.4234 0.1774 0.2263 0.096 Uiso 1 1 calc R . . C39 C -0.2648(4) 0.1305(3) 0.15701(17) 0.0654(9) Uani 1 1 d . . . H39 H -0.3166 0.096 0.1361 0.078 Uiso 1 1 calc R . . C40 C -0.1287(4) 0.1341(3) 0.13478(17) 0.0725(11) Uani 1 1 d . . . H40 H -0.0821 0.1015 0.0975 0.087 Uiso 1 1 calc R . . C41 C -0.0546(3) 0.1852(3) 0.16579(13) 0.0520(7) Uani 1 1 d . . . H41 H 0.0412 0.1888 0.1483 0.062 Uiso 1 1 calc R . . C42 C 0.1302(2) 0.27993(19) 0.40539(10) 0.0303(4) Uani 1 1 d . . . H42 H 0.0315 0.2823 0.4206 0.036 Uiso 1 1 calc R . . C43 C 0.2202(3) 0.2822(2) 0.44701(11) 0.0385(5) Uani 1 1 d . . . H43 H 0.1829 0.2875 0.4896 0.046 Uiso 1 1 calc R . . C44 C 0.3629(3) 0.2767(2) 0.42637(13) 0.0459(6) Uani 1 1 d . . . H44 H 0.4268 0.2781 0.4541 0.055 Uiso 1 1 calc R . . C45 C 0.4115(3) 0.2692(3) 0.36438(14) 0.0530(7) Uani 1 1 d . . . H45 H 0.5106 0.264 0.3486 0.064 Uiso 1 1 calc R . . C46 C 0.3154(3) 0.2691(2) 0.32523(11) 0.0389(5) Uani 1 1 d . . . H46 H 0.3506 0.2651 0.2824 0.047 Uiso 1 1 calc R . . N1 N 0.18666(18) 0.25919(14) 0.20908(7) 0.0231(3) Uani 1 1 d . . . H1 H 0.2071 0.3252 0.1937 0.028 Uiso 1 1 calc R . . N2 N -0.03869(18) 0.44229(14) 0.26209(7) 0.0237(3) Uani 1 1 d . . . N3 N -0.1111(2) 0.22805(15) 0.34906(8) 0.0279(4) Uani 1 1 d . . . H3A H -0.1084 0.1607 0.338 0.033 Uiso 1 1 calc R . . N4 N -0.11206(19) 0.22916(16) 0.21868(8) 0.0286(4) Uani 1 1 d . . . N5 N 0.17555(18) 0.27459(14) 0.34446(8) 0.0245(4) Uani 1 1 d . . . Ti1 Ti 0.01623(3) 0.29328(3) 0.277259(15) 0.01893(12) 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 C1 0.0167(9) 0.0282(10) 0.0240(9) -0.0055(7) -0.0038(7) -0.0061(7) C2 0.0257(10) 0.0261(10) 0.0285(10) -0.0043(8) -0.0016(8) -0.0043(8) C3 0.0336(12) 0.0272(11) 0.0442(13) -0.0078(9) -0.0004(10) -0.0002(9) C4 0.0314(12) 0.0379(13) 0.0428(13) -0.0187(10) 0.0033(10) -0.0008(10) C5 0.0294(11) 0.0488(14) 0.0260(10) -0.0120(9) 0.0021(8) -0.0108(10) C6 0.0249(10) 0.0365(11) 0.0231(9) -0.0045(8) -0.0031(8) -0.0089(8) C7 0.0497(14) 0.0220(10) 0.0330(11) -0.0008(8) 0.0056(10) -0.0044(10) C8 0.078(2) 0.0392(15) 0.0665(19) -0.0108(13) 0.0285(17) -0.0287(15) C9 0.092(3) 0.062(2) 0.0394(15) 0.0094(14) -0.0129(16) 0.0047(18) C10 0.0493(14) 0.0380(13) 0.0282(11) -0.0002(9) 0.0023(10) -0.0096(11) C11 0.164(5) 0.083(3) 0.051(2) 0.0172(19) -0.030(3) -0.042(3) C12 0.115(4) 0.066(2) 0.087(3) 0.003(2) -0.018(2) -0.042(2) C13 0.0261(10) 0.0217(10) 0.0305(10) -0.0023(8) 0.0013(8) -0.0022(8) C14 