Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Juan Fernandez-Baeza' _publ_contact_author_address ; Quimica Inorganica, Organica y Bioquimica Universidad de Castilla-La Mancha Facultad de Quimicas, Campus Univer Ciudad Real 13071 SPAIN ; _publ_contact_author_email JUAN.FBAEZA@UCLM.ES _publ_section_title ; Design of new heteroscorpionate ligands and their coordinative ability toward group 4 transition metals; an efficient synthetic route to obtain enantiopure ligands. ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address A.Otero ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; J.Fernandez-Baeza ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; 'Antinolo, A.' ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; J.Tejeda ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; A.Lara-Sanchez ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; ; L.Sanchez-Barba ; ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; M.Sanchez-Molina ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; S.Franco ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; I.Lopez-Solera ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; A.M.Rodriguez ; Departamento de Quimica Inorganica, Organica y Bioquimica Universidad Castilla-La Mancha Facultad de Quimicas Campus de Ciudad Real 13071-Ciudad Real Spain ; #============================================================================ data_1 _database_code_depnum_ccdc_archive 'CCDC 277594' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H56 Li2 N10 O3' _chemical_formula_weight 690.79 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 11.5670(9) _cell_length_b 17.5380(13) _cell_length_c 19.5684(15) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3969.7(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Prismatic _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.234 _exptl_crystal_size_mid 0.201 _exptl_crystal_size_min 0.188 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.156 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1488 _exptl_absorpt_coefficient_mu 0.075 _exptl_absorpt_correction_type Semi-empirical _exptl_absorpt_correction_T_min 0.67112 _exptl_absorpt_correction_T_max 1 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16055 _diffrn_reflns_av_R_equivalents 0.0526 _diffrn_reflns_av_sigmaI/netI 0.0429 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.56 _diffrn_reflns_theta_max 19.82 _reflns_number_total 3606 _reflns_number_gt 3145 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0824P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0104(13) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.00 _refine_ls_number_reflns 3606 _refine_ls_number_parameters 475 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0553 _refine_ls_R_factor_gt 0.0447 _refine_ls_wR_factor_ref 0.1301 _refine_ls_wR_factor_gt 0.1134 _refine_ls_goodness_of_fit_ref 1.108 _refine_ls_restrained_S_all 1.108 _refine_ls_shift/su_max 0.012 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Li1 Li 0.1426(6) 0.0323(4) 0.4008(4) 0.0397(19) Uani 1 1 d . . . Li2 Li 0.0760(7) 0.1560(4) 0.3568(3) 0.0401(19) Uani 1 1 d . . . O1 O 0.2095(3) 0.10229(16) 0.33453(14) 0.0348(8) Uani 1 1 d . . . O2 O 0.0397(3) 0.09750(15) 0.44051(13) 0.0345(8) Uani 1 1 d . . . N1 N 0.2914(3) -0.02898(19) 0.4199(2) 0.0389(10) Uani 1 1 d . . . N2 N 0.3481(3) -0.03691(19) 0.3584(2) 0.0377(10) Uani 1 1 d . . . N3 N 0.0896(4) -0.0381(2) 0.32549(17) 0.0382(10) Uani 1 1 d . . . N4 N 0.1836(3) -0.0585(2) 0.28724(18) 0.0353(10) Uani 1 1 d . . . N5 N 0.3379(3) 0.0992(2) 0.2409(2) 0.0417(10) Uani 1 1 d . . . N6 N -0.0834(3) 0.13525(19) 0.31540(19) 0.0376(10) Uani 1 1 d . . . N7 N -0.1678(3) 0.14475(19) 0.36357(17) 0.0335(10) Uani 1 1 d . . . N8 N 0.0161(3) 0.2564(2) 0.39829(16) 0.0327(9) Uani 1 1 d . . . N9 N -0.0845(3) 0.2424(2) 0.43308(17) 0.0344(10) Uani 1 1 d . . . N10 N -0.1103(3) 0.0765(2) 0.51895(18) 0.0394(10) Uani 1 1 d . . . C1 C 0.3671(5) -0.0523(3) 0.4662(3) 0.0466(14) Uani 1 1 d . . . C2 C 0.4700(5) -0.0738(3) 0.4359(3) 0.0476(13) Uani 1 1 d . . . H2 H 0.5356 -0.0918 0.4581 0.057 Uiso 1 1 calc R . . C3 C 0.4567(5) -0.0637(3) 0.3673(3) 0.0476(13) Uani 1 1 d . . . C4 C 0.3347(4) -0.0548(3) 0.5399(3) 0.0581(15) Uani 1 1 d . . . H4A H 0.3014 -0.0068 0.5530 0.087 Uiso 1 1 calc R . . H4B H 0.4025 -0.0643 0.5669 0.087 Uiso 1 1 calc R . . H4C H 0.2795 -0.0948 0.5472 0.087 