# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2000 # CCDC Number: 440/189 data_Compound_3 # Local code megs8 _audit_creation_date 99-08-4 _audit_creation_method CRYSTALS _publ_contact_letter ; This CIF corresponds to the manuscript entitled Ansa-linked titanium macrocycle-imido complexes N A H Male, M E G Skinner, P J Wilson, P Mountford and M Schroder ; _publ_contact_author ; Dr P Mountford Inorganic Chemistry Laboratory South Parks Road Oxford OX1 3QR ; _publ_contact_author_phone '+44 1865 272679' _publ_contact_author_fax '+44 1865 272690' _publ_contact_author_email Philip.Mountford@chem.ox.ac.uk _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo G., Guagliardi A., Burla M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. 27, 435. Carruthers, J.R. and Watkin, D.J. (1979), (Chebychev Weighting) Acta Cryst, A35, 698-699 Otwinowski, Z. & Minor, W. (1996), Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods in Enzymology 276, Ed Carter, C.W. & Sweet, R.M., Academic Press. Sheldrick, G.M. (1994 or 1995). SHELXTL/PC version 5.03. Siemens Analytical Instruments Inc, Madison WI, U.S.A. Watkin, D.J., Prout, C.K. Carruthers, R.J. & Betteridge, P. (1996) CRYSTALS Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. ; _publ_section_exptl_refinement 'no special details' _chemical_name_systematic ; [Ti{i-Pr2(CH2CH2CH2N)[9]aneN3}Cl(OTf)] ; # aka [Ti(L-1)Cl(OTf)] in the manuscript _cell_length_a 9.2840(6) _cell_angle_alpha 90 _cell_length_b 19.097(2) _cell_angle_beta 99.091(4) _cell_length_c 12.7810(7) _cell_angle_gamma 90 _cell_volume 2237.6 _symmetry_cell_setting 'Monoclinic ' _symmetry_space_group_name_H-M 'P 1 21/n 1 ' 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' 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 ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International_Tables_Vol_IV_Table_2.2B' 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International_Tables_Vol_IV_Table_2.2B' 'N ' 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International_Tables_Vol_IV_Table_2.2B' 'O ' 0.0080 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International_Tables_Vol_IV_Table_2.2B' 'F ' 0.0140 0.0100 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International_Tables_Vol_IV_Table_2.2B' 'Cl ' 0.1320 0.1590 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International_Tables_Vol_IV_Table_2.2B' 'S ' 0.1100 0.1240 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.1720 0.8669 'International_Tables_Vol_IV_Table_2.2B' 'Ti ' 0.2480 0.4460 9.7595 7.8508 7.3558 0.5000 1.6991 35.6338 1.9021 116.1050 