0.0290(11) 0.0317(12) 0.0407(12) 0.0032(9) -0.0039(9) -0.0023(9) C15 0.0350(13) 0.0338(13) 0.0714(19) 0.0103(12) -0.0094(12) 0.0051(10) C16 0.0583(18) 0.0200(12) 0.094(2) -0.0015(13) -0.0094(16) -0.0010(12) C17 0.0490(15) 0.0225(11) 0.0721(18) -0.0086(11) -0.0036(13) -0.0083(10) C18 0.0360(12) 0.0220(10) 0.0415(12) -0.0037(9) 0.0013(9) -0.0090(9) C19 0.0361(13) 0.0444(14) 0.0476(14) 0.0040(11) -0.0177(11) -0.0052(11) C20 0.0627(19) 0.070(2) 0.0463(16) -0.0098(14) -0.0202(14) -0.0019(16) C21 0.0427(17) 0.072(2) 0.095(3) -0.0041(19) -0.0326(17) -0.0068(15) C22 0.0454(13) 0.0257(11) 0.0444(13) -0.0059(9) -0.0093(10) -0.0155(10) C23 0.0395(14) 0.0520(16) 0.0642(18) -0.0092(13) -0.0097(13) -0.0118(12) C24 0.073(2) 0.0463(16) 0.0586(17) -0.0133(13) -0.0158(15) -0.0284(15) C25 0.0196(9) 0.0286(10) 0.0231(9) -0.0059(7) -0.0024(7) -0.0082(8) C26 0.0261(10) 0.0296(11) 0.0257(10) -0.0021(8) -0.0045(8) -0.0074(8) C27 0.0326(11) 0.0388(12) 0.0286(11) 0.0032(9) -0.0014(9) -0.0105(9) C28 0.0326(12) 0.0505(14) 0.0210(10) -0.0035(9) 0.0014(8) -0.0055(10) C29 0.0266(10) 0.0404(12) 0.0265(10) -0.0120(9) -0.0011(8) -0.0036(9) C30 0.0200(9) 0.0327(11) 0.0269(10) -0.0102(8) -0.0014(7) -0.0077(8) C31 0.0424(13) 0.0301(11) 0.0306(11) -0.0019(9) -0.0008(9) -0.0154(10) C32 0.0564(17) 0.0460(15) 0.0575(17) -0.0038(12) -0.0116(13) -0.0272(13) C33 0.0457(15) 0.0375(14) 0.0605(17) -0.0137(12) -0.0060(12) -0.0018(11) C34 0.0310(11) 0.0297(11) 0.0349(11) -0.0151(9) 0.0084(9) -0.0080(9) C35 0.0606(17) 0.0453(15) 0.0543(16) -0.0268(13) 0.0117(13) -0.0243(13) C36 0.0427(14) 0.0372(13) 0.0448(14) -0.0017(10) 0.0008(11) -0.0043(11) C37 0.0332(14) 0.099(3) 0.0572(17) -0.0363(17) 0.0035(12) -0.0296(15) C38 0.0475(18) 0.130(4) 0.087(3) -0.038(2) -0.0096(17) -0.050(2) C39 0.064(2) 0.0613(19) 0.090(2) -0.0272(17) -0.0452(18) -0.0159(15) C40 0.0502(18) 0.101(3) 0.076(2) -0.063(2) -0.0259(16) 0.0032(17) C41 0.0314(13) 0.086(2) 0.0442(14) -0.0390(14) -0.0053(11) -0.0081(13) C42 0.0334(11) 0.0318(11) 0.0276(10) -0.0046(8) -0.0050(8) -0.0104(9) C43 0.0506(15) 0.0378(12) 0.0315(11) -0.0062(9) -0.0137(10) -0.0126(11) C44 0.0465(15) 0.0496(15) 0.0487(15) -0.0111(12) -0.0242(12) -0.0107(12) C45 0.0303(13) 0.078(2) 0.0568(16) -0.0195(15) -0.0098(12) -0.0150(13) C46 0.0286(11) 0.0541(15) 0.0354(12) -0.0112(10) -0.0039(9) -0.0104(10) N1 0.0233(8) 0.0206(8) 0.0239(8) -0.0032(6) 0.0003(6) -0.0056(6) N2 0.0232(8) 0.0237(8) 