Uiso 1 1 calc R . . C5 C 0.5367(4) -0.0764(3) 0.3089(3) 0.0625(15) Uani 1 1 d . . . H5A H 0.5071 -0.1164 0.2804 0.094 Uiso 1 1 calc R . . H5B H 0.6115 -0.0906 0.3259 0.094 Uiso 1 1 calc R . . H5C H 0.5432 -0.0303 0.2827 0.094 Uiso 1 1 calc R . . C6 C 0.0047(4) -0.0866(3) 0.3072(2) 0.0409(13) Uani 1 1 d . . . C7 C 0.0469(5) -0.1381(3) 0.2588(2) 0.0457(13) Uani 1 1 d . . . H7 H 0.0055 -0.1773 0.2382 0.055 Uiso 1 1 calc R . . C8 C 0.1587(5) -0.1205(3) 0.2474(2) 0.0424(13) Uani 1 1 d . . . C9 C -0.1121(4) -0.0794(3) 0.3377(3) 0.0520(14) Uani 1 1 d . . . H9A H -0.1228 -0.1183 0.3715 0.078 Uiso 1 1 calc R . . H9B H -0.1695 -0.0849 0.3026 0.078 Uiso 1 1 calc R . . H9C H -0.1198 -0.0301 0.3587 0.078 Uiso 1 1 calc R . . C10 C 0.2472(4) -0.1568(3) 0.2019(2) 0.0564(15) Uani 1 1 d . . . H10A H 0.2705 -0.1211 0.1673 0.085 Uiso 1 1 calc R . . H10B H 0.2145 -0.2012 0.1806 0.085 Uiso 1 1 calc R . . H10C H 0.3133 -0.1714 0.2286 0.085 Uiso 1 1 calc R . . C11 C 0.2905(4) -0.0163(2) 0.2945(2) 0.0392(13) Uani 1 1 d . . . H11 H 0.3414 -0.0319 0.2570 0.047 Uiso 1 1 calc R . . C12 C 0.2761(4) 0.0712(2) 0.2896(2) 0.0336(12) Uani 1 1 d . . . C13 C 0.3383(4) 0.1826(2) 0.2283(2) 0.0424(13) Uani 1 1 d . . . C14 C 0.4200(5) 0.1959(3) 0.1692(3) 0.0647(17) Uani 1 1 d . . . H14A H 0.4963 0.1796 0.1817 0.097 Uiso 1 1 calc R . . H14B H 0.4213 0.2492 0.1581 0.097 Uiso 1 1 calc R . . H14C H 0.3942 0.1674 0.1302 0.097 Uiso 1 1 calc R . . C15 C 0.2182(5) 0.2095(3) 0.2074(2) 0.0532(14) Uani 1 1 d . . . H15A H 0.1900 0.1782 0.1707 0.080 Uiso 1 1 calc R . . H15B H 0.2222 0.2616 0.1925 0.080 Uiso 1 1 calc R . . H15C H 0.1668 0.2057 0.2457 0.080 Uiso 1 1 calc R . . C16 C 0.3800(4) 0.2268(3) 0.2917(2) 0.0524(14) Uani 1 1 d . . . H16A H 0.3322 0.2140 0.3301 0.079 Uiso 1 1 calc R . . H16B H 0.3751 0.2805 0.2830 0.079 Uiso 1 1 calc R . . H16C H 0.4588 0.2133 0.3014 0.079 Uiso 1 1 calc R . . C17 C -0.2730(5) 0.1223(3) 0.3403(3) 0.0405(12) Uani 1 1 d . . . C18 C -0.2562(5) 0.1001(3) 0.2741(3) 0.0483(14) Uani 1 1 d . . . H18 H -0.3122 0.0826 0.2438 0.058 Uiso 1 1 calc R . . C19 C -0.1389(5) 0.1086(2) 0.2609(2) 0.0399(13) Uani 1 1 d . . . C20 C -0.0714(5) 0.0888(3) 0.1967(2) 0.0546(14) Uani 1 1 d . . . H20A H 0.0031 0.1129 0.1984 0.082 Uiso 1 1 calc R . . H20B H -0.1128 0.1065 0.1573 0.082 Uiso 1 1 calc R . . H20C H -0.0617 0.0346 0.1939 0.082 Uiso 1 1 calc R . . C21 C -0.3773(4) 0.1217(3) 0.3841(2) 0.0564(15) Uani 1 1 d . . . H21A H -0.3645 0.0890 0.4227 0.085 Uiso 1 1 calc R . . H21B H -0.4421 0.1033 0.3583 0.085 Uiso 1 1 calc R . . H21C H -0.3931 0.1725 0.3998 0.085 Uiso 1 1 calc R . . C22 C 0.0422(4) 0.3286(3) 0.4139(2) 0.0371(12) Uani 1 1 d . . . C23 C -0.0376(4) 0.3586(3) 0.4594(2) 0.0403(12) Uani 1 1 d . . . H23 H -0.0364 0.4071 0.4786 0.048 Uiso 1 1 calc R . . C24 C -0.1179(4) 0.3034(3) 0.4703(2) 0.0378(12) Uani 1 1 d . . . C25 C 0.1468(4) 0.3649(3) 0.3844(2) 0.0450(13) Uani 1 1 d . . . H25A H 0.1841 0.3298 0.3539 0.067 Uiso 1 1 calc R . . H25B H 0.1990 0.3785 0.4206 0.067 Uiso 1 1 calc R . . H25C H 0.1248 0.4099 0.3597 0.067 Uiso 1 1 calc R . . C26 C -0.2232(4) 0.3033(3) 0.5145(2) 0.0544(15) Uani 1 1 d . . . H26A H -0.2911 0.3028 0.4862 0.082 Uiso 1 1 calc R . . H26B H -0.2236 0.3482 0.5426 0.082 Uiso 1 1 calc R . . H26C H -0.2228 0.2588 0.5431 0.082 Uiso 1 1 calc R . . C27 C -0.1373(4) 0.1667(2) 0.4322(2) 0.0326(12) Uani 1 1 d . . . H27 H -0.2093 0.1701 0.4584 0.039 Uiso 1 1 calc R . . C28 C -0.0608(5) 0.1071(2) 0.4678(2) 0.0326(11) Uani 1 1 d . . . C29 C -0.0479(4) 0.0186(3) 0.5598(2) 0.0457(14) Uani 1 1 d . . . C30 C -0.1309(5) -0.0077(3) 0.6144(3) 0.076(2) Uani 1 1 d . . . H30A H -0.1517 0.0347 0.6429 0.113 Uiso 1 1 calc R . . H30B H -0.0948 -0.0464 0.6417 0.113 Uiso 1 1 calc R . . H30C H -0.1991 -0.0282 0.5933 0.113 Uiso 1 1 calc R . . C31 C 0.0583(5) 0.0547(3) 0.5927(2) 0.0620(15) Uani 1 1 d . . . H31A H 0.1134 0.0677 0.5578 0.093 Uiso 1 1 calc R . . H31B H 0.0926 0.0192 0.6240 0.093 Uiso 1 1 calc R . . H31C H 0.0359 0.1000 0.6168 0.093 Uiso 1 1 calc R . . C32 C -0.0133(4) -0.0504(2) 0.5178(2) 0.0471(13) Uani 1 1 d . . . H32A H -0.0794 -0.0692 0.4935 0.071 Uiso 1 1 calc R . . H32B H 0.0156 -0.0895 0.5476 0.071 Uiso 1 1 calc R . . H32C H 0.0458 -0.0361 0.4859 0.071 Uiso 1 1 calc R . . O3 O 0.8840(5) 0.2060(4) 0.0307(3) 0.131(2) Uani 1 1 d . . . C33 C 0.7745(7) 0.2019(5) 0.0025(3) 0.107(3) Uani 1 1 d . . . H33A H 0.7566 0.1499 -0.0104 0.128 Uiso 1 1 