# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Schwarz, Andrew' 'Nova, Ainara' 'Clot, Eric' 'Mountford, Philip' _publ_contact_author_name 'Mountford, Philip' _publ_contact_author_email philip.mountford@chem.ox.ac.uk _publ_section_title ; Titanium alkoxyimido (Ti=N-OR) complexes: reductive N-O bond cleavage at the boundary between hydrazide and peroxide ligands ; data_COMPOUND_1 _database_code_depnum_ccdc_archive 'CCDC 813256' #TrackingRef '- Mountford Xray SI.CIF' # Local code ADS139 _chemical_name_systematic ; Ti(NOtBu)Cl2(NHMe2)2 ; _chemical_melting_point ? _publ_section_exptl_refinement ; N-bound H atoms were located from a Fourier difference map and positionally and isotropically refined. C-bound H atoms were placed in calculated positions with reference to a Fourier difference map and were refined in a riding model. ; _cell_length_a 9.64230(10) _cell_length_b 11.1483(2) _cell_length_c 16.3073(3) _cell_angle_alpha 107.0308(6) _cell_angle_beta 90.9663(7) _cell_angle_gamma 113.4410(7) _cell_volume 1519.88(4) _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1 ' _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source Ti 0.2776 0.4457 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International Tables Vol C 4.2.6.8 and 6.1.1.4' C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 _chemical_formula_sum 'C8 H23 Cl2 N3 O1 Ti1' _chemical_formula_moiety 'C8 H23 Cl2 N3 O1 Ti1' _chemical_compound_source ? _chemical_formula_weight 296.10 _cell_measurement_reflns_used 6443 _cell_measurement_theta_min 5 _cell_measurement_theta_max 27 _cell_measurement_temperature 150 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_max 0.20 _exptl_crystal_density_diffrn 1.294 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 0.898 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.84 _exptl_absorpt_correction_T_max 0.84 _diffrn_measurement_device 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'COLLECT (Nonius, 1997-2001).' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 11924 _reflns_number_total 6911 _diffrn_reflns_av_R_equivalents 0.040 _diffrn_reflns_theta_min 5.141 _diffrn_reflns_theta_max 27.494 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 26.120 _diffrn_measured_fraction_theta_full 0.991 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _reflns_limit_h_min -12 _reflns_limit_h_max 12 _reflns_limit_k_min -14 _reflns_limit_k_max 13 _reflns_limit_l_min 0 _reflns_limit_l_max 21 _oxford_diffrn_Wilson_B_factor 2.21 _oxford_diffrn_Wilson_scale 21.10 _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.35 _refine_diff_density_max 0.43 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 3876 _refine_ls_number_restraints 0 _refine_ls_number_parameters 287 _oxford_refine_ls_R_factor_ref 0.0401 _refine_ls_wR_factor_ref 0.0407 _refine_ls_goodness_of_fit_ref 1.1278 _refine_ls_shift/su_max 0.001090 # The values computed from all data _oxford_reflns_number_all 6911 _refine_ls_R_factor_all 0.0927 _refine_ls_wR_factor_all 0.1192 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 4310 _refine_ls_R_factor_gt 0.0464 _refine_ls_wR_factor_gt 0.0446 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.295 0.227 0.983E-01 0.791E-01 0.856E-03 ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (1997-2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994). Acta Cryst, A50, 411-437. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens Ti1 Ti -0.31574(6) 0.22667(6) -0.05373(4) 0.0200 1.0000 Uani . . . . . . . Ti2 Ti 0.22274(7) 0.27057(6) 0.45727(4) 0.0220 1.0000 Uani . . . . . . . N1 N -0.2613(3) 0.1592(3) 0.01416(17) 0.0216 1.0000 Uani . . . . . . . N2 N -0.1070(3) 0.2769(3) -0.11603(19) 0.0236 1.0000 Uani . . . . . . . N3 N -0.5430(3) 0.1937(3) -0.01505(18) 0.0213 1.0000 Uani . . . . . . . N4 N 0.3330(3) 0.3419(3) 0.55568(18) 0.0247 1.0000 Uani . . . . . . . N5 N 0.4123(3) 0.3052(3) 0.38030(18) 0.0235 1.0000 Uani . . . . . . . N6 N 0.0013(3) 0.2222(3) 0.5078(2) 0.0283 1.0000 Uani . . . . . . . O1 O -0.2231(3) 0.0979(2) 0.06673(15) 0.0255 1.0000 Uani . . . . . . . O2 O 0.4206(3) 0.4068(2) 0.63562(15) 0.0285 1.0000 Uani . . . . . . . C1 C -0.1120(4) 0.1970(3) 0.1461(2) 0.0259 1.0000 Uani . . . . . . . C2 C -0.1768(5) 0.2925(4) 0.1985(2) 0.0395 1.0000 Uani . . . . . . . C3 C 0.0374(4) 0.2735(4) 0.1186(3) 0.0411 1.0000 Uani . . . . . . . C4 C -0.0994(5) 0.0999(4) 0.1921(3) 0.0371 1.0000 Uani . . . . . . . C5 C -0.1087(4) 0.3299(4) -0.1890(2) 0.0363 1.0000 Uani . . . . . . . C6 C -0.0538(4) 0.1662(4) -0.1403(2) 0.0323 1.0000 Uani . . . . . . . C7 C -0.6222(4) 0.2638(4) -0.0477(2) 0.0322 1.0000 Uani . . . . . . . C8 C -0.5494(4) 0.2165(4) 0.0781(2) 0.0310 1.0000 Uani . . . . . . . C9 C 0.4360(4) 0.3109(4) 0.6779(2) 0.0284 1.0000 Uani . . . . . . . C10 C 0.5459(5) 0.4109(4) 0.7608(3) 0.0443 1.0000 Uani . . . . . . . C11 C 0.5029(5) 0.2211(4) 0.6211(3) 0.0417 1.0000 Uani . . . . . . . C12 C 0.2809(4) 0.2269(4) 0.6968(3) 0.0405 1.0000 Uani . . . . . . . C13 C 0.3657(4) 0.2460(4) 0.2855(2) 0.0324 1.0000 Uani . . . . . . . C14 C 0.5365(4) 0.2713(4) 0.4050(3) 0.0345 1.0000 Uani . . . . . . . C15 C -0.1359(4) 0.1688(5) 0.4428(3) 0.0433 1.0000 Uani . . . . . . . C16 C 0.0022(5) 0.3353(4) 0.5826(3) 0.0415 1.0000 Uani . . . . . . . Cl1 Cl -0.23510(9) 0.46682(8) 0.01232(6) 0.0300 1.0000 Uani . . . . . . . Cl2 Cl -0.45170(9) 0.06538(9) -0.18887(5) 0.0284 1.0000 Uani . . . . . . . Cl3 Cl 0.17181(10) 0.42624(9) 0.40510(6) 0.0324 1.0000 Uani . . . . . . . Cl4 Cl 0.14976(10) 0.03072(9) 0.39989(6) 0.0329 1.0000 Uani . . . . . . . H1 H -0.043(4) 0.340(4) -0.078(3) 0.029(5) 1.0000 Uiso . . . . . . . H2 H -0.597(4) 0.107(4) -0.044(2) 0.029(5) 1.0000 Uiso . . . . . . . H3 H 0.450(4) 0.388(4) 0.392(2) 0.029(5) 1.0000 Uiso . . . . . . . H4 H -0.006(4) 0.160(4) 0.526(3) 0.029(5) 1.0000 Uiso . . . . . . . H21 H -0.2700 0.2395 0.2146 0.0497 1.0000 Uiso R . . . . . . H22 H -0.1061 0.3554 0.2493 0.0497 1.0000 Uiso R . . . . . . H23 H -0.1953 0.3425 0.1648 0.0497 1.0000 Uiso R . . . . . . H31 H 0.0731 0.2087 0.0860 0.0528 1.0000 Uiso R . . . . . . H32 H 0.1111 0.3362 0.1682 0.0528 1.0000 Uiso R . . . . . . H33 H 0.0218 0.3232 0.0837 0.0528 1.0000 Uiso R . . . . . . H41 H -0.0579 0.0418 0.1571 0.0473 1.0000 Uiso R . . . . . . H42 H -0.0347 0.1524 0.2464 0.0473 1.0000 Uiso R . . . . . . H43 H -0.1983 0.0447 0.2013 0.0473 1.0000 Uiso R . . . . . . H51 H -0.1419 0.4021 -0.1727 0.0466 1.0000 Uiso R . . . . . . H52 H -0.1772 0.2566 -0.2374 0.0466 1.0000 Uiso R . . . . . . H53 H -0.0090 0.3643 -0.2041 0.0466 1.0000 Uiso R . . . . . . H61 H -0.0522 0.1335 -0.0928 0.0417 1.0000 Uiso R . . . . . . H62 H -0.1221 0.0927 -0.1886 0.0417 1.0000 Uiso R . . . . . . H63 H 0.0461 0.2004 -0.1553 0.0417 1.0000 Uiso R . . . . . . H71 H -0.6178 0.2479 -0.1079 0.0403 1.0000 Uiso R . . . . . . H72 H -0.7260 0.2290 -0.0388 0.0403 1.0000 Uiso R . . . . . . H73 H -0.5730 0.3603 -0.0172 0.0403 1.0000 Uiso R . . . . . . H81 H -0.4990 0.1705 0.0984 0.0399 1.0000 Uiso R . . . . . . H82 H -0.6531 0.1816 0.0872 0.0399 1.0000 Uiso R . . . . . . H83 H -0.5000 0.3130 0.1088 0.0399 1.0000 Uiso R . . . . . . H101 H 0.5004 0.4659 0.7950 0.0561 1.0000 Uiso R . . . . . . H102 H 0.5688 0.3607 0.7929 0.0561 1.0000 Uiso R . . . . . . H103 H 0.6375 0.4690 0.7459 0.0561 1.0000 Uiso R . . . . . . H111 H 0.4310 0.1598 0.5704 0.0509 1.0000 Uiso R . . . . . . H112 H 0.5255 0.1691 0.6519 0.0509 1.0000 Uiso R . . . . . . H113 H 0.5941 0.2774 0.6049 0.0509 1.0000 Uiso R . . . . . . H121 H 0.2159 0.1657 0.6438 0.0522 1.0000 Uiso R . . . . . . H122 H 0.2911 0.1750 0.7316 0.0522 1.0000 Uiso R . . . . . . H123 H 0.2379 0.2874 0.7269 0.0522 1.0000 Uiso R . . . . . . H131 H 0.2864 0.2685 0.2693 0.0411 1.0000 