0.0238(8) -0.0055(6) -0.0034(6) -0.0038(7) N3 0.0341(10) 0.0238(8) 0.0274(9) -0.0112(7) 0.0067(7) -0.0128(7) N4 0.0251(9) 0.0312(9) 0.0318(9) -0.0112(7) -0.0042(7) -0.0069(7) N5 0.0252(9) 0.0210(8) 0.0282(8) -0.0040(6) -0.0065(7) -0.0052(6) Ti1 0.01904(19) 0.01840(19) 0.01986(19) -0.00539(12) -0.00061(12) -0.00534(13) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C1 N1 1.390(2) . ? C1 C2 1.414(3) . ? C1 C6 1.425(3) . ? C2 C3 1.393(3) . ? C2 C7 1.520(3) . ? C3 C4 1.376(3) . ? C3 H3 0.95 . ? C4 C5 1.373(4) . ? C4 H4 0.95 . ? C5 C6 1.392(3) . ? C5 H5 0.95 . ? C6 C10 1.523(3) . ? C7 C9 1.525(4) . ? C7 C8 1.527(4) . ? C7 H7 1 . ? C8 H8A 0.98 . ? C8 H8B 0.98 . ? C8 H8C 0.98 . ? C9 H9A 0.98 . ? C9 H9B 0.98 . ? C9 H9C 0.98 . ? C10 C12 1.476(5) . ? C10 C11 1.522(4) . ? C10 H10 1 . ? C11 H11A 0.98 . ? C11 H11B 0.98 . ? C11 H11C 0.98 . ? C12 H12A 0.98 . ? C12 H12B 0.98 . ? C12 H12C 0.98 . ? C13 N2 1.382(3) . ? C13 C14 1.420(3) . ? C13 C18 1.422(3) . ? C14 C15 1.392(3) . ? C14 C19 1.508(4) . ? C15 C16 1.380(5) . ? C15 H15 0.95 . ? C16 C17 1.376(4) . ? C16 H16 0.95 . ? C17 C18 1.396(3) . ? C17 H17 0.95 . ? C18 C22 1.506(3) . ? C19 C20 1.531(4) . ? C19 C21 1.536(4) . ? C19 H19 1 . ? C20 H20A 0.98 . ? C20 H20B 0.98 . ? C20 H20C 0.98 . ? C21 H21A 0.98 . ? C21 H21B 0.98 . ? C21 H21C 0.98 . ? C22 C23 1.528(4) . ? C22 C24 1.534(3) . ? C22 H22 1 . ? C23 H23A 0.98 . ? C23 H23B 0.98 . ? C23 H23C 0.98 . ? C24 H24A 0.98 . ? C24 H24B 0.98 . ? C24 H24C 0.98 . ? C25 N3 1.397(2) . ? C25 C26 1.427(3) . ? C25 C30 1.429(3) . ? C26 C27 1.392(3) . ? C26 C31 1.523(3) . ? C27 C28 1.378(3) . ? C27 H27 0.95 . ? C28 C29 1.377(3) . ? C28 H28 0.95 . ? C29 C30 1.391(3) . ? C29 H29 0.95 . ? C30 C34 1.515(3) . ? C31 C33 1.524(4) . ? C31 C32 1.537(3) . ? C31 H31 1 . ? C32 H32A 0.98 . ? C32 H32B 0.98 . ? C32 H32C 0.98 . ? C33 H33A 0.98 . ? C33 H33B 0.98 . ? C33 H33C 0.98 . ? C34 C35 1.531(3) . ? C34 C36 1.531(4) . ? C34 H34 1 . ? C35 H35A 0.98 . ? C35 H35B 0.98 . ? C35 H35C 0.98 . ? C36 H36A 0.98 . ? C36 H36B 0.98 . ? C36 H36C 0.98 . ? C37 N4 1.329(3) . ? C37 C38 1.378(4) . ? C37 H37 0.95 . ? C38 C39 1.337(5) . ? C38 H38 0.95 . ? C39 C40 1.335(5) . ? C39 H39 0.95 . ? C40 C41 1.391(4) . ? C40 H40 0.95 . ? C41 N4 1.323(3) . ? C41 H41 0.95 . ? C42 N5 1.343(3) . ? C42 C43 1.382(3) . ? C42 H42 0.95 . ? C43 C44 1.364(4) . ? C43 H43 0.95 . ? C44 C45 1.373(4) . ? C44 H44 0.95 . ? C45 C46 1.379(3) . ? C45 H45 0.95 . ? C46 N5 1.332(3) . ? C46 H46 0.95 . ? N1 Ti1 2.0206(16) . ? N1 H1 0.88 . ? N2 Ti1 1.7230(17) . ? N3 Ti1 2.0293(17) . ? N3 H3A 0.88 . ? N4 Ti1 2.2953(17) . ? N5 Ti1 2.2669(17) . ? 