calc R . . H33B H 0.7697 0.2339 -0.0378 0.128 Uiso 1 1 calc R . . C34 C 0.6924(6) 0.2291(4) 0.0556(4) 0.108(3) Uani 1 1 d . . . H34A H 0.6377 0.2651 0.0364 0.130 Uiso 1 1 calc R . . H34B H 0.6501 0.1867 0.0754 0.130 Uiso 1 1 calc R . . C35 C 0.7664(6) 0.2662(3) 0.1074(3) 0.0789(19) Uani 1 1 d . . . H35A H 0.7671 0.2372 0.1496 0.095 Uiso 1 1 calc R . . H35B H 0.7397 0.3176 0.1170 0.095 Uiso 1 1 calc R . . C36 C 0.8840(7) 0.2674(4) 0.0752(4) 0.110(3) Uani 1 1 d . . . H36A H 0.8965 0.3148 0.0506 0.131 Uiso 1 1 calc R . . H36B H 0.9439 0.2618 0.1095 0.131 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Li1 0.037(5) 0.040(5) 0.042(4) -0.008(4) 0.000(4) 0.012(4) Li2 0.049(5) 0.034(4) 0.038(4) 0.000(4) 0.007(4) -0.003(4) O1 0.038(2) 0.0314(17) 0.0347(17) -0.0043(15) 0.0073(17) 0.0012(15) O2 0.032(2) 0.0362(18) 0.0348(16) 0.0023(14) 0.0039(17) 0.0023(15) N1 0.040(3) 0.032(2) 0.044(2) 0.008(2) 0.001(3) 0.004(2) N2 0.031(3) 0.029(2) 0.052(3) 0.000(2) -0.002(2) 0.001(2) N3 0.039(3) 0.035(2) 0.041(2) -0.0034(19) 0.010(2) -0.001(2) N4 0.036(3) 0.029(2) 0.041(2) -0.004(2) 0.001(2) -0.004(2) N5 0.047(3) 0.027(2) 0.050(2) 0.002(2) 0.015(2) 0.002(2) N6 0.049(3) 0.032(2) 0.031(2) -0.0018(18) -0.002(2) -0.004(2) N7 0.036(3) 0.035(2) 0.030(2) 0.0006(19) 0.006(2) 0.001(2) N8 0.033(3) 0.032(3) 0.033(2) 0.0027(19) -0.003(2) -0.0016(19) N9 0.040(3) 0.032(3) 0.031(2) 0.002(2) -0.002(2) 0.003(2) N10 0.045(3) 0.043(2) 0.030(2) 0.008(2) 0.007(2) 0.009(2) C1 0.052(4) 0.032(3) 0.056(4) 0.009(3) -0.006(4) -0.006(3) C2 0.034(4) 0.048(3) 0.060(4) 0.008(3) -0.010(3) 0.004(3) C3 0.039(4) 0.032(3) 0.071(4) 0.004(3) 0.001(3) -0.002(3) C4 0.055(4) 0.060(3) 0.059(4) 0.017(3) -0.013(3) -0.003(3) C5 0.039(3) 0.060(4) 0.089(4) 0.002(3) 0.005(3) 0.005(3) C6 0.050(4) 0.030(3) 0.043(3) 0.004(3) -0.008(3) -0.004(3) C7 0.054(4) 0.035(3) 0.049(3) -0.005(3) -0.007(3) -0.011(3) C8 0.059(4) 0.035(3) 0.033(3) -0.008(3) 0.003(3) 0.004(3) C9 0.038(3) 0.054(3) 0.064(3) -0.003(3) 0.001(3) -0.005(3) C10 0.070(4) 0.043(3) 0.056(3) -0.018(3) 0.008(3) -0.011(3) C11 0.039(3) 0.038(3) 0.041(3) 0.004(2) 0.005(3) 0.008(3) C12 0.035(3) 0.023(3) 0.042(3) 0.003(3) -0.003(3) -0.005(2) C13 0.054(4) 0.025(3) 0.048(3) 0.002(2) 0.008(3) -0.001(2) C14 0.082(4) 0.037(3) 0.075(4) 0.009(3) 0.040(3) 0.003(3) C15 0.069(4) 0.039(3) 0.052(3) 0.003(3) 0.002(3) 0.009(3) C16 0.063(4) 0.033(3) 0.060(3) 0.001(3) 0.000(3) -0.006(3) C17 0.033(4) 0.041(3) 0.048(3) -0.002(2) -0.005(3) -0.002(3) C18 0.051(4) 0.049(3) 0.045(3) 0.000(3) -0.007(3) -0.013(3) C19 0.050(4) 0.035(3) 0.035(3) 0.000(2) 0.000(3) -0.005(3) C20 0.066(4) 0.055(3) 0.042(3) -0.009(3) 0.001(3) -0.005(3) C21 0.038(4) 0.072(4) 0.060(3) -0.008(3) 0.000(3) -0.002(3) C22 0.041(3) 0.029(3) 0.041(3) 0.003(2) -0.013(3) -0.002(3) C23 0.042(3) 0.033(3) 0.046(3) -0.006(3) -0.004(3) 0.005(3) C24 0.044(4) 0.036(3) 0.033(3) -0.009(3) -0.009(3) 0.013(3) C25 0.051(3) 0.030(3) 0.054(3) 0.002(2) -0.004(3) 0.000(3) C26 0.060(4) 0.055(3) 0.049(3) -0.011(3) 0.006(3) 0.016(3) C27 0.034(3) 0.037(3) 0.027(3) -0.005(2) 0.001(2) 0.002(2) C28 0.038(4) 0.030(3) 0.029(3) -0.003(2) -0.004(3) 0.004(2) C29 0.046(3) 0.051(3) 0.040(3) 0.013(3) 0.006(3) 0.012(3) C30 0.079(4) 0.082(4) 0.066(3) 0.045(3) 0.032(4) 0.035(4) C31 0.076(4) 0.060(4) 0.050(3) 0.002(3) -0.013(3) 0.022(3) C32 0.056(3) 0.036(3) 0.049(3) 0.012(3) 0.007(3) 0.007(3) O3 0.117(5) 0.158(5) 0.117(4) -0.076(4) 0.023(4) -0.001(4) C33 0.089(6) 0.152(7) 0.079(5) -0.044(5) -0.001(5) -0.041(5) C34 0.093(6) 0.079(5) 0.153(7) -0.035(5) 0.026(6) -0.014(4) C35 0.108(6) 0.048(4) 0.080(4) -0.004(3) 0.018(5) 0.005(4) C36 0.131(7) 0.101(6) 0.097(5) -0.010(5) 0.007(5) -0.049(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Li1 O2 1.825(8) . ? Li1 O1 1.946(8) . ? Li1 N3 2.017(8) . ? Li1 N1 2.063(8) . ? Li1 Li2 2.459(10) . ? Li1 C12 2.755(9) . ? Li2 O1 1.860(8) . ? Li2 O2 1.978(7) . ? Li2 N6 2.047(8) . ? Li2 N8 2.059(8) . ? O1 C12 1.290(5) . ? O2 C28 1.291(5) . ? N1 C1 1.324(6) . ? N1 N2 1.377(5) . ? N2 C3 1.353(6) . ? N2 C11 1.462(6) . ? N3 C6 1.347(5) . ? N3 N4 1.368(5) . ? N4 C8 1.368(5) . ? N4 C11 1.449(6) . ? N5 C12 1.287(5) . ? N5 C13 1.484(6) . ? N6 C19 1.330(5) . ? N6 N7 1.367(4) . ? N7 C17 1.358(6) . ? N7 C27 1.442(5) . ? N8 C22 1.337(5) . ? N8 N9 1.370(5) . ? N9 C24 1.351(5) . ? N9 C27 1.462(6) . ? N10 C28 1.271(5) . ? N10 C29 1.480(6) . ? C1 C2 1.382(7) . ? C1 C4 1.491(7) . ? C2 C3 1.363(7) . ? C3 