1.2807 'International_Tables_Vol_IV_Table_2.2B' _chemical_formula_sum ' C16 H32 Cl1 F3 N4 O3 S1 Ti1 ' _chemical_formula_moiety ' C16 H32 Cl1 F3 N4 O3 S1 Ti1 ' _chemical_compound_source ; H2L-1 + [Ti(NBu-t)Cl2(py(3] in benzene ; _chemical_formula_weight 500.86 _cell_measurement_reflns_used 16824 _cell_measurement_theta_min 0 _cell_measurement_theta_max 27 _cell_measurement_temperature 170 _cell_formula_units_Z 4.00 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_min 0.25 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_max 0.50 _exptl_crystal_density_diffrn 1.49 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_method none _exptl_crystal_F_000 1048 _exptl_absorpt_coefficient_mu 0.64 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.726 _exptl_absorpt_correction_T_max 0.852 _diffrn_reflns_av_sigmaI/netI 0.0617 _diffrn_measurement_device-type 'Enraf-nonius DIP2000 ' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71069 _diffrn_measurement_method \w _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% 0.00 _diffrn_ambient_temperature 170 _diffrn_reflns_number 16824 _reflns_number_total 4207 _diffrn_reflns_av_R_equivalents 0.06 _reflns_number_observed 2780 _diffrn_reflns_theta_min 1.07 _diffrn_reflns_theta_max 26.43 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _reflns_limit_h_min -11 _reflns_limit_h_max 11 _reflns_limit_k_min 0 _reflns_limit_k_max 23 _reflns_limit_l_min 0 _reflns_limit_l_max 15 _atom_sites_solution_primary 'direct methods' _atom_sites_solution_hydrogens geometric _reflns_observed_criterion >3\s(I) _refine_diff_density_min -0.48 _refine_diff_density_max 0.43 _refine_ls_number_reflns 2780 _refine_ls_number_parameters 262 _refine_ls_R_factor_obs 0.0526 _refine_ls_wR_factor_obs 0.0359 _refine_ls_goodness_of_fit_obs 1.17 _refine_ls_shift/esd_max 0.0003 _refine_ls_structure_factor_coef F _refine_ls_extinction_method none _refine_ls_matrix_type full _refine_ls_weighting_scheme 'Chebychev polynomial' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_number_restraints 0 _refine_ls_abs_structure_flack none _refine_ls_extinction_coef none _computing_data_collection 'DIP2000 software Xpress (MAC Science, 1989)' _computing_data_reduction ; DIP2000 software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; DIP2000 software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_structure_solution 'SIR92 (Altomare, et al, 1994)' _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin et al, 1996) ; _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1994)' _computing_publication_material ; CRYSTALS Issue 10 (Watkin et al, 1996) ; loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type Ti1 0.64184(5) 0.26458(3) 0.67237(4) 0.0225 1.0000 Uani N1 0.5039(3) 0.2053(1) 0.6503(2) 0.0289 1.0000 Uani N3 0.8378(3) 0.1913(1) 0.6904(2) 0.0262 1.0000 Uani N6 0.6548(3) 0.2315(1) 0.8433(2) 0.0250 1.0000 Uani N9 0.8308(3) 0.3402(1) 0.7689(2) 0.0250 1.0000 Uani C1 0.9589(3) 0.3118(2) 0.7254(3) 0.0282 1.0000 Uani C2 0.9736(3) 0.2328(2) 0.7338(3) 0.0289 1.0000 Uani C4 0.8050(3) 0.1393(2) 0.7705(2) 0.0268 1.0000 Uani C5 0.7645(3) 0.1734(2) 0.8689(2) 0.0253 1.0000 Uani C7 0.7020(3) 0.2936(2) 0.9111(2) 0.0278 1.0000 Uani C8 0.8424(3) 0.3249(2) 0.8850(2) 0.0278 1.0000 Uani C31 0.8625(3) 0.1532(2) 0.5900(2) 0.0275 1.0000 Uani C32 0.7284(4) 0.1174(2) 0.5313(3) 0.0360 1.0000 Uani C33 0.9876(4) 0.0993(2) 0.6083(3) 0.0386 1.0000 Uani C61 0.5096(3) 0.2090(2) 0.8696(3) 0.0292 1.0000 Uani C62 0.4414(3) 0.1462(2) 0.8060(3) 0.0318 1.0000 Uani C63 0.3963(3) 0.1629(2) 0.6883(3) 0.0317 1.0000 Uani C91 0.8223(3) 0.4188(2) 0.7549(3) 0.0296 1.0000 Uani C92 0.9584(4) 0.4578(2) 0.8098(3) 0.0380 1.0000 Uani C93 0.7880(4) 0.4431(2) 0.6408(3) 0.0391 1.0000 Uani C100 0.3564(4) 0.4526(2) 0.6221(3) 0.0398 1.0000 Uani S1 0.36238(8) 0.36951(4) 0.69385(6) 0.0284 1.0000 Uani O1 0.5171(2) 0.3507(1) 0.6990(2) 0.0288 1.0000 Uani O2 0.3284(3) 0.3872(2) 0.7952(2) 0.0509 1.0000 Uani O3 0.2621(2) 0.3260(1) 0.6276(2) 0.0367 1.0000 Uani F1 0.4413(3) 0.5004(1) 0.6756(2) 0.0675 1.0000 Uani F2 0.4007(2) 0.4450(1) 0.5294(2) 0.0486 1.0000 Uani F3 0.2207(3) 0.4767(1) 0.6048(3) 0.0740 1.0000 Uani Cl1 0.68151(8) 0.29780(4) 0.49958(6) 0.0324 1.0000 Uani H11 1.0460(3) 0.3331(2) 0.7624(3) 0.0315 1.0000 Uiso H12 0.9481(3) 0.3236(2) 0.6516(3) 0.0315 1.0000 Uiso H21 0.9984(3) 0.2219(2) 0.8078(3) 0.0361 1.0000 Uiso H22 1.0510(3) 0.2179(2) 0.6973(3) 0.0361 1.0000 Uiso H41 0.8892(3) 0.1102(2) 0.7904(2) 0.0312 1.0000 Uiso H42 0.7243(3) 0.1110(2) 0.7389(2) 0.0312 1.0000 Uiso H51 0.8513(3) 0.1929(2) 0.9091(2) 0.0312 1.0000 Uiso H52 0.7247(3) 0.1388(2) 0.9106(2) 0.0312 1.0000 Uiso H71 0.7161(3) 0.2795(2) 0.9841(2) 0.0367 1.0000 Uiso H72 0.6266(3) 0.3284(2) 0.8991(2) 0.0367 1.0000 Uiso H81 0.8629(3) 0.3677(2) 0.9239(2) 0.0362 1.0000 Uiso H82 0.9205(3) 0.2923(2) 0.9052(2) 0.0362 1.0000 Uiso H311 0.8910(3) 0.1909(2) 0.5479(2) 0.0340 1.0000 Uiso H321 0.7515(4) 0.0948(2) 0.4689(3) 0.0468 1.0000 Uiso H322 0.6958(4) 0.0831(2) 0.5772(3) 0.0468 1.0000 Uiso H323 0.6526(4) 0.1513(2) 0.5114(3) 0.0468 1.0000 Uiso H331 0.9984(4) 0.0780(2) 0.5420(3) 0.0434 1.0000 Uiso H332 1.0773(4) 0.1217(2) 0.6380(3) 0.0434 1.0000 Uiso H333 0.9639(4) 