Uiso R . . . . . . H132 H 0.4504 0.2816 0.2570 0.0411 1.0000 Uiso R . . . . . . H133 H 0.3295 0.1483 0.2690 0.0411 1.0000 Uiso R . . . . . . H141 H 0.5680 0.3105 0.4660 0.0448 1.0000 Uiso R . . . . . . H142 H 0.6209 0.3069 0.3763 0.0448 1.0000 Uiso R . . . . . . H143 H 0.5000 0.1736 0.3883 0.0448 1.0000 Uiso R . . . . . . H151 H -0.1363 0.0951 0.3951 0.0536 1.0000 Uiso R . . . . . . H152 H -0.2254 0.1364 0.4684 0.0536 1.0000 Uiso R . . . . . . H153 H -0.1339 0.2416 0.4231 0.0536 1.0000 Uiso R . . . . . . H161 H 0.0904 0.3680 0.6240 0.0522 1.0000 Uiso R . . . . . . H162 H -0.0870 0.3033 0.6085 0.0522 1.0000 Uiso R . . . . . . H163 H 0.0045 0.4085 0.5632 0.0522 1.0000 Uiso 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 0.0183(3) 0.0183(3) 0.0218(3) 0.0068(2) 0.0023(2) 0.0061(2) Ti2 0.0226(3) 0.0210(3) 0.0233(3) 0.0098(3) 0.0043(3) 0.0083(3) N1 0.0187(13) 0.0206(14) 0.0241(14) 0.0074(12) 0.0016(11) 0.0070(11) N2 0.0235(15) 0.0213(15) 0.0231(15) 0.0071(12) 0.0025(12) 0.0068(12) N3 0.0216(14) 0.0220(15) 0.0206(14) 0.0074(12) 0.0023(11) 0.0092(12) N4 0.0261(15) 0.0280(16) 0.0217(15) 0.0120(13) 0.0030(12) 0.0104(12) N5 0.0284(15) 0.0181(14) 0.0214(15) 0.0045(12) 0.0042(12) 0.0085(12) N6 0.0257(15) 0.0331(18) 0.0344(17) 0.0184(15) 0.0103(13) 0.0151(14) O1 0.0255(12) 0.0239(12) 0.0258(12) 0.0113(10) -0.0041(10) 0.0072(10) O2 0.0308(13) 0.0236(13) 0.0261(13) 0.0109(10) -0.0025(10) 0.0049(10) C1 0.0226(17) 0.0243(18) 0.0223(17) 0.0074(15) -0.0039(14) 0.0020(14) C2 0.044(2) 0.043(2) 0.029(2) 0.0026(18) -0.0032(17) 0.022(2) C3 0.0242(19) 0.045(2) 0.046(2) 0.020(2) -0.0040(17) 0.0026(17) C4 0.037(2) 0.038(2) 0.033(2) 0.0182(18) -0.0060(17) 0.0092(18) C5 0.035(2) 0.043(2) 0.034(2) 0.0196(18) 0.0113(17) 0.0141(18) C6 0.0287(19) 0.035(2) 0.037(2) 0.0107(17) 0.0125(16) 0.0176(16) C7 0.0291(19) 0.037(2) 0.036(2) 0.0163(17) 0.0032(16) 0.0166(17) C8 0.0280(19) 0.038(2) 0.0294(19) 0.0111(16) 0.0077(15) 0.0154(16) C9 0.0274(18) 0.0300(19) 0.0281(18) 0.0165(16) 0.0024(15) 0.0074(15) C10 0.044(2) 0.038(2) 0.038(2) 0.0162(19) -0.0140(19) 0.0031(19) C11 0.050(3) 0.048(3) 0.041(2) 0.025(2) 0.0076(19) 0.026(2) C12 0.036(2) 0.042(2) 0.043(2) 0.024(2) 0.0053(18) 0.0083(18) C13 0.037(2) 0.035(2) 0.0236(18) 0.0093(16) 0.0060(16) 0.0138(17) C14 0.0306(19) 0.047(2) 0.035(2) 0.0184(18) 0.0098(16) 0.0211(18) C15 0.029(2) 0.052(3) 0.049(3) 0.025(2) 0.0081(18) 0.0105(18) C16 0.043(2) 0.046(2) 0.048(3) 0.020(2) 0.020(2) 0.028(2) Cl1 0.0237(4) 0.0200(4) 0.0412(5) 0.0058(4) 0.0041(4) 0.0072(3) Cl2 0.0254(4) 0.0287(5) 0.0239(4) 0.0037(4) 0.0017(3) 0.0078(3) Cl3 0.0337(5) 0.0329(5) 0.0406(5) 0.0211(4) 0.0085(4) 0.0173(4) Cl4 0.0367(5) 0.0213(4) 0.0378(5) 0.0103(4) 0.0118(4) 0.0088(4) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.2091(3) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.688(3) yes Ti1 . N2 . 2.214(3) yes Ti1 . N3 . 2.208(3) yes Ti1 . Cl1 . 2.3577(10) yes Ti1 . Cl2 . 2.3483(10) yes Ti2 . N4 . 1.691(3) yes Ti2 . N5 . 2.206(3) yes Ti2 . N6 . 2.221(3) yes Ti2 . Cl3 . 2.3464(10) yes Ti2 . Cl4 . 2.3528(11) yes N1 . O1 . 1.368(3) yes N2 . C5 . 1.478(4) yes N2 . C6 . 1.471(4) yes N2 . H1 . 0.81(4) no N3 . C7 . 1.477(4) yes N3 . C8 . 1.471(4) yes N3 . H2 . 0.87(4) no N4 . O2 . 1.364(3) yes N5 . C13 . 1.474(4) yes N5 . C14 . 1.474(4) yes N5 . H3 . 0.81(4) no N6 . C15 . 1.478(5) yes N6 . C16 . 1.473(5) yes N6 . H4 . 0.82(4) no O1 . C1 . 1.489(4) yes O2 . C9 . 1.481(4) yes C1 . C2 . 1.506(5) yes C1 . C3 . 1.507(5) yes C1 . C4 . 1.526(5) yes C2 . H21 . 0.950 no C2 . H22 . 0.950 no C2 . H23 . 0.950 no C3 . H31 . 0.950 no C3 . H32 . 0.950 no C3 . H33 . 0.950 no C4 . H41 . 0.950 no C4 . H42 . 0.950 no C4 . H43 . 0.950 no C5 . H51 . 0.950 no C5 . H52 . 0.950 no C5 . H53 . 0.950 no C6 . H61 . 0.950 no C6 . H62 . 0.950 no C6 . H63 . 0.950 no C7 . H71 . 0.950 no C7 . H72 . 0.950 no C7 . H73 . 0.950 no C8 . H81 . 0.950 no C8 . H82 . 0.950 no C8 . H83 . 0.950 no C9 . C10 . 1.524(5) yes C9 . C11 . 1.507(5) yes C9 . C12 . 1.509(5) yes C10 . H101 . 0.950 no C10 . H102 . 0.950 no C10 . H103 . 0.950 no C11 . H111 . 0.950 no C11 . H112 . 0.950 no C11 . H113 . 0.950 no C12 . H121 . 0.950 no C12 . H122 . 0.950 no C12 . H123 . 0.950 no C13 . H131 . 0.950 no C13 . H132 . 0.950 no C13 . H133 . 0.950 no C14 . H141 . 0.950 no C14 . H142 . 0.950 no C14 . H143 . 0.950 no C15 . H151 . 0.950 no C15 . H152 . 0.950 no C15 . H153 . 0.950 no C16 . H161 . 0.950 no C16 . H162 . 0.950 no C16 . H163 . 0.950 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 96.72(12) yes N1 . Ti1 . N3 . 97.12(12) yes N2 . Ti1 . N3 . 166.11(10) yes N1 . Ti1 . Cl1 . 110.50(10) yes N2 . Ti1 . Cl1 . 87.27(8) yes N3 . Ti1 . Cl1 . 88.98(8) yes N1 . Ti1 . Cl2 . 114.62(10) yes N2 . Ti1 . Cl2 . 87.75(8) yes N3 . Ti1 . Cl2 . 85.44(8) yes Cl1 . Ti1 . Cl2 . 134.88(4) yes N4 . Ti2 . N5 . 96.48(12) yes N4 . Ti2 . N6 . 95.64(13) yes N5 . Ti2 . N6 . 167.75(11) yes N4 . Ti2 . Cl3 . 114.95(10) yes N5 . Ti2 . Cl3 . 85.53(8) yes N6 . Ti2 . Cl3 . 87.76(9) yes N4 . Ti2 . Cl4 . 112.35(10) yes N5 . Ti2 . Cl4 . 89.50(8) yes N6 . Ti2 . Cl4 . 87.53(9) yes Cl3 . Ti2 . Cl4 . 132.70(4) yes Ti1 . N1 . O1 . 177.0(2) yes Ti1 . N2 . C5 . 116.2(2) yes Ti1 . N2 . C6 . 114.3(2) yes C5 . N2 . C6 . 110.1(3) yes Ti1 . N2 . H1 . 103(3) no C5 . N2 . H1 . 106(3) no C6 . N2 . H1 . 106(3) no Ti1 . N3 . C7 . 115.6(2) yes Ti1 . N3 . C8 . 115.2(2) yes C7 . N3 . C8 . 110.3(3) yes Ti1 . N3 . H2 . 102(2) no C7 . N3 . H2 . 104(2) no C8 . N3 . H2 . 109(3) no Ti2 . N4 . O2 . 176.4(2) yes Ti2 . N5 . C13 . 115.2(2) yes Ti2 . N5 . C14 . 116.7(2) yes C13 . N5 . C14 . 109.4(3) yes Ti2 . N5 . H3 . 103(3) no C13 . N5 . H3 . 106(3) no C14 . N5 . H3 . 106(3) no Ti2 . N6 . C15 . 116.0(2) yes Ti2 . N6 . C16 . 113.6(2) yes C15 . N6 . C16 . 110.4(3) yes Ti2 . N6 . H4 . 103(3) no C15 . N6 . H4 . 107(3) no C16 . N6 . H4 . 106(3) no N1 . O1 . C1 . 114.2(2) yes N4 . O2 . C9 . 113.9(2) yes O1 . C1 . C2 . 109.6(3) yes O1 . C1 . C3 . 108.4(3) yes C2 . C1 . C3 . 112.6(3) yes O1 . C1 . C4 . 101.8(3) yes C2 . C1 . C4 . 112.0(3) yes C3 . C1 . C4 . 111.8(3) yes C1 . C2 . H21 . 109.3 no C1 . C2 . H22 . 109.6 no H21 . C2 . H22 . 109.5 no C1 . C2 . H23 . 109.5 no H21 . C2 . H23 . 109.5 no H22 . C2 . H23 . 109.5 no C1 . C3 . H31 . 109.1 no C1 . C3 . H32 . 110.0 no H31 . C3 . H32 . 109.5 no C1 . C3 . H33 . 109.2 no H31 . C3 . H33 . 109.5 no H32 . C3 . H33 . 109.5 no C1 . C4 . H41 . 109.4 no C1 . C4 . H42 . 109.7 no H41 . C4 . H42 . 109.5 no C1 . C4 . H43 . 109.3 no H41 . C4 . H43 . 109.5 no H42 . C4 . H43 . 109.5 no N2 . C5 . H51 . 109.7 no N2 . C5 . H52 . 108.9 no H51 . C5 . H52 . 109.5 no N2 . C5 . H53 . 109.8 no H51 . C5 . H53 . 109.5 no H52 . C5 . H53 . 109.5 no N2 . C6 . H61 . 109.4 no N2 . C6 . H62 . 108.9 no H61 . C6 . H62 . 109.5 no N2 . C6 . H63 . 110.1 no H61 . C6 . H63 . 109.5 no H62 . C6 . H63 . 109.5 no N3 . C7 . H71 . 109.5 no N3 . C7 . H72 . 109.9 no H71 . C7 . H72 . 109.5 no N3 . C7 . H73 . 109.0 no H71 . C7 . H73 . 109.5 no H72 . C7 . H73 . 109.5 no N3 . C8 . H81 . 109.8 no N3 . C8 . H82 . 109.5 no H81 . C8 . H82 . 109.5 no N3 . C8 . H83 . 109.0 no H81 . C8 . H83 . 109.5 no H82 . C8 . H83 . 109.5 no O2 . C9 . C10 . 101.9(3) yes O2 . C9 . C11 . 110.1(3) yes C10 . C9 . C11 . 111.7(3) yes O2 . C9 . C12 . 108.6(3) yes C10 . C9 . C12 . 111.8(3) yes C11 . C9 . C12 . 112.2(3) yes C9 . C10 . H101 . 109.5 no C9 . C10 . H102 . 109.9 no H101 . C10 . H102 . 109.5 no C9 . C10 . H103 . 109.0 no H101 . C10 . H103 . 109.5 no H102 . C10 . H103 . 109.5 no C9 . C11 . H111 . 109.2 no C9 . C11 . H112 . 109.5 no H111 . C11 . H112 . 109.5 no C9 . C11 . H113 . 109.7 no H111 . C11 . H113 . 109.5 no H112 . C11 . H113 . 109.5 no C9 . C12 . H121 . 109.4 no C9 . C12 . H122 . 109.7 no H121 . C12 . H122 . 