C5 1.487(7) . ? C6 C7 1.397(6) . ? C6 C9 1.483(6) . ? C7 C8 1.348(7) . ? C8 C10 1.499(7) . ? C11 C12 1.547(6) . ? C13 C14 1.512(6) . ? C13 C15 1.522(7) . ? C13 C16 1.541(6) . ? C17 C18 1.368(6) . ? C17 C21 1.480(6) . ? C18 C19 1.389(7) . ? C19 C20 1.519(6) . ? C22 C23 1.386(6) . ? C22 C25 1.484(6) . ? C23 C24 1.359(6) . ? C24 C26 1.494(7) . ? C27 C28 1.536(6) . ? C29 C30 1.509(6) . ? C29 C32 1.517(6) . ? C29 C31 1.525(7) . ? O3 C33 1.383(8) . ? O3 C36 1.385(8) . ? C33 C34 1.485(8) . ? C34 C35 1.478(8) . ? C35 C36 1.500(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Li1 O1 98.5(4) . . ? O2 Li1 N3 119.8(4) . . ? O1 Li1 N3 91.2(3) . . ? O2 Li1 N1 142.5(4) . . ? O1 Li1 N1 96.8(3) . . ? N3 Li1 N1 93.9(3) . . ? O2 Li1 Li2 52.5(3) . . ? O1 Li1 Li2 48.2(2) . . ? N3 Li1 Li2 100.9(3) . . ? N1 Li1 Li2 141.7(4) . . ? O2 Li1 C12 123.1(4) . . ? O1 Li1 C12 25.09(15) . . ? N3 Li1 C12 75.2(3) . . ? N1 Li1 C12 78.7(3) . . ? Li2 Li1 C12 71.3(3) . . ? O1 Li2 O2 96.1(3) . . ? O1 Li2 N6 124.4(4) . . ? O2 Li2 N6 92.5(3) . . ? O1 Li2 N8 143.6(4) . . ? O2 Li2 N8 92.6(3) . . ? N6 Li2 N8 90.3(3) . . ? O1 Li2 Li1 51.3(3) . . ? O2 Li2 Li1 47.0(2) . . ? N6 Li2 Li1 105.3(3) . . ? N8 Li2 Li1 136.2(4) . . ? C12 O1 Li2 150.3(3) . . ? C12 O1 Li1 115.2(3) . . ? Li2 O1 Li1 80.4(3) . . ? C28 O2 Li1 147.7(4) . . ? C28 O2 Li2 117.8(4) . . ? Li1 O2 Li2 80.5(3) . . ? C1 N1 N2 104.6(4) . . ? C1 N1 Li1 146.7(4) . . ? N2 N1 Li1 106.9(3) . . ? C3 N2 N1 111.4(4) . . ? C3 N2 C11 128.3(4) . . ? N1 N2 C11 120.4(4) . . ? C6 N3 N4 105.6(3) . . ? C6 N3 Li1 143.3(4) . . ? N4 N3 Li1 108.5(3) . . ? N3 N4 C8 110.7(4) . . ? N3 N4 C11 119.4(3) . . ? C8 N4 C11 129.9(4) . . ? C12 N5 C13 120.0(4) . . ? C19 N6 N7 104.5(4) . . ? C19 N6 Li2 144.6(4) . . ? N7 N6 Li2 110.4(3) . . ? C17 N7 N6 111.9(3) . . ? C17 N7 C27 127.6(4) . . ? N6 N7 C27 120.0(4) . . ? C22 N8 N9 104.3(4) . . ? C22 N8 Li2 145.5(4) . . ? N9 N8 Li2 109.2(3) . . ? C24 N9 N8 111.7(4) . . ? C24 N9 C27 127.3(4) . . ? N8 N9 C27 120.8(4) . . ? C28 N10 C29 119.7(4) . . ? N1 C1 C2 111.1(4) . . ? N1 C1 C4 120.3(5) . . ? C2 C1 C4 128.5(5) . . ? C3 C2 C1 106.8(5) . . ? N2 C3 C2 106.0(5) . . ? N2 C3 C5 122.1(5) . . ? C2 C3 C5 131.9(5) . . ? N3 C6 C7 109.5(4) . . ? N3 C6 C9 120.2(4) . . ? C7 C6 C9 130.3(5) . . ? C8 C7 C6 107.4(4) . . ? C7 C8 N4 106.8(4) . . ? C7 C8 C10 131.0(5) . . ? N4 C8 C10 122.2(5) . . ? N4 C11 N2 110.2(3) . . ? N4 C11 C12 114.1(4) . . ? N2 C11 C12 110.4(4) . . ? N5 C12 O1 132.5(4) . . ? N5 C12 C11 111.3(4) . . ? O1 C12 C11 116.1(4) . . ? N5 C12 Li1 171.9(3) . . ? O1 C12 Li1 39.7(2) . . ? C11 C12 Li1 76.4(3) . . ? N5 C13 C14 106.4(4) . . ? N5 C13 C15 110.4(4) . . ? C14 C13 C15 108.5(4) . . ? N5 C13 C16 111.3(4) . . ? C14 C13 C16 110.0(4) . . ? C15 C13 C16 110.3(4) . . ? N7 C17 C18 105.8(4) . . ? N7 C17 C21 122.6(4) . . ? C18 C17 C21 131.6(5) . . ? C17 C18 C19 106.5(5) . . ? N6 C19 C18 111.1(4) . . ? N6 C19 C20 119.7(5) . . ? C18 C19 C20 129.1(5) . . ? N8 C22 C23 110.9(4) . . ? N8 C22 C25 120.1(4) . . ? C23 C22 C25 129.0(5) . . ? C24 C23 C22 106.6(4) . . ? N9 C24 C23 106.5(4) . . ? N9 C24 C26 122.9(4) . . ? C23 C24 C26 130.5(4) . . ? N7 C27 N9 110.8(3) . . ? N7 C27 C28 112.5(3) . . ? N9 C27 C28 111.9(3) . . ? N10 C28 O2 132.6(4) . . ? N10 C28 C27 112.6(4) . . ? O2 C28 C27 114.8(4) . . ? N10 C29 C30 106.4(4) . . ? N10 C29 C32 112.5(4) . . ? C30 C29 C32 107.9(4) . . ? N10 C29 C31 109.6(4) . . ? C30 C29 C31 110.0(4) . . ? C32 C29 C31 110.3(4) . . ? C33 O3 C36 106.8(6) . . ? O3 C33 C34 106.9(5) . . ? C35 C34 C33 104.5(6) . . ? C34 C35 C36 104.0(5) . . ? O3 C36 C35 104.7(6) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 19.82 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.312 _refine_diff_density_min -0.182 _refine_diff_density_rms 0.057 #=================END data_6 _database_code_depnum_ccdc_archive 'CCDC 277595' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H59 Cl10 N10 S2 Ti2' _chemical_formula_weight 1146.35 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 37.375(5) _cell_length_b 9.892(3) _cell_length_c 30.905(3) _cell_angle_alpha 90.00 _cell_angle_beta 97.57(2) _cell_angle_gamma 90.00 _cell_volume 11326(4) _cell_formula_units_Z 8 _cell_measurement_temperature 230(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.345 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4728 _exptl_absorpt_coefficient_mu 0.862 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 