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 C1 C2 119.90(17) . . ? N1 C1 C6 121.72(18) . . ? C2 C1 C6 118.36(18) . . ? C3 C2 C1 119.49(19) . . ? C3 C2 C7 118.49(19) . . ? C1 C2 C7 122.01(18) . . ? C4 C3 C2 121.9(2) . . ? C4 C3 H3 119 . . ? C2 C3 H3 119 . . ? C5 C4 C3 118.9(2) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? C4 C5 C6 122.0(2) . . ? C4 C5 H5 119 . . ? C6 C5 H5 119 . . ? C5 C6 C1 119.3(2) . . ? C5 C6 C10 120.51(19) . . ? C1 C6 C10 120.24(19) . . ? C2 C7 C9 111.7(2) . . ? C2 C7 C8 112.0(2) . . ? C9 C7 C8 111.3(3) . . ? C2 C7 H7 107.2 . . ? C9 C7 H7 107.2 . . ? C8 C7 H7 107.2 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C12 C10 C11 111.9(3) . . ? C12 C10 C6 112.3(2) . . ? C11 C10 C6 114.2(2) . . ? C12 C10 H10 105.9 . . ? C11 C10 H10 105.9 . . ? C6 C10 H10 105.9 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N2 C13 C14 119.9(2) . . ? N2 C13 C18 120.29(19) . . ? C14 C13 C18 119.81(19) . . ? C15 C14 C13 118.5(2) . . ? C15 C14 C19 122.4(2) . . ? C13 C14 C19 119.1(2) . . ? C16 C15 C14 121.5(3) . . ? C16 C15 H15 119.3 . . ? C14 C15 H15 119.3 . . ? C17 C16 C15 120.2(2) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C16 C17 C18 121.1(3) . . ? C16 C17 H17 119.4 . . ? C18 C17 H17 119.4 . . ? C17 C18 C13 118.8(2) . . ? C17 C18 C22 121.3(2) . . ? C13 C18 C22 119.78(19) . . ? C14 C19 C20 110.7(2) . . ? C14 C19 C21 113.7(2) . . ? C20 C19 C21 111.1(2) . . ? C14 C19 H19 107 . . ? C20 C19 H19 107 . . ? C21 C19 H19 107 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C19 C21 H21A 109.5 . . ? C19 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C19 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C18 C22 C23 109.0(2) . . ? C18 C22 C24 115.7(2) . . ? C23 C22 C24 109.6(2) . . ? C18 C22 H22 107.4 . . ? C23 C22 H22 107.4 . . ? C24 C22 H22 107.4 . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? N3 C25 C26 121.35(18) . . ? N3 C25 C30 120.59(18) . . ? C26 C25 C30 118.05(18) . . ? C27 C26 C25 119.3(2) . . ? C27 C26 C31 118.46(19) . . ? C25 C26 C31 122.19(18) . . ? C28 C27 C26 122.3(2) . . ? C28 C27 H27 118.8 . . ? C26 C27 H27 118.8 . . ? C29 C28 C27 118.3(2) . . ? C29 C28 H28 120.8 . . ? C27 C28 H28 120.8 . . ? C28 C29 C30 122.7(2) . . ? C28 C29 H29 118.6 . . ? C30 C29 H29 118.6 . . ? C29 