109.5 no C9 . C12 . H123 . 109.3 no H121 . C12 . H123 . 109.5 no H122 . C12 . H123 . 109.5 no N5 . C13 . H131 . 109.6 no N5 . C13 . H132 . 110.1 no H131 . C13 . H132 . 109.5 no N5 . C13 . H133 . 108.6 no H131 . C13 . H133 . 109.5 no H132 . C13 . H133 . 109.5 no N5 . C14 . H141 . 109.7 no N5 . C14 . H142 . 109.8 no H141 . C14 . H142 . 109.5 no N5 . C14 . H143 . 108.9 no H141 . C14 . H143 . 109.5 no H142 . C14 . H143 . 109.5 no N6 . C15 . H151 . 109.9 no N6 . C15 . H152 . 109.7 no H151 . C15 . H152 . 109.5 no N6 . C15 . H153 . 108.8 no H151 . C15 . H153 . 109.5 no H152 . C15 . H153 . 109.5 no N6 . C16 . H161 . 109.4 no N6 . C16 . H162 . 110.0 no H161 . C16 . H162 . 109.5 no N6 . C16 . H163 . 108.9 no H161 . C16 . H163 . 109.5 no H162 . C16 . H163 . 109.5 no #===end data_COMPOUND_3 _database_code_depnum_ccdc_archive 'CCDC 813257' #TrackingRef '- Mountford Xray SI.CIF' # Local code ADS141 _chemical_name_systematic ; Ti(NOtBu)Cl2(py)3 ; _chemical_melting_point ? _refine_special_details ; Hydrogen atoms were placed geometrically with reference to a Fourier difference map and refined in a riding model. ; _cell_length_a 8.79620(10) _cell_length_b 21.8932(3) _cell_length_c 11.4868(2) _cell_angle_alpha 90 _cell_angle_beta 97.1358(6) _cell_angle_gamma 90 _cell_volume 2194.96(5) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ti 0.2776 0.4457 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 _chemical_formula_sum 'C19 H24 Cl2 N4 O1 Ti1' _chemical_formula_moiety 'C19 H24 Cl2 N4 O1 Ti1' _chemical_compound_source ? _chemical_formula_weight 443.23 _cell_measurement_reflns_used 4544 _cell_measurement_theta_min 5 _cell_measurement_theta_max 27 _cell_measurement_temperature 150 _exptl_crystal_description block _exptl_crystal_colour 'dark purple' _exptl_crystal_size_min 0.400 _exptl_crystal_size_mid 0.400 _exptl_crystal_size_max 0.500 _exptl_crystal_density_diffrn 1.341 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 920 _exptl_absorpt_coefficient_mu 0.649 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.77 _exptl_absorpt_correction_T_max 0.77 _diffrn_measurement_device 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'COLLECT (Nonius, 2001).' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 8673 _reflns_number_total 4991 _diffrn_reflns_av_R_equivalents 0.028 _diffrn_reflns_theta_min 5.140 _diffrn_reflns_theta_max 27.478 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 26.104 _diffrn_measured_fraction_theta_full 0.990 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _reflns_limit_h_min -11 _reflns_limit_h_max 11 _reflns_limit_k_min 0 _reflns_limit_k_max 28 _reflns_limit_l_min 0 _reflns_limit_l_max 14 _oxford_diffrn_Wilson_B_factor 2.01 _oxford_diffrn_Wilson_scale 9.87 _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.26 _refine_diff_density_max 0.52 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 3235 _refine_ls_number_restraints 0 _refine_ls_number_parameters 244 _oxford_refine_ls_R_factor_ref 0.0323 _refine_ls_wR_factor_ref 0.0307 _refine_ls_goodness_of_fit_ref 1.1111 _refine_ls_shift/su_max 0.0003448 _refine_ls_shift/su_mean 3.4503958 # The values computed from all data _oxford_reflns_number_all 4991 _refine_ls_R_factor_all 0.0675 _refine_ls_wR_factor_all 0.0673 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 3570 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_gt 0.0335 _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment none _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.292 -0.198E-02 0.312E-01 ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994). Acta Cryst, A50, 411-437. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens Ti1 Ti 0.21843(4) 0.383343(17) 0.21071(3) 0.0180 1.0000 Uani . . . . . . . N1 N 0.11897(19) 0.31612(8) 0.19999(15) 0.0206 1.0000 Uani . . . . . . . N2 N 0.3383(2) 0.48239(8) 0.21965(16) 0.0239 1.0000 Uani . . . . . . . N3 N 0.4290(2) 0.34559(8) 0.14797(15) 0.0232 1.0000 Uani . . . . . . . N4 N 0.0324(2) 0.43612(8) 0.28273(15) 0.0206 1.0000 Uani . . . . . . . Cl1 Cl 0.13014(7) 0.41458(3) 0.01317(5) 0.0290 1.0000 Uani . . . . . . . Cl2 Cl 0.34939(7) 0.37148(3) 0.40886(5) 0.0295 1.0000 Uani . . . . . . . O1 O 0.03049(17) 0.26641(7) 0.17402(13) 0.0258 1.0000 Uani . . . . . . . C1 C 0.0557(3) 0.21759(10) 0.26373(19) 0.0249 1.0000 Uani . . . . . . . C2 C 0.2180(3) 0.19488(11) 0.2667(2) 0.0310 1.0000 Uani . . . . . . . C3 C 0.0245(3) 0.24259(12) 0.3809(2) 0.0353 1.0000 Uani . . . . . . . C4 C -0.0594(3) 0.16952(13) 0.2184(3) 0.0463 1.0000 Uani . . . . . . . C5 C 0.3809(3) 0.51099(12) 0.1265(2) 0.0371 1.0000 Uani . . . . . . . C6 C 0.4382(4) 0.57002(13) 0.1308(3) 0.0483 1.0000 Uani . . . . . . . C7 C 0.4488(3) 0.60176(12) 0.2344(3) 0.0434 1.0000 Uani . . . . . . . C8 C 0.4072(3) 0.57308(11) 0.3315(2) 0.0347 1.0000 Uani . . . . . . . C9 C 0.3541(3) 0.51379(11) 0.3207(2) 0.0275 1.0000 Uani . . . . . . . C10 C -0.0390(3) 0.48375(10) 0.22605(19) 0.0252 1.0000 Uani . . . . . . . C11 C -0.1589(3) 0.51451(11) 0.2673(2) 0.0307 1.0000 Uani . . . . . . . C12 C -0.2080(3) 0.49622(12) 0.3707(2) 0.0349 1.0000 Uani . . . . . . . C13 C -0.1361(3) 0.44709(12) 0.4294(2) 0.0369 1.0000 Uani . . . . . . . C14 C -0.0176(3) 0.41854(11) 0.3833(2) 0.0288 1.0000 Uani . . . . . . . C15 C 0.5717(3) 0.36568(12) 0.1856(2) 0.0327 1.0000 Uani . . . . . . . C16 C 0.7007(3) 0.34094(13) 0.1466(2) 0.0400 1.0000 Uani . . . . . . . C17 C 0.6841(3) 0.29362(12) 0.0662(2) 0.0377 1.0000 Uani . . . . . . . C18 C 0.5395(3) 0.27239(12) 0.0281(2) 0.0320 1.0000 Uani . . . . . . . C19 C 0.4154(3) 0.29934(10) 0.0711(2) 0.0264 1.0000 Uani . . . . . . . H21 H 0.2380 0.1634 0.3238 0.0380 1.0000 Uiso R . . . . . . H22 H 0.2888 0.2275 0.2859 0.0380 1.0000 Uiso R . . . . . . H23 H 0.2338 0.1789 0.1917 0.0380 1.0000 Uiso R . . . . . . H31 H 0.0406 0.2118 0.4395 0.0435 1.0000 Uiso R . . . . . . H32 H 0.0918 0.2761 0.4033 0.0435 1.0000 Uiso R . . . . . . H33 H -0.0786 0.2568 0.3764 0.0435 1.0000 Uiso R . . . . . . H41 H -0.0540 0.1352 0.2697 0.0573 1.0000 Uiso R . . . . . . H42 H -0.1615 0.1857 0.2113 0.0573 1.0000 Uiso R . . . . . . H43 H -0.0403 0.1558 0.1422 0.0573 1.0000 Uiso R . . . . . . H51 H 0.3704 0.4895 0.0529 0.0443 1.0000 Uiso R . . . . . . H61 H 0.4692 0.5888 0.0613 0.0583 1.0000 Uiso R . . . . . . H71 H 0.4857 0.6431 0.2392 0.0521 1.0000 Uiso R . . . . . . H81 H 0.4141 0.5940 0.4054 0.0426 1.0000 Uiso R . . . . . . H91 H 0.3266 0.4934 0.3898 0.0346 1.0000 Uiso R . . . . . . H101 H -0.0054 0.4971 0.1539 0.0301 1.0000 Uiso R . . . . . . H111 H -0.2075 0.5482 0.2237 0.0370 1.0000 Uiso R . . . . . . H121 H -0.2910 0.5171 0.4011 0.0417 1.0000 Uiso R . . . . . . H131 H -0.1681 0.4331 0.5017 0.0438 1.0000 Uiso R . . . . . . H141 H 0.0321 0.3842 0.4248 0.0352 1.0000 Uiso R . . . . . . H151 H 0.5833 0.3983 0.2427 0.0396 1.0000 Uiso R . . . . . . H161 H 0.8012 0.3567 0.1751 0.0483 1.0000 Uiso R . . . . . . H171 H 0.7724 0.2761 0.0368 0.0464 1.0000 Uiso R . . . . . . H181 H 0.5236 0.2389 -0.0268 0.0391 1.0000 Uiso R . . . . . . H191 H 0.3142 0.2845 0.0448 0.0325 1.0000 Uiso 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 0.02021(18) 0.01672(18) 0.01704(18) 0.00048(15) 0.00273(14) 0.00216(16) N1 0.0177(9) 0.0209(9) 0.0239(9) -0.0005(7) 0.0046(7) 0.0013(7) N2 0.0233(9) 0.0227(10) 0.0268(9) -0.0028(8) 0.0068(7) -0.0029(8) N3 0.0218(9) 0.0242(9) 0.0235(9) -0.0029(7) 0.0021(7) -0.0015(8) N4 0.0209(9) 0.0209(9) 0.0201(9) 0.0001(7) 0.0035(7) 0.0014(7) Cl1 0.0425(3) 0.0250(3) 0.0184(2) 0.0003(2) -0.0005(2) 0.0043(2) Cl2 0.0341(3) 0.0321(3) 0.0206(2) 0.0005(2) -0.0037(2) 0.0066(2) O1 0.0271(8) 0.0223(8) 0.0267(8) 0.0053(6) -0.0016(6) -0.0064(7) C1 0.0262(12) 0.0229(11) 0.0253(11) 0.0058(9) 0.0025(9) -0.0005(9) C2 0.0320(13) 