230(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'four circle diffractometer Nonius-Mach3' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% ? _diffrn_reflns_number 17943 _diffrn_reflns_av_R_equivalents 0.0679 _diffrn_reflns_av_sigmaI/netI 0.1008 _diffrn_reflns_limit_h_min -44 _diffrn_reflns_limit_h_max 44 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 2.13 _diffrn_reflns_theta_max 25.00 _reflns_number_total 9969 _reflns_number_gt 4900 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius (control program)' _computing_cell_refinement 'Nonius (control program)' _computing_data_reduction 'XRAY80 (Stewart, 1976)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1855P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9969 _refine_ls_number_parameters 568 _refine_ls_number_restraints 24 _refine_ls_R_factor_all 0.1794 _refine_ls_R_factor_gt 0.0839 _refine_ls_wR_factor_ref 0.3082 _refine_ls_wR_factor_gt 0.2532 _refine_ls_goodness_of_fit_ref 1.031 _refine_ls_restrained_S_all 1.031 _refine_ls_shift/su_max 0.069 _refine_ls_shift/su_mean 0.004 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.34308(4) 0.17169(19) 0.53333(5) 0.0588(5) Uani 1 1 d . . . Ti2 Ti 0.29518(4) 0.30848(15) 0.28108(5) 0.0446(4) Uani 1 1 d . . . Cl1 Cl 0.33129(8) 0.0470(3) 0.47299(9) 0.0915(10) Uani 1 1 d . . . Cl2 Cl 0.33898(8) 0.0138(3) 0.58454(9) 0.0885(9) Uani 1 1 d . . . Cl3 Cl 0.28919(6) 0.2596(4) 0.53827(9) 0.0850(9) Uani 1 1 d . . . Cl4 Cl 0.28172(8) 0.4727(3) 0.32568(8) 0.0770(8) Uani 1 1 d . . . Cl5 Cl 0.24170(6) 0.2904(3) 0.23978(7) 0.0611(6) Uani 1 1 d . . . Cl6 Cl 0.32342(7) 0.4441(3) 0.23862(9) 0.0736(7) Uani 1 1 d . . . Cl7 Cl 0.48595(6) 0.6116(3) 0.57005(8) 0.0701(7) Uani 1 1 d . . . Cl8 Cl 0.39261(8) 0.7779(3) 0.37642(12) 0.1002(11) Uani 1 1 d . . . S1 S 0.36545(6) 0.3234(3) 0.59577(7) 0.0616(7) Uani 1 1 d . . . S2 S 0.35441(7) 0.2926(3) 0.32977(9) 0.0691(7) Uani 1 1 d . . . N1 N 0.40074(19) 0.1281(8) 0.5351(2) 0.0537(18) Uani 1 1 d . . . N2 N 0.42662(17) 0.2271(7) 0.5379(2) 0.0450(16) Uani 1 1 d . . . N3 N 0.35739(16) 0.3405(7) 0.4956(2) 0.0484(17) Uani 1 1 d . . . N4 N 0.39069(15) 0.4052(7) 0.5034(2) 0.0452(17) Uani 1 1 d . . . N5 N 0.42158(17) 0.4913(8) 0.6072(2) 0.0520(18) Uani 1 1 d . . . H5 H 0.4407 0.5208 0.5970 0.062 Uiso 1 1 calc R . . N6 N 0.28053(16) 0.1545(7) 0.3255(2) 0.0440(16) Uani 1 1 d . . . N7 N 0.30176(16) 0.0400(6) 0.3367(2) 0.0412(15) Uani 1 1 d . . . N8 N 0.31528(15) 0.1320(6) 0.2501(2) 0.0388(14) Uani 1 1 d . . . N9 N 0.33154(15) 0.0245(6) 0.2729(2) 0.0392(15) Uani 1 1 d . . . N10 N 0.39338(17) 0.0795(8) 0.3579(2) 0.058(2) Uani 1 1 d . A . H10 H 0.3941 -0.0083 0.3597 0.069 Uiso 1 1 calc R . . C1 C 0.4023(2) 0.4021(9) 0.5832(2) 0.047(2) Uani 1 1 d . . . C2 C 0.41674(18) 0.3680(8) 0.5399(2) 0.0384(18) Uani 1 1 d . . . H2 H 0.4387 0.4226 0.5385 0.046 Uiso 1 1 calc R . . C3 C 0.4189(3) 0.0128(11) 0.5326(3) 0.065(3) Uani 1 1 d . . . C4 C 0.4551(3) 0.0403(11) 0.5341(3) 0.069(3) Uani 1 1 d . . . H4 H 0.4735 -0.0242 0.5333 0.083 Uiso 1 1 calc R . . C5 C 0.4598(2) 0.1730(10) 0.5367(3) 0.055(2) Uani 1 1 d . . . C6 C 0.4027(4) -0.1255(12) 0.5289(5) 0.115(5) Uani 1 1 d . . . H6A H 0.4212 -0.1922 0.5379 0.173 Uiso 1 1 calc R . . H6B H 0.3926 -0.1422 0.4988 0.173 Uiso 1 1 calc R . . H6C H 0.3838 -0.1318 0.5475 0.173 Uiso 1 1 calc R . . C7 C 0.4928(2) 0.2571(11) 0.5362(3) 0.068(3) Uani 1 1 d . . . H7A H 0.5139 0.1996 0.5404 0.102 Uiso 1 1 calc R . . H7B H 0.4941 0.3235 0.5595 0.102 Uiso 1 1 calc R . . H7C H 0.4917 0.3031 0.5083 0.102 Uiso 1 1 calc R . . C8 C 0.3411(2) 0.3983(11) 0.4595(3) 0.061(3) Uani 1 1 d . . . C9 C 0.3628(2) 0.4964(10) 0.4442(3) 0.058(2) Uani 1 1 d . . . H9 H 0.3570 0.5508 0.4193 0.070 Uiso 1 1 calc R . . C10 C 0.3947(2) 0.4990(9) 0.4724(3) 0.050(2) Uani 1 1 d . . . C11 C 0.3043(2) 0.3562(14) 0.4378(3) 0.089(4) Uani 1 1 d . . . H11A H 0.3068 0.2813 0.4181 0.134 Uiso 1 1 calc R . . H11B H 0.2929 0.4318 0.4214 0.134 Uiso 1 1 calc R . . H11C H 0.2896 0.3283 0.4598 0.134 Uiso 1 1 calc R . . C12 C 0.4286(2) 0.5731(10) 0.4697(3) 0.060(2) Uani 1 1 d . . . H12A H 0.4356 0.6216 0.4968 0.090 Uiso 1 1 calc R . . H12B H 0.4250 0.6368 0.4456 0.090 Uiso 1 1 calc R . . H12C H 0.4475 0.5096 0.4649 0.090 Uiso 1 1 calc R . . C13 C 0.4148(3) 0.5493(12) 0.6504(3) 0.071(3) Uani 1 1 d . . . C14 C 0.3803(3) 0.6350(14) 0.6438(4) 0.109(4) Uani 1 1 d . . . H14A H 0.3834 0.7090 0.6240 0.163 Uiso 1 1 calc