C30 C25 118.9(2) . . ? C29 C30 C34 119.82(19) . . ? C25 C30 C34 121.14(18) . . ? C26 C31 C33 110.16(19) . . ? C26 C31 C32 112.8(2) . . ? C33 C31 C32 111.5(2) . . ? C26 C31 H31 107.4 . . ? C33 C31 H31 107.4 . . ? C32 C31 H31 107.4 . . ? C31 C32 H32A 109.5 . . ? C31 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C31 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C31 C33 H33A 109.5 . . ? C31 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? C31 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C30 C34 C35 114.2(2) . . ? C30 C34 C36 109.75(18) . . ? C35 C34 C36 110.0(2) . . ? C30 C34 H34 107.5 . . ? C35 C34 H34 107.5 . . ? C36 C34 H34 107.5 . . ? C34 C35 H35A 109.5 . . ? C34 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? C34 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C34 C36 H36A 109.5 . . ? C34 C36 H36B 109.5 . . ? H36A C36 H36B 109.5 . . ? C34 C36 H36C 109.5 . . ? H36A C36 H36C 109.5 . . ? H36B C36 H36C 109.5 . . ? N4 C37 C38 123.4(3) . . ? N4 C37 H37 118.3 . . ? C38 C37 H37 118.3 . . ? C39 C38 C37 120.1(3) . . ? C39 C38 H38 120 . . ? C37 C38 H38 120 . . ? C40 C39 C38 117.7(3) . . ? C40 C39 H39 121.1 . . ? C38 C39 H39 121.1 . . ? C39 C40 C41 120.4(3) . . ? C39 C40 H40 119.8 . . ? C41 C40 H40 119.8 . . ? N4 C41 C40 122.6(3) . . ? N4 C41 H41 118.7 . . ? C40 C41 H41 118.7 . . ? N5 C42 C43 123.2(2) . . ? N5 C42 H42 118.4 . . ? C43 C42 H42 118.4 . . ? C44 C43 C42 119.4(2) . . ? C44 C43 H43 120.3 . . ? C42 C43 H43 120.3 . . ? C43 C44 C45 118.1(2) . . ? C43 C44 H44 121 . . ? C45 C44 H44 121 . . ? C44 C45 C46 119.5(2) . . ? C44 C45 H45 120.3 . . ? C46 C45 H45 120.3 . . ? N5 C46 C45 123.3(2) . . ? N5 C46 H46 118.3 . . ? C45 C46 H46 118.3 . . ? C1 N1 Ti1 144.60(14) . . ? C1 N1 H1 107.7 . . ? Ti1 N1 H1 107.7 . . ? C13 N2 Ti1 175.80(15) . . ? C25 N3 Ti1 154.45(14) . . ? C25 N3 H3A 102.8 . . ? Ti1 N3 H3A 102.8 . . ? C41 N4 C37 115.7(2) . . ? C41 N4 Ti1 123.51(16) . . ? C37 N4 Ti1 120.50(16) . . ? C46 N5 C42 116.46(18) . . ? C46 N5 Ti1 122.10(14) . . ? C42 N5 Ti1 121.13(14) . . ? N2 Ti1 N1 99.41(7) . . ? N2 Ti1 N3 113.50(7) . . ? N1 Ti1 N3 147.04(7) . . ? N2 Ti1 N5 100.04(7) . . ? N1 Ti1 N5 88.65(6) . . ? N3 Ti1 N5 87.38(7) . . ? N2 Ti1 N4 104.20(7) . . ? N1 Ti1 N4 87.41(7) . . ? N3 Ti1 N4 83.04(7) . . ? N5 Ti1 N4 155.76(6) . . ? # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|\-=[];'`,./ # END of CIF _database_code_depnum_ccdc_archive 'CCDC 931109'