0.0271(13) 0.0349(13) 0.0051(10) 0.0078(10) 0.0046(10) C3 0.0390(14) 0.0356(14) 0.0340(13) 0.0128(11) 0.0150(11) 0.0073(11) C4 0.0485(17) 0.0322(15) 0.0562(18) 0.0105(13) -0.0021(14) -0.0126(13) C5 0.0473(16) 0.0324(14) 0.0341(13) -0.0013(11) 0.0147(12) -0.0083(12) C6 0.0579(19) 0.0359(15) 0.0549(18) 0.0065(13) 0.0221(15) -0.0155(13) C7 0.0316(14) 0.0267(13) 0.073(2) -0.0069(13) 0.0093(13) -0.0061(11) C8 0.0263(12) 0.0310(13) 0.0463(15) -0.0172(12) 0.0027(11) -0.0022(10) C9 0.0247(11) 0.0288(12) 0.0288(12) -0.0061(10) 0.0029(9) 0.0001(9) C10 0.0299(12) 0.0212(11) 0.0247(11) 0.0041(9) 0.0043(9) 0.0022(9) C11 0.0295(12) 0.0301(13) 0.0323(12) 0.0035(10) 0.0032(10) 0.0086(10) C12 0.0308(13) 0.0397(14) 0.0354(13) -0.0013(11) 0.0093(10) 0.0109(11) C13 0.0407(14) 0.0439(15) 0.0292(13) 0.0080(11) 0.0165(11) 0.0105(12) C14 0.0335(13) 0.0285(12) 0.0255(11) 0.0052(10) 0.0085(9) 0.0081(10) C15 0.0251(12) 0.0348(14) 0.0370(13) -0.0122(11) -0.0004(10) -0.0021(10) C16 0.0199(12) 0.0473(16) 0.0521(16) -0.0107(13) 0.0013(11) 0.0002(11) C17 0.0253(13) 0.0443(16) 0.0437(15) -0.0083(12) 0.0046(11) 0.0094(11) C18 0.0332(13) 0.0329(13) 0.0303(12) -0.0112(10) 0.0049(10) 0.0018(11) C19 0.0230(11) 0.0283(12) 0.0277(11) -0.0051(10) 0.0019(9) -0.0007(9) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.3122(3) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.7087(18) yes Ti1 . N2 . 2.4078(18) yes Ti1 . N3 . 2.2278(18) yes Ti1 . N4 . 2.2439(17) yes Ti1 . Cl1 . 2.4045(6) yes Ti1 . Cl2 . 2.4338(6) yes N1 . O1 . 1.350(2) yes N2 . C5 . 1.333(3) yes N2 . C9 . 1.342(3) yes N3 . C15 . 1.350(3) yes N3 . C19 . 1.339(3) yes N4 . C10 . 1.343(3) yes N4 . C14 . 1.343(3) yes O1 . C1 . 1.482(3) yes C1 . C2 . 1.508(3) yes C1 . C3 . 1.510(3) yes C1 . C4 . 1.507(3) yes C2 . H21 . 0.953 no C2 . H22 . 0.955 no C2 . H23 . 0.956 no C3 . H31 . 0.951 no C3 . H32 . 0.958 no C3 . H33 . 0.954 no C4 . H41 . 0.951 no C4 . H42 . 0.960 no C4 . H43 . 0.961 no C5 . C6 . 1.386(4) yes C5 . H51 . 0.962 no C6 . C7 . 1.371(4) yes C6 . H61 . 0.967 no C7 . C8 . 1.368(4) yes C7 . H71 . 0.961 no C8 . C9 . 1.380(3) yes C8 . H81 . 0.960 no C9 . H91 . 0.967 no C10 . C11 . 1.383(3) yes C10 . H101 . 0.959 no C11 . C12 . 1.373(3) yes C11 . H111 . 0.961 no C12 . C13 . 1.381(4) yes C12 . H121 . 0.963 no C13 . C14 . 1.376(3) yes C13 . H131 . 0.961 no C14 . H141 . 0.966 no C15 . C16 . 1.381(3) yes C15 . H151 . 0.966 no C16 . C17 . 1.384(4) yes C16 . H161 . 0.967 no C17 . C18 . 1.373(3) yes C17 . H171 . 0.964 no C18 . C19 . 1.385(3) yes C18 . H181 . 0.966 no C19 . H191 . 0.960 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 175.08(8) yes N1 . Ti1 . N3 . 95.50(8) yes N2 . Ti1 . N3 . 88.33(6) yes N1 . Ti1 . N4 . 94.57(7) yes N2 . Ti1 . N4 . 81.72(6) yes N3 . Ti1 . N4 . 169.74(7) yes N1 . Ti1 . Cl1 . 94.27(6) yes N2 . Ti1 . Cl1 . 82.68(5) yes N3 . Ti1 . Cl1 . 89.10(5) yes N4 . Ti1 . Cl1 . 92.10(5) yes N1 . Ti1 . Cl2 . 98.86(6) yes N2 . Ti1 . Cl2 . 84.40(5) yes N3 . Ti1 . Cl2 . 86.97(5) yes N4 . Ti1 . Cl2 . 89.56(5) yes Cl1 . Ti1 . Cl2 . 166.59(3) yes Ti1 . N1 . O1 . 170.57(15) yes Ti1 . N2 . C5 . 123.66(16) yes Ti1 . N2 . C9 . 119.74(15) yes C5 . N2 . C9 . 116.4(2) yes Ti1 . N3 . C15 . 123.57(15) yes Ti1 . N3 . C19 . 118.97(14) yes C15 . N3 . C19 . 117.43(19) yes Ti1 . N4 . C10 . 122.65(14) yes Ti1 . N4 . C14 . 120.09(14) yes C10 . N4 . C14 . 117.16(18) yes N1 . O1 . C1 . 113.30(15) yes O1 . C1 . C2 . 108.22(17) yes O1 . C1 . C3 . 109.31(18) yes C2 . C1 . C3 . 112.08(19) yes O1 . C1 . C4 . 103.16(18) yes C2 . C1 . C4 . 111.8(2) yes C3 . C1 . C4 . 111.9(2) yes C1 . C2 . H21 . 110.3 no C1 . C2 . H22 . 110.3 no H21 . C2 . H22 . 108.8 no C1 . C2 . H23 . 110.1 no H21 . C2 . H23 . 108.7 no H22 . C2 . H23 . 108.6 no C1 . C3 . H31 . 110.3 no C1 . C3 . H32 . 110.0 no H31 . C3 . H32 . 108.7 no C1 . C3 . H33 . 110.3 no H31 . C3 . H33 . 109.0 no H32 . C3 . H33 . 108.5 no C1 . C4 . H41 . 111.0 no C1 . C4 . H42 . 110.6 no H41 . C4 . H42 . 108.6 no C1 . C4 . H43 . 110.3 no H41 . C4 . H43 . 108.5 no H42 . C4 . H43 . 107.8 no N2 . C5 . C6 . 123.2(2) yes N2 . C5 . H51 . 118.0 no C6 . C5 . H51 . 118.8 no C5 . C6 . C7 . 119.2(3) yes C5 . C6 . H61 . 120.4 no C7 . C6 . H61 . 120.4 no C6 . C7 . C8 . 118.6(2) yes C6 . C7 . H71 . 120.9 no C8 . C7 . H71 . 120.5 no C7 . C8 . C9 . 118.7(2) yes C7 . C8 . H81 . 120.5 no C9 . C8 . H81 . 120.7 no C8 . C9 . N2 . 123.8(2) yes C8 . C9 . H91 . 118.6 no N2 . C9 . H91 . 117.6 no N4 . C10 . C11 . 122.8(2) yes N4 . C10 . H101 . 118.7 no C11 . C10 . H101 . 118.5 no C10 . C11 . C12 . 119.3(2) yes C10 . C11 . H111 . 120.2 no C12 . C11 . H111 . 120.5 no C11 . C12 . C13 . 118.4(2) yes C11 . C12 . H121 . 120.6 no C13 . C12 . H121 . 121.0 no C12 . C13 . C14 . 119.3(2) yes C12 . C13 . H131 . 120.3 no C14 . C13 . H131 . 120.4 no C13 . C14 . N4 . 123.0(2) yes C13 . C14 . H141 . 118.8 no N4 . C14 . H141 . 118.1 no N3 . C15 . C16 . 122.5(2) yes N3 . C15 . H151 . 118.3 no C16 . C15 . H151 . 119.2 no C15 . C16 . C17 . 119.2(2) yes C15 . C16 . H161 . 120.2 no C17 . C16 . H161 . 120.6 no C16 . C17 . C18 . 118.8(2) yes C16 . C17 . H171 . 120.6 no C18 . C17 . H171 . 120.5 no C17 . C18 . C19 . 118.8(2) yes C17 . C18 . H181 . 121.2 no C19 . C18 . H181 . 120.0 no C18 . C19 . N3 . 123.2(2) yes C18 . C19 . H191 . 119.0 no N3 . C19 . H191 . 117.8 no #===end data_COMPOUND_4a _database_code_depnum_ccdc_archive 'CCDC 813258' #TrackingRef '- Mountford Xray SI.CIF' # Local code ADS148 _chemical_name_systematic Ti(N2NMe)(NOtBu)(py) _chemical_melting_point ? _refine_special_details ; The hydrogens were placed geometrically and refined in a riding model ; _cell_length_a 10.0550(2) _cell_length_b 15.5409(3) _cell_length_c 17.4207(4) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2722.22(10) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_space_group_name_Hall 'P 2ac 2ab' 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 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Si 0.0817 0.0704 6.2915 2.4386 3.0353 32.3337 1.9891 0.6785 1.5410 81.6937 1.1407 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ti 0.2776 0.4457 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 _chemical_formula_sum 'C20 H43 N5 O1 Si2 Ti1' _chemical_formula_moiety 'C20 H43 N5 O1 Si2 Ti1' _chemical_compound_source ? _chemical_formula_weight 473.67 _cell_measurement_reflns_used 3372 _cell_measurement_theta_min 5 _cell_measurement_theta_max 27 _cell_measurement_temperature 150 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_min 0.100 _exptl_crystal_size_mid 0.200 _exptl_crystal_size_max 0.200 _exptl_crystal_density_diffrn 1.156 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1024 _exptl_absorpt_coefficient_mu 0.421 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.92 _exptl_absorpt_correction_T_max 0.96 _diffrn_measurement_device 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'COLLECT (Nonius, 2001).' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 22523 _reflns_number_total 6101 _diffrn_reflns_av_R_equivalents 0.073 _diffrn_reflns_theta_min 5.102 _diffrn_reflns_theta_max 27.455 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 26.631 _diffrn_measured_fraction_theta_full 0.990 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _reflns_limit_h_min -13 _reflns_limit_h_max 13 _reflns_limit_k_min 0 _reflns_limit_k_max 20 _reflns_limit_l_min 0 _reflns_limit_l_max 22 _oxford_diffrn_Wilson_B_factor 2.29 _oxford_diffrn_Wilson_scale 10.90 _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.28 _refine_diff_density_max 0.50 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 4299 _refine_ls_number_restraints 0 _refine_ls_number_parameters 263 _oxford_refine_ls_R_factor_ref 0.0390 _refine_ls_wR_factor_ref 0.0457 _refine_ls_goodness_of_fit_ref 0.9268 _refine_ls_shift/su_max 0.0006135 _refine_ls_shift/su_mean 0.0012877 # The values computed from all data _oxford_reflns_number_all 6101 _refine_ls_R_factor_all 0.0696 _refine_ls_wR_factor_all 0.0790 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 4759 _refine_ls_R_factor_gt 0.0457 _refine_ls_wR_factor_gt 0.0513 _refine_ls_abs_structure_Flack -0.02(3) _refine_ls_abs_structure_details 'Flack (1983), 1762 Friedel-pairs' _chemical_absolute_configuration ad _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment constr _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.743 0.245 0.577 0.352E-01 0.189 ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Flack, H. D. (1983). Acta Cryst. A39, 876-881. Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994). Acta Cryst, A50, 411-437. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens Ti1 Ti 0.30601(5) 0.51160(3) 0.64241(3) 0.0232 1.0000 Uani . . . . . . . N1 N 0.4445(2) 0.57026(16) 0.66760(14) 0.0263 1.0000 Uani . . . . . . . N2 N 0.1715(2) 0.60321(16) 0.62098(14) 0.0281 1.0000 Uani . . . . . . . N3 N 0.3714(3) 0.43052(17) 0.56010(14) 0.0313 1.0000 Uani . . . . . . . N4 N 0.1143(3) 0.43033(17) 0.61787(15) 0.0335 1.0000 Uani . . . . . . . N5 N 0.2937(3) 0.44835(16) 0.75512(13) 0.0299 1.0000 Uani . . . . . . . Si1 Si 0.19997(9) 0.71097(5) 0.63912(5) 0.0286 1.0000 Uani . . . . . . . Si2 Si 0.53048(10) 0.42128(6) 0.52386(5) 0.0363 1.0000 Uani . . . . . . . O1 O 0.5523(2) 0.62136(14) 0.68691(13) 0.0342 1.0000 Uani . . . . . . . C1 C 0.6341(3) 0.5892(2) 0.7510(2) 0.0358 1.0000 Uani . . . . . . . C2 C 0.7555(4) 0.6466(3) 0.7457(3) 0.0503 1.0000 Uani . . . . . . . C3 C 0.5592(4) 0.6006(3) 0.8255(2) 0.0607 1.0000 Uani . . . . . . . C4 C 0.6719(4) 0.4964(2) 0.7384(2) 0.0463 1.0000 Uani . . . . . . . C5 C 0.0430(3) 0.5773(2) 0.5882(2) 0.0383 1.0000 Uani . . . . . . . C6 C 0.0541(4) 0.4843(3) 0.5583(2) 0.0450 1.0000 Uani . . . . . . . C7 C 0.2785(4) 0.3660(2) 0.5307(2) 0.0429 1.0000 Uani . . . . . . . C8 C 0.1650(4) 0.3487(2) 0.5848(2) 0.0524 1.0000 Uani . . . . . . . C9 C 0.0200(4) 0.4112(3) 0.6786(3) 0.0641 1.0000 Uani . . . . . . . C10 C 0.3277(4) 0.7577(3) 0.5730(2) 0.0471 1.0000 Uani . . . . . . . C11 C 0.0433(4) 0.7752(2) 0.6262(2) 0.0458 1.0000 Uani . . . . . . . C12 C 0.2542(5) 0.7303(2) 0.7402(2) 0.0502 1.0000 Uani . . . . . . . C13 C 0.6245(4) 0.5249(3) 0.5202(2) 0.0482 1.0000 Uani . . . . . . . C14 C 0.6267(4) 0.3374(3) 0.5769(2) 0.0495 1.0000 Uani . . . . . . . C15 C 0.5282(5) 0.3820(3) 0.4212(2) 0.0640 1.0000 Uani . . . . . . . C16 C 0.3585(3) 0.3750(2) 0.7684(2) 0.0368 1.0000 Uani . . . . . . . C17 C 0.3623(4) 0.3357(2) 0.8394(2) 0.0449 1.0000 Uani . . . . . . . C18 C 0.2982(4) 0.3750(2) 0.89992(19) 0.0468 1.0000 Uani . . . . . . . C19 C 0.2305(4) 0.4505(3) 0.88749(19) 0.0423 1.0000 Uani . . . . . . . C20 C 0.2310(3) 0.4851(2) 0.81389(18) 0.0349 1.0000 Uani . . . . . . . H21 H 0.7996 0.6374 0.6981 0.0625 1.0000 Uiso R . . . . . . H22 H 0.8145 0.6337 0.7867 0.0625 1.0000 Uiso R . . . . . . H23 H 0.7282 0.7049 0.7491 0.0625 1.0000 Uiso R . . . . . . H31 H 0.4846 0.5632 0.8263 0.0730 1.0000 Uiso R . . . . . . H32 H 0.6162 0.5874 0.8673 0.0730 1.0000 Uiso R . . . . . . H33 H 0.5299 0.6585 0.8297 0.0730 1.0000 Uiso R . . . . . . H41 H 0.5952 0.4610 0.7417 0.0597 1.0000 Uiso R . . . . . . H42 H 0.7342 0.4795 0.7765 0.0597 1.0000 Uiso R . . . . . . H43 H 0.7109 0.4906 0.6890 0.0597 1.0000 Uiso R . . . . . . H51 H -0.0233 0.5790 0.6270 0.0454 1.0000 Uiso R . . . . . . H52 H 0.0193 0.6152 0.5477 0.0454 1.0000 Uiso R . . . . . . H61 H -0.0313 0.4627 0.5450 0.0574 1.0000 Uiso R . . . . . . H62 H 0.1097 0.4840 0.5142 0.0574 1.0000 Uiso R . . . . . . H71 H 0.3257 0.3140 0.5219 0.0532 1.0000 Uiso R . . . . . . H72 H 0.2426 0.3863 0.4836 0.0532 1.0000 Uiso R . . . . . . H81 H 0.1964 0.3133 0.6254 0.0659 1.0000 Uiso R . . . . . . H82 H 0.0949 0.3202 0.5586 0.0659 1.0000 Uiso R . . . . . . H91 H 0.0626 0.3765 0.7162 0.0841 1.0000 Uiso R . . . . . . H92 H -0.0105 0.4629 0.7017 0.0841 1.0000 Uiso R . . . . . . H93 H -0.0535 0.3807 0.6576 0.0841 1.0000 Uiso R . . . . . . H101 H 0.4089 0.7269 0.5779 0.0566 1.0000 Uiso R . . . . . . H102 H 0.3418 0.8164 0.5861 0.0566 1.0000 Uiso R . . . . . . H103 H 0.2969 0.7539 0.5216 0.0566 1.0000 Uiso R . . . . . . H111 H -0.0244 0.7532 0.6588 0.0565 1.0000 Uiso R . . . . . . H112 H 0.0601 0.8337 0.6387 0.0565 1.0000 Uiso R . . . . . . H113 H 0.0152 0.7712 0.5742 0.0565 1.0000 Uiso R . . . . . . H121 H 0.1907 0.7065 0.7746 0.0587 1.0000 Uiso R . . . . . . H122 H 0.2615 0.7904 0.7489 0.0587 1.0000 Uiso R . . . . . . H123 H 0.3381 0.7038 0.7485 0.0587 1.0000 Uiso R . . . . . . H131 H 0.5733 0.5667 0.4935 0.0608 1.0000 Uiso R . . . . . . H132 H 0.6408 0.5443 0.5710 0.0608 1.0000 Uiso R . . . . . . H133 H 0.7068 0.5166 0.4944 0.0608 1.0000 Uiso R . . . . . . H141 H 0.5776 0.2852 0.5778 0.0613 1.0000 Uiso R . . . . . . H142 H 0.6430 0.3560 0.6280 0.0613 1.0000 Uiso R . . . . . . H143 H 0.7091 0.3283 0.5514 0.0613 1.0000 Uiso R . . . . . . H151 H 0.6167 0.3776 0.4024 0.0743 1.0000 Uiso R . . . . . . H152 H 0.4797 0.4215 0.3904 0.0743 1.0000 Uiso R . . . . . . H153 H 0.4868 0.3271 0.4192 0.0743 1.0000 Uiso R . . . . . . H161 H 0.4022 0.3482 0.7263 0.0465 1.0000 Uiso R . . . . . . H171 H 0.4090 0.2832 0.8467 0.0557 1.0000 Uiso R . . . . . . H181 H 0.3005 0.3500 0.9497 0.0565 1.0000 Uiso R . . . . . . H191 H 0.1849 0.4784 0.9283 0.0535 1.0000 Uiso R . . . . . . H201 H 0.1846 0.5374 0.8047 0.0427 1.0000 Uiso 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 0.0240(2) 0.0257(2) 0.0199(2) -0.0019(2) 0.0009(2) 0.0005(2) N1 0.0241(12) 0.0269(12) 0.0280(12) -0.0027(10) -0.0032(10) 0.0001(10) N2 0.0190(12) 0.0348(14) 0.0304(13) -0.0025(10) -0.0007(9) -0.0014(10) N3 0.0379(14) 0.0287(14) 0.0273(13) -0.0069(11) 0.0020(11) 0.0011(11) N4 0.0359(15) 0.0317(14) 0.0328(14) 0.0001(11) -0.0022(11) -0.0092(12) N5 0.0345(13) 0.0324(12) 0.0229(11) -0.0004(10) 0.0008(11) -0.0006(11) Si1 0.0299(4) 0.0295(4) 0.0263(4) -0.0017(3) -0.0008(4) 0.0035(3) Si2 0.0419(5) 0.0449(5) 0.0222(4) -0.0005(4) 0.0032(4) 0.0166(4) O1 0.0306(11) 0.0312(11) 0.0409(12) 0.0034(10) -0.0122(10) -0.0030(9) C1 0.0309(16) 0.0388(19) 0.0378(17) -0.0023(15) -0.0130(14) 0.0015(13) C2 0.0369(19) 0.052(2) 0.062(2) -0.005(2) -0.0172(19) -0.0087(16) C3 0.049(2) 0.094(4) 0.039(2) -0.011(2) -0.0096(18) 0.012(2) C4 0.0383(18) 0.043(2) 0.058(2) 0.0037(17) -0.0165(16) 0.0052(16) C5 0.0262(16) 0.0437(18) 0.0449(19) 0.0022(16) -0.0080(14) -0.0013(15) C6 0.0394(18) 0.050(2) 0.046(2) -0.0077(18) -0.0078(15) -0.0075(17) C7 0.052(2) 0.0372(18) 0.0400(18) -0.0121(15) -0.0052(17) -0.0005(15) C8 0.059(3) 0.042(2) 0.056(2) -0.0002(17) -0.0115(19) -0.0135(18) C9 0.047(2) 0.088(3) 0.057(2) 0.013(2) 0.005(2) -0.027(2) C10 0.041(2) 0.048(2) 0.051(2) -0.0032(17) 0.0090(17) -0.0108(17) C11 0.0427(19) 0.0349(18) 0.060(2) 0.0037(16) -0.0022(18) 0.0078(15) C12 0.073(3) 0.039(2) 0.0379(19) -0.0112(16) -0.0123(18) 0.0166(18) C13 0.0368(19) 0.063(3) 0.0451(19) 0.0124(18) 0.0148(16) 0.0120(18) C14 0.058(2) 0.048(2) 0.042(2) -0.0078(17) -0.0071(18) 0.0177(18) C15 0.069(3) 0.091(3) 0.0318(19) -0.009(2) 0.004(2) 0.037(3) C16 0.0391(18) 0.0323(17) 0.0390(18) -0.0011(14) -0.0064(15) 0.0004(14) C17 0.051(2) 0.0369(19) 0.047(2) 0.0118(15) -0.0127(17) 0.0002(16) C18 0.058(2) 0.053(2) 0.0297(16) 0.0096(15) -0.0080(18) -0.014(2) C19 0.043(2) 0.057(2) 0.0270(15) 0.0012(15) 0.0024(14) -0.0066(17) C20 0.0367(17) 0.0373(17) 0.0306(15) -0.0007(14) 0.0045(13) 0.0000(14) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.3053(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.721(2) yes Ti1 . N2 . 1.999(3) yes Ti1 . N3 . 2.019(2) yes Ti1 . N4 . 