R . . H14B H 0.3755 0.6710 0.6717 0.163 Uiso 1 1 calc R . . H14C H 0.3602 0.5792 0.6315 0.163 Uiso 1 1 calc R . . C15 C 0.4103(4) 0.4321(14) 0.6833(3) 0.110(5) Uani 1 1 d . . . H15A H 0.3905 0.3741 0.6713 0.165 Uiso 1 1 calc R . . H15B H 0.4053 0.4699 0.7108 0.165 Uiso 1 1 calc R . . H15C H 0.4324 0.3797 0.6880 0.165 Uiso 1 1 calc R . . C16 C 0.4475(3) 0.6402(15) 0.6650(4) 0.112(5) Uani 1 1 d . . . H16A H 0.4688 0.5846 0.6724 0.168 Uiso 1 1 calc R . . H16B H 0.4431 0.6923 0.6903 0.168 Uiso 1 1 calc R . . H16C H 0.4513 0.7012 0.6414 0.168 Uiso 1 1 calc R . . C17 C 0.3639(2) 0.1308(9) 0.3382(3) 0.049(2) Uani 1 1 d . . . C18 C 0.33595(19) 0.0227(8) 0.3200(2) 0.0413(18) Uani 1 1 d . . . H18 H 0.3457 -0.0669 0.3297 0.050 Uiso 1 1 calc R . . C19 C 0.2514(2) 0.1358(10) 0.3449(3) 0.052(2) Uani 1 1 d . . . C20 C 0.2538(2) 0.0138(10) 0.3686(3) 0.056(2) Uani 1 1 d . . . H20 H 0.2367 -0.0210 0.3854 0.067 Uiso 1 1 calc R . . C21 C 0.2859(2) -0.0438(8) 0.3622(3) 0.045(2) Uani 1 1 d . . . C22 C 0.2206(3) 0.2325(11) 0.3414(3) 0.073(3) Uani 1 1 d . . . H22A H 0.2273 0.3108 0.3596 0.110 Uiso 1 1 calc R . . H22B H 0.1998 0.1888 0.3510 0.110 Uiso 1 1 calc R . . H22C H 0.2147 0.2611 0.3112 0.110 Uiso 1 1 calc R . . C23 C 0.3012(3) -0.1764(9) 0.3786(3) 0.062(2) Uani 1 1 d . . . H23A H 0.3032 -0.2360 0.3542 0.093 Uiso 1 1 calc R . . H23B H 0.2855 -0.2170 0.3976 0.093 Uiso 1 1 calc R . . H23C H 0.3250 -0.1622 0.3949 0.093 Uiso 1 1 calc R . . C24 C 0.3165(2) 0.1020(8) 0.2076(2) 0.0428(19) Uani 1 1 d . . . C25 C 0.3344(2) -0.0209(9) 0.2049(3) 0.050(2) Uani 1 1 d . . . H25 H 0.3393 -0.0631 0.1791 0.060 Uiso 1 1 calc R . . C26 C 0.3435(2) -0.0691(9) 0.2463(3) 0.049(2) Uani 1 1 d . . . C27 C 0.2998(2) 0.1864(10) 0.1708(3) 0.055(2) Uani 1 1 d . . . H27A H 0.2740 0.1920 0.1716 0.082 Uiso 1 1 calc R . . H27B H 0.3043 0.1461 0.1434 0.082 Uiso 1 1 calc R . . H27C H 0.3101 0.2765 0.1733 0.082 Uiso 1 1 calc R . . C28 C 0.3601(3) -0.1983(10) 0.2611(3) 0.076(3) Uani 1 1 d . . . H28A H 0.3803 -0.1817 0.2835 0.114 Uiso 1 1 calc R . . H28B H 0.3686 -0.2440 0.2366 0.114 Uiso 1 1 calc R . . H28C H 0.3425 -0.2545 0.2728 0.114 Uiso 1 1 calc R . . C29 C 0.4270(2) 0.1545(9) 0.3784(3) 0.064(3) Uani 1 1 d D . . C30 C 0.4184(5) 0.256(2) 0.4110(6) 0.052(5) Uiso 0.51(3) 1 d PD A 1 H30A H 0.4403 0.2808 0.4298 0.077 Uiso 0.51(3) 1 calc PR A 1 H30B H 0.4012 0.2181 0.4285 0.077 Uiso 0.51(3) 1 calc PR A 1 H30C H 0.4081 0.3361 0.3960 0.077 Uiso 0.51(3) 1 calc PR A 1 C32 C 0.4445(6) 0.212(2) 0.3437(6) 0.078(8) Uiso 0.51(3) 1 d PD A 1 H32A H 0.4698 0.2282 0.3543 0.117 Uiso 0.51(3) 1 calc PR A 1 H32B H 0.4330 0.2967 0.3343 0.117 Uiso 0.51(3) 1 calc PR A 1 H32C H 0.4427 0.1496 0.3193 0.117 Uiso 0.51(3) 1 calc PR A 1 C31 C 0.4498(7) 0.0427(19) 0.4030(9) 0.093(9) Uiso 0.51(3) 1 d PD A 1 H31A H 0.4585 -0.0184 0.3822 0.140 Uiso 0.51(3) 1 calc PR A 1 H31B H 0.4352 -0.0070 0.4212 0.140 Uiso 0.51(3) 1 calc PR A 1 H31C H 0.4702 0.0830 0.4211 0.140 Uiso 0.51(3) 1 calc PR A 1 C30A C 0.4201(5) 0.200(3) 0.4220(5) 0.054(6) Uiso 0.49(3) 1 d PD A 2 H30D H 0.4418 0.2408 0.4372 0.082 Uiso 0.49(3) 1 calc PR A 2 H30E H 0.4134 0.1224 0.4386 0.082 Uiso 0.49(3) 1 calc PR A 2 H30F H 0.4006 0.2650 0.4190 0.082 Uiso 0.49(3) 1 calc PR A 2 C31A C 0.4575(5) 0.063(2) 0.3794(8) 0.073(8) Uiso 0.49(3) 1 d PD A 2 H31D H 0.4602 0.0354 0.3498 0.109 Uiso 0.49(3) 1 calc PR A 2 H31E H 0.4532 -0.0167 0.3965 0.109 Uiso 0.49(3) 1 calc PR A 2 H31F H 0.4793 0.1077 0.3925 0.109 Uiso 0.49(3) 1 calc PR A 2 C32A C 0.4331(9) 0.281(3) 0.3513(10) 0.128(12) Uiso 0.49(3) 1 d PD A 2 H32D H 0.4518 0.3368 0.3673 0.192 Uiso 0.49(3) 1 calc PR A 2 H32E H 0.4109 0.3327 0.3459 0.192 Uiso 0.49(3) 1 calc PR A 2 H32F H 0.4406 0.2543 0.3237 0.192 Uiso 0.49(3) 1 calc PR A 2 C50 C 0.5282(9) 0.359(3) 0.6576(10) 0.043(9) Uiso 0.25 1 d PD B 1 H50A H 0.5236 0.4389 0.6388 0.052 Uiso 0.25 1 calc PR B 1 H50B H 0.5503 0.3161 0.6504 0.052 Uiso 0.25 1 calc PR B 1 Cl20 Cl 0.4932(3) 0.2493(11) 0.6470(3) 0.048(3) Uiso 0.25 1 d PD B 1 Cl21 Cl 0.5349(4) 0.4108(13) 0.7117(4) 0.075(3) Uiso 0.25 1 d PD B 1 C50A C 0.5358(7) 0.396(3) 0.6529(8) 0.028(7) Uiso 0.25 1 d PD C 2 H50C H 0.5269 0.4766 0.6364 0.034 Uiso 0.25 1 calc PR C 2 H50D H 0.5560 0.3586 0.6397 0.034 Uiso 0.25 1 calc PR C 2 Cl24 Cl 0.5020(4) 0.2784(14) 0.6524(4) 0.069(4) Uiso 0.25 1 d PD C 2 Cl25 Cl 0.5493(4) 0.4373(14) 0.7068(4) 0.088(4) Uiso 0.25 1 d PD C 2 C51 C 0.4461(17) 0.066(6) 0.7139(11) 