0.0640(2) 0.6563(3) 0.0434 1.0000 Uiso H611 0.5224(3) 0.1978(2) 0.9437(3) 0.0394 1.0000 Uiso H612 0.4433(3) 0.2476(2) 0.8553(3) 0.0394 1.0000 Uiso H621 0.3562(3) 0.1314(2) 0.8339(3) 0.0379 1.0000 Uiso H622 0.5117(3) 0.1090(2) 0.8132(3) 0.0379 1.0000 Uiso H631 0.3049(3) 0.1874(2) 0.6783(3) 0.0379 1.0000 Uiso H632 0.3861(3) 0.1202(2) 0.6481(3) 0.0379 1.0000 Uiso H911 0.7387(3) 0.4296(2) 0.7875(3) 0.0355 1.0000 Uiso H921 0.9459(4) 0.5073(2) 0.7991(3) 0.0487 1.0000 Uiso H922 0.9738(4) 0.4478(2) 0.8843(3) 0.0487 1.0000 Uiso H923 1.0412(4) 0.4423(2) 0.7796(3) 0.0487 1.0000 Uiso H931 0.7832(4) 0.4933(2) 0.6388(3) 0.0545 1.0000 Uiso H932 0.8642(4) 0.4275(2) 0.6035(3) 0.0545 1.0000 Uiso H933 0.6965(4) 0.4240(2) 0.6077(3) 0.0545 1.0000 Uiso 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 0.0174(2) 0.0317(3) 0.0183(3) 0.0029(2) 0.0030(2) 0.0007(2) N1 0.022(1) 0.037(2) 0.027(2) 0.001(1) 0.004(1) 0.002(1) N3 0.022(1) 0.034(2) 0.022(1) 0.003(1) 0.003(1) 0.003(1) N6 0.022(1) 0.033(1) 0.021(1) 0.003(1) 0.006(1) 0.000(1) N9 0.019(1) 0.030(1) 0.026(1) 0.003(1) 0.004(1) 0.001(1) C1 0.014(1) 0.037(2) 0.034(2) 0.002(1) 0.005(1) -0.000(1) C2 0.017(1) 0.038(2) 0.031(2) -0.002(1) 0.003(1) -0.001(1) C4 0.024(1) 0.032(2) 0.025(2) 0.005(1) 0.004(1) 0.006(1) C5 0.028(1) 0.028(2) 0.020(2) 0.004(1) 0.002(1) 0.002(1) C7 0.030(2) 0.036(2) 0.018(2) -0.001(1) 0.004(1) 0.001(1) C8 0.027(2) 0.030(2) 0.026(2) -0.001(1) 0.004(1) -0.004(1) C31 0.025(1) 0.035(2) 0.024(2) -0.003(1) 0.007(1) 0.003(1) C32 0.035(2) 0.044(2) 0.031(2) -0.008(1) 0.008(2) -0.001(1) C33 0.032(2) 0.044(2) 0.041(2) -0.007(2) 0.009(2) 0.005(1) C61 0.027(2) 0.040(2) 0.023(2) 0.001(1) 0.011(1) -0.003(1) C62 0.028(2) 0.033(2) 0.037(2) 0.003(1) 0.014(2) -0.004(1) C63 0.025(1) 0.034(2) 0.038(2) -0.000(1) 0.006(1) -0.006(1) C91 0.026(2) 0.033(2) 0.031(2) 0.002(1) 0.005(1) 0.000(1) C92 0.034(2) 0.030(2) 0.048(2) 0.001(2) 0.000(2) -0.002(1) C93 0.039(2) 0.034(2) 0.042(2) 0.008(2) 0.003(2) 0.001(2) C100 0.038(2) 0.037(2) 0.042(2) -0.005(2) -0.001(2) 0.006(2) S1 0.0237(4) 0.0371(5) 0.0253(4) 0.0014(3) 0.0063(3) 0.0044(3) O1 0.020(1) 0.039(1) 0.028(1) 0.0023(9) 0.0034(9) 0.0020(9) O2 0.044(1) 0.085(2) 0.027(1) -0.002(1) 0.013(1) 0.015(1) O3 0.022(1) 0.042(1) 0.046(2) 0.001(1) 0.005(1) -0.003(1) F1 0.090(2) 0.039(1) 0.068(2) -0.010(1) -0.003(2) -0.013(1) F2 0.054(1) 0.053(1) 0.037(1) 0.012(1) 0.003(1) -0.010(1) F3 0.051(1) 0.067(2) 0.103(2) 0.026(2) 0.010(1) 0.028(1) Cl1 0.0296(4) 0.0470(5) 0.0209(4) 0.0061(3) 0.0053(3) -0.0023(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 . 1.699(3) yes Ti1 . N3 . 