2.344(3) yes Ti1 . N5 . 2.199(2) yes N1 . O1 . 1.385(3) yes N2 . Si1 . 1.728(3) yes N2 . C5 . 1.469(4) yes N3 . Si2 . 1.725(3) yes N3 . C7 . 1.463(4) yes N4 . C6 . 1.465(5) yes N4 . C8 . 1.483(5) yes N4 . C9 . 1.452(5) yes N5 . C16 . 1.334(4) yes N5 . C20 . 1.331(4) yes Si1 . C10 . 1.871(4) yes Si1 . C11 . 1.879(4) yes Si1 . C12 . 1.868(4) yes Si2 . C13 . 1.868(4) yes Si2 . C14 . 1.868(4) yes Si2 . C15 . 1.890(4) yes O1 . C1 . 1.474(4) yes C1 . C2 . 1.514(5) yes C1 . C3 . 1.512(5) yes C1 . C4 . 1.506(5) yes C2 . H21 . 0.950 no C2 . H22 . 0.950 no C2 . H23 . 0.950 no C3 . H31 . 0.950 no C3 . H32 . 0.950 no C3 . H33 . 0.950 no C4 . H41 . 0.950 no C4 . H42 . 0.950 no C4 . H43 . 0.950 no C5 . C6 . 1.540(5) yes C5 . H51 . 0.950 no C5 . H52 . 0.950 no C6 . H61 . 0.950 no C6 . H62 . 0.950 no C7 . C8 . 1.504(6) yes C7 . H71 . 0.950 no C7 . H72 . 0.950 no C8 . H81 . 0.950 no C8 . H82 . 0.950 no C9 . H91 . 0.950 no C9 . H92 . 0.950 no C9 . H93 . 0.950 no C10 . H101 . 0.950 no C10 . H102 . 0.950 no C10 . H103 . 0.950 no C11 . H111 . 0.950 no C11 . H112 . 0.950 no C11 . H113 . 0.950 no C12 . H121 . 0.950 no C12 . H122 . 0.950 no C12 . H123 . 0.950 no C13 . H131 . 0.950 no C13 . H132 . 0.950 no C13 . H133 . 0.950 no C14 . H141 . 0.950 no C14 . H142 . 0.950 no C14 . H143 . 0.950 no C15 . H151 . 0.950 no C15 . H152 . 0.950 no C15 . H153 . 0.950 no C16 . C17 . 1.381(5) yes C16 . H161 . 0.950 no C17 . C18 . 1.378(6) yes C17 . H171 . 0.950 no C18 . C19 . 1.374(6) yes C18 . H181 . 0.950 no C19 . C20 . 1.391(5) yes C19 . H191 . 0.950 no C20 . H201 . 0.950 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 102.58(11) yes N1 . Ti1 . N3 . 104.36(12) yes N2 . Ti1 . N3 . 122.16(10) yes N1 . Ti1 . N4 . 175.74(11) yes N2 . Ti1 . N4 . 78.07(10) yes N3 . Ti1 . N4 . 78.58(11) yes N1 . Ti1 . N5 . 93.14(11) yes N2 . Ti1 . N5 . 116.55(10) yes N3 . Ti1 . N5 . 111.93(10) yes N4 . Ti1 . N5 . 82.85(9) yes Ti1 . N1 . O1 . 177.0(2) yes Ti1 . N2 . Si1 . 122.97(13) yes Ti1 . N2 . C5 . 118.2(2) yes Si1 . N2 . C5 . 118.9(2) yes Ti1 . N3 . Si2 . 127.86(15) yes Ti1 . N3 . C7 . 117.9(2) yes Si2 . N3 . C7 . 114.0(2) yes Ti1 . N4 . C6 . 99.26(19) yes Ti1 . N4 . C8 . 104.4(2) yes C6 . N4 . C8 . 110.9(3) yes Ti1 . N4 . C9 . 121.0(2) yes C6 . N4 . C9 . 111.3(3) yes C8 . N4 . C9 . 109.4(3) yes Ti1 . N5 . C16 . 120.6(2) yes Ti1 . N5 . C20 . 121.4(2) yes C16 . N5 . C20 . 117.8(3) yes N2 . Si1 . C10 . 112.17(15) yes N2 . Si1 . C11 . 110.73(15) yes C10 . Si1 . C11 . 107.18(18) yes N2 . Si1 . C12 . 112.11(15) yes C10 . Si1 . C12 . 108.5(2) yes C11 . Si1 . C12 . 105.84(18) yes N3 . Si2 . C13 . 114.19(15) yes N3 . Si2 . C14 . 110.95(17) yes C13 . Si2 . C14 . 110.86(19) yes N3 . Si2 . C15 . 111.23(18) yes C13 . Si2 . C15 . 104.6(2) yes C14 . Si2 . C15 . 104.42(19) yes N1 . O1 . C1 . 115.2(2) yes O1 . C1 . C2 . 101.8(3) yes O1 . C1 . C3 . 109.4(3) yes C2 . C1 . C3 . 112.6(3) yes O1 . C1 . C4 . 110.8(3) yes C2 . C1 . C4 . 110.6(3) yes C3 . C1 . C4 . 111.3(3) yes C1 . C2 . H21 . 109.9 no C1 . C2 . H22 . 109.5 no H21 . C2 . H22 . 109.5 no C1 . C2 . H23 . 109.0 no H21 . C2 . H23 . 109.5 no H22 . C2 . H23 . 109.5 no C1 . C3 . H31 . 109.5 no C1 . C3 . H32 . 109.4 no H31 . C3 . H32 . 109.5 no C1 . C3 . H33 . 109.5 no H31 . C3 . H33 . 109.5 no H32 . C3 . H33 . 109.5 no C1 . C4 . H41 . 110.0 no C1 . C4 . H42 . 109.3 no H41 . C4 . H42 . 109.5 no C1 . C4 . H43 . 109.1 no H41 . C4 . H43 . 109.5 no H42 . C4 . H43 . 109.5 no N2 . C5 . C6 . 109.0(3) yes N2 . C5 . H51 . 109.5 no C6 . C5 . H51 . 108.6 no N2 . C5 . H52 . 109.8 no C6 . C5 . H52 . 110.5 no H51 . C5 . H52 . 109.5 no C5 . C6 . N4 . 109.1(3) yes C5 . C6 . H61 . 110.4 no N4 . C6 . H61 . 110.1 no C5 . C6 . H62 . 108.7 no N4 . C6 . H62 . 109.0 no H61 . C6 . H62 . 109.5 no N3 . C7 . C8 . 112.8(3) yes N3 . C7 . H71 . 108.7 no C8 . C7 . H71 . 109.1 no N3 . C7 . H72 . 108.5 no C8 . C7 . H72 . 108.2 no H71 . C7 . H72 . 109.5 no C7 . C8 . N4 . 110.6(3) yes C7 . C8 . H81 . 108.6 no N4 . C8 . H81 . 108.7 no C7 . C8 . H82 . 110.1 no N4 . C8 . H82 . 109.3 no H81 . C8 . H82 . 109.5 no N4 . C9 . H91 . 108.9 no N4 . C9 . H92 . 110.2 no H91 . C9 . H92 . 109.5 no N4 . C9 . H93 . 109.3 no H91 . C9 . H93 . 109.5 no H92 . C9 . H93 . 109.5 no Si1 . C10 . H101 . 109.8 no Si1 . C10 . H102 . 109.2 no H101 . C10 . H102 . 109.5 no Si1 . C10 . H103 . 109.4 no H101 . C10 . H103 . 109.5 no H102 . C10 . H103 . 109.5 no Si1 . C11 . H111 . 109.8 no Si1 . C11 . H112 . 109.4 no H111 . C11 . H112 . 109.5 no Si1 . C11 . H113 . 109.2 no H111 . C11 . H113 . 109.5 no H112 . C11 . H113 . 109.5 no Si1 . C12 . H121 . 109.6 no Si1 . C12 . H122 . 109.3 no H121 . C12 . H122 . 109.5 no Si1 . C12 . H123 . 109.5 no H121 . C12 . H123 . 109.5 no H122 . C12 . H123 . 109.5 no Si2 . C13 . H131 . 109.3 no Si2 . C13 . H132 . 109.2 no H131 . C13 . H132 . 109.5 no Si2 . C13 . H133 . 109.9 no H131 . C13 . H133 . 109.5 no H132 . C13 . H133 . 109.5 no Si2 . C14 . H141 . 109.5 no Si2 . C14 . H142 . 109.9 no H141 . C14 . H142 . 109.5 no Si2 . C14 . H143 . 108.9 no H141 . C14 . H143 . 109.5 no H142 . C14 . H143 . 109.5 no Si2 . C15 . H151 . 109.8 no Si2 . C15 . H152 . 109.4 no H151 . C15 . H152 . 109.5 no Si2 . C15 . H153 . 109.2 no H151 . C15 . H153 . 109.5 no H152 . C15 . H153 . 109.5 no N5 . C16 . C17 . 123.1(3) yes N5 . C16 . H161 . 117.8 no C17 . C16 . H161 . 119.0 no C16 . C17 . C18 . 118.5(3) yes C16 . C17 . H171 . 120.8 no C18 . C17 . H171 . 120.6 no C17 . C18 . C19 . 119.3(3) yes C17 . C18 . H181 . 120.4 no C19 . C18 . H181 . 120.3 no C18 . C19 . C20 . 118.3(3) yes C18 . C19 . H191 . 120.7 no C20 . C19 . H191 . 120.9 no C19 . C20 . N5 . 123.0(3) yes C19 . C20 . H201 . 119.0 no N5 . C20 . H201 . 118.1 no #===end data_COMPOUND_5 _database_code_depnum_ccdc_archive 'CCDC 813259' #TrackingRef '- Mountford Xray SI.CIF' # Local code ADS143 _chemical_name_systematic ; Ti{MeN(CH2CH2NSiMe3)(CH2CH2NC(Me)C(Ph)NSiMe3)(OtBu) ; _chemical_melting_point ? _refine_special_details ; Hydrogen atoms were placed geometrically with reference to a Fourier difference map and refined in a riding model. ; _cell_length_a 9.83180(10) _cell_length_b 17.1954(2) _cell_length_c 17.3784(2) _cell_angle_alpha 90 _cell_angle_beta 102.9629(7) _cell_angle_gamma 90 _cell_volume 2863.15(6) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Si 0.0817 0.0704 6.2915 2.4386 3.0353 32.3337 1.9891 0.6785 1.5410 81.6937 1.1407 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ti 0.2776 0.4457 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 _chemical_formula_sum 'C24 H46 N4 O1 Si2 Ti1' _chemical_formula_moiety 'C24 H46 N4 O1 Si2 Ti1' _chemical_compound_source ? _chemical_formula_weight 510.73 _cell_measurement_reflns_used 6497 _cell_measurement_theta_min 5 _cell_measurement_theta_max 27 _cell_measurement_temperature 150 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_min 0.200 _exptl_crystal_size_mid 0.300 _exptl_crystal_size_max 0.300 _exptl_crystal_density_diffrn 1.185 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1104 _exptl_absorpt_coefficient_mu 0.405 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.89 _exptl_absorpt_correction_T_max 0.92 _diffrn_measurement_device 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'COLLECT (Nonius, 2001).' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 11552 _reflns_number_total 6518 _diffrn_reflns_av_R_equivalents 0.026 _diffrn_reflns_theta_min 5.162 _diffrn_reflns_theta_max 27.483 _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 26.933 _diffrn_measured_fraction_theta_full 0.992 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _reflns_limit_h_min -12 _reflns_limit_h_max 12 _reflns_limit_k_min 0 _reflns_limit_k_max 22 _reflns_limit_l_min 0 _reflns_limit_l_max 22 _oxford_diffrn_Wilson_B_factor 1.77 _oxford_diffrn_Wilson_scale 11.07 _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.36 _refine_diff_density_max 0.29 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 4752 _refine_ls_number_restraints 0 _refine_ls_number_parameters 289 _oxford_refine_ls_R_factor_ref 0.0407 _refine_ls_wR_factor_ref 0.0412 _refine_ls_goodness_of_fit_ref 1.1347 _refine_ls_shift/su_max 0.0014391 _refine_ls_shift/su_mean 4.1260219 # The values computed from all data _oxford_reflns_number_all 6518 _refine_ls_R_factor_all 0.0626 _refine_ls_wR_factor_all 0.0575 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 5083 _refine_ls_R_factor_gt 0.0439 _refine_ls_wR_factor_gt 0.0435 _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment none _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 1.20 1.59 1.24 0.617 0.296 ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994). Acta Cryst, A50, 411-437. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens Ti1 Ti 0.63857(3) 0.21194(2) 0.710003(19) 0.0181 1.0000 Uani . . . . . . . N1 N 0.49103(16) 0.22686(9) 0.61296(9) 0.0200 1.0000 Uani . . . . . . . N2 N 0.48472(17) 0.21563(10) 0.76204(9) 0.0240 1.0000 Uani . . . . . . . N3 N 0.74680(17) 0.12636(10) 0.67920(10) 0.0232 1.0000 Uani . . . . . . . N4 N 0.69922(18) 0.13580(10) 0.82266(10) 0.0257 1.0000 Uani . . . . . . . O1 O 0.74755(14) 0.29752(8) 0.72997(8) 0.0254 1.0000 Uani . . . . . . . Si1 Si 0.40691(6) 0.15590(3) 0.54809(3) 0.0221 1.0000 Uani . . . . . . . Si2 Si 0.88378(6) 0.14239(3) 0.63281(3) 0.0255 1.0000 Uani . . . . . . . C1 C 0.7874(2) 0.37384(12) 0.75739(12) 0.0258 1.0000 Uani . . . . . . . C2 C 0.6742(4) 0.43011(16) 0.7196(2) 0.0704 1.0000 Uani . . . . . . . C3 C 0.9222(4) 0.3932(2) 0.7349(3) 0.0749 1.0000 Uani . . . . . . . C4 C 0.8053(4) 0.37530(19) 0.84586(16) 0.0652 1.0000 Uani . . . . . . . C5 C 0.4643(2) 0.17648(14) 0.83211(12) 0.0290 1.0000 Uani . . . . . . . C6 C 0.6088(2) 0.15463(15) 0.87813(13) 0.0338 1.0000 Uani . . . . . . . C7 C 0.7467(2) 0.05123(12) 0.71944(13) 0.0302 1.0000 Uani . . . . . . . C8 C 0.6677(2) 0.05893(13) 0.78551(13) 0.0317 1.0000 Uani . . . . . . . C9 C 0.8463(2) 0.14069(15) 0.86579(14) 0.0372 1.0000 Uani . . . . . . . C10 C 0.8461(3) 0.22890(14) 0.56719(14) 0.0355 1.0000 Uani . . . . . . . C11 C 0.9124(3) 0.05546(15) 0.57329(15) 0.0392 1.0000 Uani . . . . . . . C12 C 1.0508(2) 0.16053(16) 0.70734(15) 0.0401 1.0000 Uani . . . . . . . C13 C 0.5217(2) 0.11881(15) 0.48456(13) 0.0337 1.0000 Uani . . . . . . . C14 C 0.3563(3) 0.07236(13) 0.60416(14) 0.0339 1.0000 Uani . . . . . . . C15 C 0.2411(2) 0.19221(14) 0.48229(13) 0.0322 1.0000 Uani . . . . . . . C16 C 0.3241(2) 0.32703(13) 0.76631(12) 0.0280 1.0000 Uani . . . . . . . C17 C 0.39733(19) 0.27288(11) 0.72111(11) 0.0214 1.0000 Uani . . . . . . . C18 C 0.40324(19) 0.27964(11) 0.64292(11) 0.0197 1.0000 Uani . . . . . . . C19 C 0.3348(2) 0.34235(11) 0.58983(11) 0.0207 1.0000 Uani . . . . . . . C20 C 0.1965(2) 0.36520(12) 0.58584(12) 0.0258 1.0000 Uani . . . . . . . C21 C 0.1327(2) 0.42104(14) 0.53212(13) 0.0342 1.0000 Uani . . . . . . . C22 C 0.2050(3) 0.45566(14) 0.48150(13) 0.0373 1.0000 Uani . . . . . . . C23 C 0.3414(3) 0.43399(13) 0.48417(13) 0.0332 1.0000 Uani . . . . . . . C24 C 0.4051(2) 0.37749(12) 0.53763(12) 0.0266 1.0000 Uani . . . . . . . H21 H 0.6995 0.4814 0.7375 0.0897 1.0000 Uiso R . . . . . . H22 H 0.5890 0.4162 0.7332 0.0897 1.0000 Uiso R . . . . . . H23 H 0.6628 0.4279 0.6639 0.0897 1.0000 Uiso R . . . . . . H31 H 0.9511 0.4441 0.7527 0.0941 1.0000 Uiso R . . . . . . H32 H 0.9915 0.3567 0.7587 0.0941 1.0000 Uiso R . . . . . . H33 H 0.9096 0.3908 0.6791 0.0941 1.0000 Uiso R . . . . . . H41 H 0.8321 0.4259 0.8655 0.0819 1.0000 Uiso R . . . . . . H42 H 0.8757 0.3391 0.8688 0.0819 1.0000 Uiso R . . . . . . H43 H 0.7199 0.3613 0.8591 0.0819 1.0000 Uiso R . . . . . . H51 H 0.4199 0.2103 0.8622 0.0374 1.0000 Uiso R . . . . . . H52 H 0.4088 0.1312 0.8181 0.0374 1.0000 Uiso R . . . . . . H61 H 0.6480 0.1970 0.9107 0.0428 1.0000 Uiso R . . . . . . H62 H 0.6029 0.1105 0.9101 0.0428 1.0000 Uiso R . . . . . . H71 H 0.8402 0.0358 0.7411 0.0384 1.0000 Uiso R . . . . . . H72 H 0.7024 0.0134 0.6824 0.0384 1.0000 Uiso R . . . . . . H81 H 0.6967 0.0193 0.8238 0.0398 1.0000 Uiso R . . . . . . H82 H 0.5702 0.0545 0.7642 0.0398 1.0000 Uiso R . . . . . . H91 H 0.9055 0.1290 0.8310 0.0469 1.0000 Uiso R . . . . . . H92 H 0.8627 0.1046 0.9083 0.0469 1.0000 Uiso R . . . . . . H93 H 0.8652 0.1919 0.8860 0.0469 1.0000 Uiso R . . . . . . H101 H 0.9211 0.2373 0.5419 0.0437 1.0000 Uiso R . . . . . . H102 H 0.8351 0.2733 0.5977 0.0437 1.0000 Uiso R . . . . . . H103 H 0.7625 0.2203 0.5284 0.0437 1.0000 Uiso R . . . . . . H111 H 0.9875 0.0652 0.5484 0.0494 1.0000 Uiso R . . . . . . H112 H 0.9341 0.0118 0.6073 0.0494 1.0000 Uiso R . . . . . . H113 H 0.8299 0.0452 0.5343 0.0494 1.0000 Uiso R . . . . . . H121 H 1.1246 0.1691 0.6812 0.0518 1.0000 Uiso R . . . . . . H122 H 1.0403 0.2050 0.7379 0.0518 1.0000 Uiso R . . . . . . H123 H 1.0718 0.1165 0.7410 0.0518 1.0000 Uiso R . . . . . . H131 H 0.4730 0.0803 0.4498 0.0436 1.0000 Uiso R . . . . . . H132 H 0.6035 0.0967 0.5167 0.0436 1.0000 Uiso R . . . . . . H133 H 0.5468 0.1605 0.4547 0.0436 1.0000 Uiso R . . . . . . H141 H 0.3105 0.0340 0.5682 0.0427 1.0000 Uiso R . . . . . . H142 H 0.4376 0.0506 0.6372 0.0427 1.0000 Uiso R . . . . . . H143 H 0.2951 0.0900 0.6357 0.0427 1.0000 Uiso R . . . . . . H151 H 0.1990 0.1517 0.4480 0.0410 1.0000 Uiso R . . . . . . H152 H 0.1787 0.2088 0.5136 0.0410 1.0000 Uiso R . . . . . . H153 H 0.2617 0.2347 0.4519 0.0410 1.0000 Uiso R . . . . . . H201 H 0.1458 0.3419 0.6204 0.0326 1.0000 Uiso R . . . . . . H211 H 0.0389 0.4358 0.5302 0.0422 1.0000 Uiso R . . . . . . H221 H 0.1609 0.4939 0.4449 0.0458 1.0000 Uiso R . . . . . . H231 H 0.3916 0.4577 0.4497 0.0412 1.0000 Uiso R . . . . . . H241 H 0.4985 0.3624 0.5388 0.0340 1.0000 Uiso R . . . . . . H161 H 0.3842 0.3391 0.8157 0.0335 1.0000 Uiso R . . . . . . H162 H 0.2420 0.3026 0.7748 0.0335 1.0000 Uiso R . . . . . . H163 H 0.2997 0.3735 0.7369 0.0335 1.0000 Uiso 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 0.01929(16) 0.01719(16) 0.01751(16) 0.00022(13) 0.00374(12) 0.00101(13) N1 0.0202(7) 0.0208(8) 0.0193(7) 0.0007(6) 0.0047(6) 0.0021(6) N2 0.0252(8) 0.0287(9) 0.0187(8) 0.0051(7) 0.0064(6) 0.0049(7) N3 0.0257(8) 0.0197(8) 0.0238(8) 0.0008(7) 0.0048(7) 0.0037(6) N4 0.0286(9) 0.0273(9) 0.0200(8) 0.0040(7) 0.0033(7) 0.0029(7) O1 0.0257(7) 0.0219(7) 0.0281(7) -0.0035(6) 0.0048(6) -0.0025(6) Si1 0.0231(3) 0.0230(3) 0.0201(3) -0.0025(2) 0.0048(2) 0.0010(2) Si2 0.0224(3) 0.0286(3) 0.0256(3) -0.0040(2) 0.0058(2) 0.0047(2) C1 0.0266(10) 0.0195(10) 0.0318(11) -0.0066(8) 0.0078(8) -0.0062(8) C2 0.069(2) 0.0264(14) 0.095(3) -0.0068(15) -0.0246(18) 0.0051(13) C3 0.066(2) 0.0536(19) 0.124(3) -0.035(2) 0.060(2) -0.0317(16) C4 0.111(3) 0.0477(17) 0.0369(14) -0.0150(13) 0.0173(16) -0.0246(18) C5 0.0308(11) 0.0337(12) 0.0241(10) 0.0074(9) 0.0094(9) 0.0027(9) C6 0.0419(12) 0.0390(13) 0.0216(10) 0.0053(9) 0.0098(9) 0.0053(10) C7 0.0361(11) 0.0200(10) 0.0338(11) 0.0030(9) 0.0063(9) 0.0083(9) C8 0.0388(12) 0.0235(11) 0.0318(11) 0.0057(9) 0.0054(9) 0.0003(9) C9 0.0345(12) 0.0437(14) 0.0293(11) 0.0058(10) -0.0015(9) 0.0070(10) C10 0.0370(12) 0.0391(13) 0.0338(12) 0.0032(10) 0.0154(10) 0.0011(10) C11 0.0370(12) 0.0424(14) 0.0381(13) -0.0097(11) 0.0082(10) 0.0122(11) C12 0.0276(11) 0.0525(15) 0.0395(13) -0.0087(11) 0.0058(10) 0.0017(10) C13 0.0320(11) 0.0412(13) 0.0269(11) -0.0094(10) 0.0048(9) 0.0042(10) C14 0.0413(13) 0.0258(11) 0.0335(12) -0.0036(9) 0.0057(10) -0.0080(9) C15 0.0287(11) 0.0353(12) 0.0299(11) -0.0075(9) 0.0008(9) 0.0001(9) C16 0.0302(11) 0.0319(12) 0.0230(10) -0.0011(8) 0.0085(8) 0.0055(9) C17 0.0183(9) 0.0235(10) 0.0222(9) 0.0003(7) 0.0041(7) -0.0001(7) C18 0.0177(8) 0.0200(9) 0.0212(9) -0.0008(7) 0.0042(7) 0.0009(7) C19 0.0227(9) 0.0205(9) 0.0171(9) -0.0022(7) 0.0005(7) 0.0015(7) C20 0.0220(9) 0.0274(11) 0.0270(10) -0.0019(8) 0.0038(8) 0.0015(8) C21 0.0305(11) 0.0347(12) 0.0342(12) -0.0012(9) 0.0006(9) 0.0136(9) C22 0.0460(13) 0.0344(13) 0.0288(11) 0.0074(10) 0.0030(10) 0.0161(11) C23 0.0436(13) 0.0314(12) 0.0261(11) 0.0056(9) 0.0110(9) 0.0061(10) C24 0.0264(10) 0.0276(11) 0.0254(10) 0.0029(8) 0.0048(8) 0.0049(8) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.3032(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ti1 . N1 . 