0.116(19) Uiso 0.25 1 d PD D 1 H51A H 0.4721 0.0621 0.7122 0.139 Uiso 0.25 1 calc PR D 1 H51B H 0.4404 0.1512 0.7273 0.139 Uiso 0.25 1 calc PR D 1 Cl22 Cl 0.4217(4) 0.0481(14) 0.6627(5) 0.077(4) Uiso 0.25 1 d PD D 1 Cl23 Cl 0.4329(5) -0.0683(19) 0.7424(6) 0.114(5) Uiso 0.25 1 d PD D 1 C51A C 0.4596(12) -0.003(5) 0.6959(8) 0.083(13) Uiso 0.25 1 d PD E 2 H51C H 0.4734 -0.0845 0.6911 0.099 Uiso 0.25 1 calc PR E 2 H51D H 0.4766 0.0731 0.6976 0.099 Uiso 0.25 1 calc PR E 2 Cl26 Cl 0.4297(5) 0.0200(19) 0.6517(6) 0.109(6) Uiso 0.25 1 d PD E 2 Cl27 Cl 0.4461(7) -0.018(3) 0.7436(8) 0.151(8) Uiso 0.25 1 d PD E 2 C61 C 0.2940(7) 0.700(3) 0.5093(9) 0.211(10) Uiso 1 1 d . . . H61A H 0.3055 0.7786 0.4976 0.253 Uiso 1 1 calc R . . H61B H 0.2904 0.6315 0.4862 0.253 Uiso 1 1 calc R . . C60 C 0.3175(6) 0.647(2) 0.5454(8) 0.203(10) Uiso 1 1 d . . . H60A H 0.3033 0.6118 0.5670 0.305 Uiso 1 1 calc R . . H60B H 0.3333 0.7177 0.5583 0.305 Uiso 1 1 calc R . . H60C H 0.3319 0.5743 0.5354 0.305 Uiso 1 1 calc R . . C62 C 0.2604(8) 0.738(4) 0.5205(8) 0.247(13) Uiso 1 1 d . . . H62A H 0.2499 0.6660 0.5365 0.297 Uiso 1 1 calc R . . H62B H 0.2624 0.8204 0.5384 0.297 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ti1 0.0484(9) 0.0912(13) 0.0374(9) -0.0019(8) 0.0078(7) -0.0258(9) Ti2 0.0492(8) 0.0461(9) 0.0374(8) 0.0009(7) 0.0017(6) 0.0053(7) Cl1 0.094(2) 0.118(2) 0.0612(16) -0.0232(16) 0.0065(14) -0.0479(18) Cl2 0.100(2) 0.103(2) 0.0643(17) 0.0143(15) 0.0178(15) -0.0424(17) Cl3 0.0410(12) 0.152(3) 0.0624(16) 0.0045(17) 0.0072(11) -0.0191(14) Cl4 0.111(2) 0.0621(16) 0.0559(15) -0.0101(12) 0.0045(14) 0.0276(14) Cl5 0.0467(12) 0.0909(18) 0.0439(12) 0.0047(12) -0.0005(9) 0.0158(11) Cl6 0.0872(18) 0.0604(15) 0.0745(17) 0.0119(13) 0.0163(14) -0.0105(13) Cl7 0.0487(12) 0.101(2) 0.0588(14) -0.0055(13) 0.0014(10) -0.0252(12) Cl8 0.0730(18) 0.103(2) 0.122(3) 0.053(2) 0.0023(17) 0.0244(16) S1 0.0475(12) 0.101(2) 0.0391(12) -0.0110(12) 0.0145(9) -0.0223(13) S2 0.0634(15) 0.0534(14) 0.0814(18) -0.0009(13) -0.0244(13) -0.0111(12) N1 0.054(4) 0.058(5) 0.049(4) 0.001(4) 0.008(3) -0.005(4) N2 0.037(4) 0.064(5) 0.033(4) 0.001(3) 0.003(3) -0.005(3) N3 0.032(3) 0.079(5) 0.033(4) 0.006(3) -0.001(3) -0.011(3) N4 0.031(3) 0.072(5) 0.032(3) 0.009(3) 0.003(3) -0.002(3) N5 0.039(4) 0.080(5) 0.038(4) -0.010(4) 0.012(3) -0.008(4) N6 0.038(3) 0.055(4) 0.039(4) -0.002(3) 0.004(3) 0.010(3) N7 0.035(3) 0.049(4) 0.039(4) 0.003(3) 0.000(3) 0.001(3) N8 0.036(3) 0.045(4) 0.035(3) -0.005(3) 0.006(3) 0.003(3) N9 0.032(3) 0.046(4) 0.037(4) -0.002(3) -0.003(3) 0.000(3) N10 0.040(4) 0.076(5) 0.054(4) -0.011(4) -0.007(3) 0.015(4) C1 0.035(4) 0.076(6) 0.031(4) 0.003(4) 0.003(3) -0.004(4) C2 0.028(4) 0.058(5) 0.029(4) 0.002(4) 0.001(3) -0.005(3) C3 0.075(7) 0.069(7) 0.052(6) -0.007(5) 0.013(5) -0.002(5) C4 0.072(7) 0.068(7) 0.067(7) 0.000(5) 0.005(5) 0.010(5) C5 0.050(5) 0.073(7) 0.041(5) 0.005(5) 0.008(4) 0.003(5) C6 0.115(11) 0.056(7) 0.174(15) -0.006(8) 0.012(10) -0.008(7) C7 0.040(5) 0.090(7) 0.076(7) 0.000(6) 0.014(5) -0.001(5) C8 0.037(4) 0.099(8) 0.046(5) 0.002(5) -0.002(4) -0.004(5) C9 0.044(5) 0.082(7) 0.047(5) 0.014(5) 0.001(4) 0.003(5) C10 0.043(4) 0.069(6) 0.039(5) 0.003(4) 0.006(4) -0.003(4) C11 0.042(5) 0.165(12) 0.055(6) 0.016(7) -0.014(4) -0.032(6) C12 0.045(5) 0.068(6) 0.066(6) 0.010(5) 0.004(4) -0.012(4) C13 0.060(6) 0.099(8) 0.054(6) -0.028(6) 0.009(5) -0.008(5) C14 0.106(10) 0.122(11) 0.103(10) -0.033(9) 0.032(8) 0.030(9) C15 0.160(13) 0.141(12) 0.029(5) -0.007(7) 0.010(6) -0.012(10) C16 0.099(9) 0.152(13) 0.088(9) -0.058(9) 0.022(7) -0.049(9) C17 0.034(4) 0.074(6) 0.038(4) -0.005(4) -0.002(3) 0.000(4) C18 0.037(4) 0.047(5) 0.039(4) 0.003(4) 0.001(3) 0.003(3) C19 0.043(5) 0.075(6) 0.038(5) -0.002(4) 0.006(4) 0.009(4) C20 0.042(5) 0.080(7) 0.047(5) 0.004(5) 0.011(4) -0.004(4) C21 0.044(4) 0.053(5) 0.037(4) 0.000(4) -0.001(4) 0.001(4) C22 0.060(6) 0.099(8) 0.064(6) 0.009(6) 0.022(5) 0.022(6) C23 0.072(6) 0.059(6) 0.055(6) 0.010(5) 0.009(5) -0.004(5) C24 0.039(4) 0.053(5) 0.038(5) 0.000(4) 0.011(3) -0.006(4) C25 0.039(4) 0.063(6) 0.049(5) -0.016(4) 0.010(4) -0.003(4) C26 0.038(4) 0.063(6) 0.047(5) -0.008(4) 0.004(4) 0.001(4) C27 0.053(5) 0.072(6) 0.038(5) 0.006(4) 0.005(4) -0.004(4) C28 0.089(7) 0.067(7) 0.070(7) -0.007(6) 0.005(6) 0.035(6) C29 0.039(5) 0.084(7) 0.063(6) -0.017(5) -0.011(4) 0.004(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 N3 