2.278(2) yes Ti1 . N6 . 2.259(3) yes Ti1 . N9 . 2.449(3) yes Ti1 . O1 . 2.070(2) yes Ti1 . Cl1 . 2.3817(9) yes N1 . C63 . 1.430(4) yes N3 . C2 . 1.519(4) yes N3 . C4 . 1.492(4) yes N3 . C31 . 1.523(4) yes N6 . C5 . 1.506(4) yes N6 . C7 . 1.493(4) yes N6 . C61 . 1.502(3) yes N9 . C1 . 1.492(3) yes N9 . C8 . 1.499(4) yes N9 . C91 . 1.514(4) yes C1 . C2 . 1.517(5) yes C4 . C5 . 1.515(4) yes C7 . C8 . 1.518(4) yes C31 . C32 . 1.512(4) yes C31 . C33 . 1.542(4) yes C61 . C62 . 1.528(5) yes C62 . C63 . 1.530(5) yes C91 . C92 . 1.537(5) yes C91 . C93 . 1.515(5) yes C100 . S1 . 1.830(4) yes C100 . F1 . 1.323(4) yes C100 . F2 . 1.322(4) yes C100 . F3 . 1.326(4) yes S1 . O1 . 1.472(2) yes S1 . O2 . 1.421(2) yes S1 . O3 . 1.422(2) yes 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 . N3 . 100.1(1) yes N1 . Ti1 . N6 . 84.1(1) yes N3 . Ti1 . N6 . 79.11(9) yes N1 . Ti1 . N9 . 159.6(1) yes N3 . Ti1 . N9 . 79.29(9) yes N6 . Ti1 . N9 . 75.71(9) yes N1 . Ti1 . O1 . 97.5(1) yes N3 . Ti1 . O1 . 158.44(9) yes N6 . Ti1 . O1 . 90.50(9) yes N9 . Ti1 . O1 . 79.85(8) yes N1 . Ti1 . Cl1 . 104.26(9) yes N3 . Ti1 . Cl1 . 91.10(7) yes N6 . Ti1 . Cl1 . 168.19(7) yes N9 . Ti1 . Cl1 . 96.12(6) yes O1 . Ti1 . Cl1 . 96.51(6) yes Ti1 . N1 . C63 . 150.5(2) yes Ti1 . N3 . C2 . 108.6(2) yes Ti1 . N3 . C4 . 103.4(2) yes C2 . N3 . C4 . 110.1(2) yes Ti1 . N3 . C31 . 115.6(2) yes C2 . N3 . C31 . 109.3(2) yes C4 . N3 . C31 . 109.6(2) yes Ti1 . N6 . C5 . 110.2(2) yes Ti1 . N6 . C7 . 107.8(2) yes C5 . N6 . C7 . 109.4(2) yes Ti1 . N6 . C61 . 112.5(2) yes C5 . N6 . C61 . 109.9(2) yes C7 . N6 . C61 . 106.8(2) yes Ti1 . N9 . C1 . 98.5(2) yes Ti1 . N9 . C8 . 108.5(2) yes C1 . N9 . C8 . 111.2(2) yes Ti1 . N9 . C91 . 120.4(2) yes C1 . N9 . C91 . 110.2(2) yes C8 . N9 . C91 . 107.7(2) yes N9 . C1 . C2 . 113.7(2) yes N3 . C2 . C1 . 115.7(2) yes N3 . C4 . C5 . 112.8(2) yes N6 . C5 . C4 . 112.7(2) yes N6 . C7 . C8 . 111.6(2) yes N9 . C8 . C7 . 111.4(2) yes N3 . C31 . C32 . 114.3(2) yes N3 . C31 . C33 . 113.6(3) yes C32 . C31 . C33 . 108.4(3) yes N6 . C61 . C62 . 114.7(2) yes C61 . C62 . C63 . 112.7(3) yes N1 . C63 . C62 . 110.7(3) yes N9 . C91 . C92 . 113.7(3) yes N9 . C91 . C93 . 114.6(3) yes C92 . C91 . C93 . 108.9(3) yes S1 . C100 . F1 . 111.8(3) yes S1 . C100 . F2 . 111.3(2) yes F1 . C100 . F2 . 107.2(3) yes S1 . C100 . F3 . 109.7(3) yes F1 . C100 . F3 . 108.7(3) yes F2 . C100 . F3 . 108.1(3) yes C100 . S1 . O1 . 100.7(1) yes C100 . S1 . O2 . 104.9(2) yes O1 . S1 . O2 . 111.9(1) yes C100 . S1 . O3 . 104.1(2) yes O1 . S1 . O3 . 115.2(1) yes O2 . S1 . O3 . 117.6(2) yes Ti1 . O1 . S1 . 138.9(1) yes #===end