1.9790(16) yes Ti1 . N2 . 1.9297(16) yes Ti1 . N3 . 1.9596(17) yes Ti1 . N4 . 2.3193(17) yes Ti1 . O1 . 1.8076(14) yes Ti1 . C17 . 2.6394(19) yes Ti1 . C18 . 2.6187(18) yes N1 . Si1 . 1.7393(17) yes N1 . C18 . 1.429(2) yes N2 . C5 . 1.444(2) yes N2 . C17 . 1.393(2) yes N3 . Si2 . 1.7397(18) yes N3 . C7 . 1.469(3) yes N4 . C6 . 1.486(3) yes N4 . C8 . 1.473(3) yes N4 . C9 . 1.474(3) yes O1 . C1 . 1.421(2) yes Si1 . C13 . 1.859(2) yes Si1 . C14 . 1.865(2) yes Si1 . C15 . 1.876(2) yes Si2 . C10 . 1.860(2) yes Si2 . C11 . 1.875(2) yes Si2 . C12 . 1.875(2) yes C1 . C2 . 1.509(4) yes C1 . C3 . 1.502(3) yes C1 . C4 . 1.508(3) yes C2 . H21 . 0.950 no C2 . H22 . 0.950 no C2 . H23 . 0.950 no C3 . H31 . 0.950 no C3 . H32 . 0.950 no C3 . H33 . 0.950 no C4 . H41 . 0.950 no C4 . H42 . 0.950 no C4 . H43 . 0.950 no C5 . C6 . 1.513(3) yes C5 . H51 . 0.950 no C5 . H52 . 0.950 no C6 . H61 . 0.950 no C6 . H62 . 0.950 no C7 . C8 . 1.530(3) yes C7 . H71 . 0.950 no C7 . H72 . 0.950 no C8 . H81 . 0.950 no C8 . H82 . 0.950 no C9 . H91 . 0.950 no C9 . H92 . 0.950 no C9 . H93 . 0.950 no C10 . H101 . 0.950 no C10 . H102 . 0.950 no C10 . H103 . 0.950 no C11 . H111 . 0.950 no C11 . H112 . 0.950 no C11 . H113 . 0.950 no C12 . H121 . 0.950 no C12 . H122 . 0.950 no C12 . H123 . 0.950 no C13 . H131 . 0.950 no C13 . H132 . 0.950 no C13 . H133 . 0.950 no C14 . H141 . 0.950 no C14 . H142 . 0.950 no C14 . H143 . 0.950 no C15 . H151 . 0.950 no C15 . H152 . 0.950 no C15 . H153 . 0.950 no C16 . C17 . 1.502(3) yes C16 . H161 . 0.950 no C16 . H162 . 0.950 no C16 . H163 . 0.950 no C17 . C18 . 1.378(3) yes C18 . C19 . 1.479(3) yes C19 . C20 . 1.402(3) yes C19 . C24 . 1.395(3) yes C20 . C21 . 1.387(3) yes C20 . H201 . 0.950 no C21 . C22 . 1.384(4) yes C21 . H211 . 0.950 no C22 . C23 . 1.383(3) yes C22 . H221 . 0.950 no C23 . C24 . 1.392(3) yes C23 . H231 . 0.950 no C24 . H241 . 0.950 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ti1 . N2 . 83.88(7) yes N1 . Ti1 . N3 . 101.75(7) yes N2 . Ti1 . N3 . 133.12(7) yes N1 . Ti1 . N4 . 142.47(7) yes N2 . Ti1 . N4 . 72.73(6) yes N3 . Ti1 . N4 . 75.76(6) yes N1 . Ti1 . O1 . 110.34(7) yes N2 . Ti1 . O1 . 112.12(7) yes N3 . Ti1 . O1 . 109.21(7) yes N4 . Ti1 . O1 . 105.57(6) yes N1 . Ti1 . C17 . 60.79(6) yes N2 . Ti1 . C17 . 30.79(6) yes N3 . Ti1 . C17 . 150.47(7) yes N4 . Ti1 . C17 . 103.15(6) yes O1 . Ti1 . C17 . 99.58(6) yes N1 . Ti1 . C18 . 32.59(6) yes N2 . Ti1 . C18 . 59.13(6) yes N3 . Ti1 . C18 . 133.78(6) yes N4 . Ti1 . C18 . 131.37(6) yes O1 . Ti1 . C18 . 98.63(6) yes C17 . Ti1 . C18 . 30.38(6) yes Ti1 . N1 . Si1 . 127.77(9) yes Ti1 . N1 . C18 . 99.15(11) yes Si1 . N1 . C18 . 116.32(12) yes Ti1 . N2 . C5 . 130.66(14) yes Ti1 . N2 . C17 . 104.04(12) yes C5 . N2 . C17 . 125.01(16) yes Ti1 . N3 . Si2 . 122.13(9) yes Ti1 . N3 . C7 . 118.17(13) yes Si2 . N3 . C7 . 116.30(13) yes Ti1 . N4 . C6 . 110.28(13) yes Ti1 . N4 . C8 . 98.49(12) yes C6 . N4 . C8 . 112.46(18) yes Ti1 . N4 . C9 . 115.73(14) yes C6 . N4 . C9 . 108.59(17) yes C8 . N4 . C9 . 111.11(18) yes Ti1 . O1 . C1 . 157.41(13) yes N1 . Si1 . C13 . 111.21(9) yes N1 . Si1 . C14 . 110.21(9) yes C13 . Si1 . C14 . 108.34(11) yes N1 . Si1 . C15 . 112.55(9) yes C13 . Si1 . C15 . 108.21(10) yes C14 . Si1 . C15 . 106.11(11) yes N3 . Si2 . C10 . 110.02(9) yes N3 . Si2 . C11 . 110.93(10) yes C10 . Si2 . C11 . 109.47(11) yes N3 . Si2 . C12 . 110.80(10) yes C10 . Si2 . C12 . 108.28(12) yes C11 . Si2 . C12 . 107.27(11) yes O1 . C1 . C2 . 108.99(18) yes O1 . C1 . C3 . 108.09(18) yes C2 . C1 . C3 . 110.6(3) yes O1 . C1 . C4 . 108.53(19) yes C2 . C1 . C4 . 109.8(3) yes C3 . C1 . C4 . 110.7(3) yes C1 . C2 . H21 . 109.9 no C1 . C2 . H22 . 109.7 no H21 . C2 . H22 . 109.5 no C1 . C2 . H23 . 108.9 no H21 . C2 . H23 . 109.5 no H22 . C2 . H23 . 109.5 no C1 . C3 . H31 . 109.6 no C1 . C3 . H32 . 109.2 no H31 . C3 . H32 . 109.5 no C1 . C3 . H33 . 109.6 no H31 . C3 . H33 . 109.5 no H32 . C3 . H33 . 109.5 no C1 . C4 . H41 . 109.9 no C1 . C4 . H42 . 108.9 no H41 . C4 . H42 . 109.5 no C1 . C4 . H43 . 109.5 no H41 . C4 . H43 . 109.5 no H42 . C4 . H43 . 109.5 no N2 . C5 . C6 . 105.65(17) yes N2 . C5 . H51 . 110.2 no C6 . C5 . H51 . 110.7 no N2 . C5 . H52 . 110.2 no C6 . C5 . H52 . 110.5 no H51 . C5 . H52 . 109.5 no C5 . C6 . N4 . 109.79(17) yes C5 . C6 . H61 . 109.4 no N4 . C6 . H61 . 109.4 no C5 . C6 . H62 . 109.5 no N4 . C6 . H62 . 109.3 no H61 . C6 . H62 . 109.5 no N3 . C7 . C8 . 109.62(17) yes N3 . C7 . H71 . 109.4 no C8 . C7 . H71 . 109.6 no N3 . C7 . H72 . 109.2 no C8 . C7 . H72 . 109.6 no H71 . C7 . H72 . 109.5 no C7 . C8 . N4 . 108.31(17) yes C7 . C8 . H81 . 109.9 no N4 . C8 . H81 . 109.6 no C7 . C8 . H82 . 109.8 no N4 . C8 . H82 . 109.7 no H81 . C8 . H82 . 109.5 no N4 . C9 . H91 . 109.6 no N4 . C9 . H92 . 109.6 no H91 . C9 . H92 . 109.5 no N4 . C9 . H93 . 109.2 no H91 . C9 . H93 . 109.5 no H92 . C9 . H93 . 109.5 no Si2 . C10 . H101 . 109.6 no Si2 . C10 . H102 . 109.4 no H101 . C10 . H102 . 109.5 no Si2 . C10 . H103 . 109.4 no H101 . C10 . H103 . 109.5 no H102 . C10 . H103 . 109.5 no Si2 . C11 . H111 . 109.9 no Si2 . C11 . H112 . 109.1 no H111 . C11 . H112 . 109.5 no Si2 . C11 . H113 . 109.4 no H111 . C11 . H113 . 109.5 no H112 . C11 . H113 . 109.5 no Si2 . C12 . H121 . 109.9 no Si2 . C12 . H122 . 109.4 no H121 . C12 . H122 . 109.5 no Si2 . C12 . H123 . 109.1 no H121 . C12 . H123 . 109.5 no H122 . C12 . H123 . 109.5 no Si1 . C13 . H131 . 109.3 no Si1 . C13 . H132 . 109.6 no H131 . C13 . H132 . 109.5 no Si1 . C13 . H133 . 109.4 no H131 . C13 . H133 . 109.5 no H132 . C13 . H133 . 109.5 no Si1 . C14 . H141 . 109.6 no Si1 . C14 . H142 . 109.4 no H141 . C14 . H142 . 109.5 no Si1 . C14 . H143 . 109.5 no H141 . C14 . H143 . 109.5 no H142 . C14 . H143 . 109.5 no Si1 . C15 . H151 . 109.6 no Si1 . C15 . H152 . 109.6 no H151 . C15 . H152 . 109.5 no Si1 . C15 . H153 . 109.2 no H151 . C15 . H153 . 109.5 no H152 . C15 . H153 . 109.5 no C17 . C16 . H161 . 109.5 no C17 . C16 . H162 . 109.3 no H161 . C16 . H162 . 109.5 no C17 . C16 . H163 . 109.5 no H161 . C16 . H163 . 109.5 no H162 . C16 . H163 . 109.5 no C16 . C17 . N2 . 118.97(16) yes C16 . C17 . Ti1 . 145.94(13) yes N2 . C17 . Ti1 . 45.17(9) yes C16 . C17 . C18 . 126.49(18) yes N2 . C17 . C18 . 113.93(17) yes Ti1 . C17 . C18 . 73.98(11) yes N1 . C18 . C17 . 117.92(16) yes N1 . C18 . Ti1 . 48.25(8) yes C17 . C18 . Ti1 . 75.64(11) yes N1 . C18 . C19 . 117.60(16) yes C17 . C18 . C19 . 124.24(17) yes Ti1 . C18 . C19 . 146.56(13) yes C18 . C19 . C20 . 122.36(18) yes C18 . C19 . C24 . 119.93(17) yes C20 . C19 . C24 . 117.57(18) yes C19 . C20 . C21 . 121.0(2) yes C19 . C20 . H201 . 119.4 no C21 . C20 . H201 . 119.6 no C20 . C21 . C22 . 120.4(2) yes C20 . C21 . H211 . 119.9 no C22 . C21 . H211 . 119.7 no C21 . C22 . C23 . 119.7(2) yes C21 . C22 . H221 . 120.2 no C23 . C22 . H221 . 120.1 no C22 . C23 . C24 . 119.9(2) yes C22 . C23 . H231 . 120.1 no C24 . C23 . H231 . 120.0 no C19 . C24 . C23 . 121.5(2) yes C19 . C24 . H241 . 119.1 no C23 . C24 . H241 . 119.5 no #===end