2.144(7) . ? Ti1 N1 2.192(7) . ? Ti1 Cl3 2.217(3) . ? Ti1 Cl1 2.231(3) . ? Ti1 Cl2 2.243(3) . ? Ti1 S1 2.500(3) . ? Ti2 N6 2.168(7) . ? Ti2 N8 2.173(6) . ? Ti2 Cl4 2.230(3) . ? Ti2 Cl5 2.233(3) . ? Ti2 Cl6 2.236(3) . ? Ti2 S2 2.512(3) . ? S1 C1 1.672(8) . ? S2 C17 1.652(9) . ? N1 C3 1.335(12) . ? N1 N2 1.371(9) . ? N2 C5 1.354(10) . ? N2 C2 1.445(10) . ? N3 C8 1.328(11) . ? N3 N4 1.392(8) . ? N4 C10 1.357(10) . ? N4 C2 1.437(9) . ? N5 C1 1.307(10) . ? N5 C13 1.505(11) . ? N6 C19 1.324(10) . ? N6 N7 1.400(8) . ? N7 C21 1.335(10) . ? N7 C18 1.450(9) . ? N8 C24 1.351(9) . ? N8 N9 1.373(8) . ? N9 C26 1.350(10) . ? N9 C18 1.444(10) . ? N10 C17 1.292(10) . ? N10 C29 1.523(10) . ? C1 C2 1.544(10) . ? C3 C4 1.375(13) . ? C3 C6 1.494(15) . ? C4 C5 1.326(13) . ? C5 C7 1.489(13) . ? C8 C9 1.389(13) . ? C8 C11 1.506(11) . ? C9 C10 1.382(12) . ? C10 C12 1.475(11) . ? C13 C14 1.535(15) . ? C13 C16 1.535(14) . ? C13 C15 1.564(16) . ? C17 C18 1.547(11) . ? C19 C20 1.408(13) . ? C19 C22 1.488(12) . ? C20 C21 1.365(11) . ? C21 C23 1.494(12) . ? C24 C25 1.394(11) . ? C24 C27 1.483(11) . ? C25 C26 1.366(12) . ? C26 C28 1.467(12) . ? C29 C32 1.444(15) . ? C29 C31A 1.455(15) . ? C29 C30A 1.475(14) . ? C29 C30 1.490(14) . ? C29 C31 1.536(16) . ? C29 C32A 1.542(17) . ? C50 Cl20 1.70(2) . ? C50 Cl21 1.74(2) . ? C50A Cl24 1.72(2) . ? C50A Cl25 1.72(2) . ? C51 Cl23 1.70(4) . ? C51 Cl22 1.73(4) . ? C51A Cl27 1.63(3) . ? C51A Cl26 1.67(3) . ? C61 C62 1.40(3) . ? C61 C60 1.43(3) . ? C62 C62 1.42(5) 7_566 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N3 Ti1 N1 81.5(3) . . ? N3 Ti1 Cl3 91.5(2) . . ? N1 Ti1 Cl3 167.1(2) . . ? N3 Ti1 Cl1 90.7(2) . . ? N1 Ti1 Cl1 89.8(2) . . ? Cl3 Ti1 Cl1 101.14(13) . . ? N3 Ti1 Cl2 166.15(19) . . ? N1 Ti1 Cl2 90.2(2) . . ? Cl3 Ti1 Cl2 94.43(13) . . ? Cl1 Ti1 Cl2 100.39(14) . . ? N3 Ti1 S1 82.54(19) . . ? N1 Ti1 S1 82.6(2) . . ? Cl3 Ti1 S1 85.76(11) . . ? Cl1 Ti1 S1 170.50(11) . . ? Cl2 Ti1 S1 85.43(11) . . ? N6 Ti2 N8 81.1(2) . . ? N6 Ti2 Cl4 91.39(18) . . ? N8 Ti2 Cl4 167.71(19) . . ? N6 Ti2 Cl5 91.37(18) . . ? N8 Ti2 Cl5 91.10(18) . . ? Cl4 Ti2 Cl5 98.85(11) . . ? N6 Ti2 Cl6 166.15(18) . . ? N8 Ti2 Cl6 90.33(18) . . ? Cl4 Ti2 Cl6 95.05(12) . . ? Cl5 Ti2 Cl6 99.71(11) . . ? N6 Ti2 S2 81.55(18) . . ? N8 Ti2 S2 83.41(17) . . ? Cl4 Ti2 S2 85.88(11) . . ? Cl5 Ti2 S2 171.62(11) . . ? Cl6 Ti2 S2 86.69(11) . . ? C1 S1 Ti1 107.6(3) . . ? C17 S2 Ti2 108.0(3) . . ? C3 N1 N2 104.7(7) . . ? C3 N1 Ti1 132.3(6) . . ? N2 N1 Ti1 123.0(5) . . ? C5 N2 N1 110.9(7) . . ? C5 N2 C2 128.4(7) . . ? N1 N2 C2 120.6(6) . . ? C8 N3 N4 104.4(6) . . ? C8 N3 Ti1 132.2(6) . . ? N4 N3 Ti1 123.0(5) . . ? C10 N4 N3 111.9(6) . . ? C10 N4 C2 127.0(6) . . ? N3 N4 C2 121.1(6) . . ? C1 N5 C13 128.1(7) . . ? C19 N6 N7 104.4(6) . . ? C19 N6 Ti2 132.6(6) . . ? N7 N6 Ti2 122.9(4) . . ? C21 N7 N6 111.5(6) . . ? C21 N7 C18 128.2(7) . . ? N6 N7 C18 120.3(6) . . ? C24 N8 N9 104.9(6) . . ? C24 N8 Ti2 131.5(5) . . ? N9 N8 Ti2 123.5(4) . . ? C26 N9 N8 112.3(6) . . ? C26 N9 C18 127.0(7) . . ? N8 N9 C18 120.7(6) . . ? C17 N10 C29 127.6(8) . . ? N5 C1 C2 114.2(7) . . ? N5 C1 S1 126.3(6) . . ? C2 C1 S1 119.5(6) . . ? N4 C2 N2 111.3(6) . . ? N4 C2 C1 110.2(6) . . ? N2 C2 C1 111.6(6) . . ? N1 C3 C4 109.5(9) . . ? N1 C3 C6 125.6(10) . . ? C4 C3 C6 124.9(10) . . ? C5 C4 C3 108.6(9) . . ? C4 C5 N2 106.2(8) . . ? C4 C5 C7 130.9(9) . . ? N2 C5 C7 122.8(9) . . ? N3 C8 C9 111.3(7) . . ? N3 C8 C11 123.1(9) . . ? C9 C8 C11 125.6(9) . . ? C10 C9 C8 107.0(8) . . ? N4 C10 C9 105.4(7) . . ? N4 C10 C12 123.8(7) . . ? C9 C10 C12 130.4(8) . . ? N5 C13 C14 109.2(8) . . ? N5 C13 C16 105.3(8) . . ? C14 C13 C16 109.7(11) . . ? N5 C13 C15 109.7(9) . . ? C14 C13 C15 109.6(10) . . ? C16 C13 C15 113.2(10) . . ? N10 C17 C18 113.1(8) . . ? N10 C17 S2 127.4(7) . . ? C18 C17 S2 119.5(6) . . ? N9 C18 N7 111.6(6) . . ? N9 C18 C17 109.9(6) . . ? N7 C18 C17 111.9(6) . . ? N6 C19 C20 110.8(7) . . ? N6 C19 C22 123.4(8) . . ? C20 C19 C22 125.8(8) . . ? C21 C20 C19 106.2(7) . . ? N7 C21 C20 107.1(7) . . ? N7 C21 C23 124.4(7) . . ? C20 C21 C23 128.5(8) . . ? N8 C24 C25 109.1(7) . . ? N8 C24 C27 123.8(7) . . ? C25 C24 C27 127.0(7) . . ? C26 C25 C24 108.1(7) . . ? N9 C26 C25 105.5(7) . . ? N9 C26 C28 124.7(8) . . ? C25 C26 C28 129.6(8) . . ? C32 C29 C31A 80.2(11) . . ? C32 C29 C30A 135.3(13) . . ? C31A C29 C30A 113.5(11) . . ? C32 C29 C30 113.3(11) . . ? C31A C29 C30 130.2(12) . . ? C30A C29 C30 25.5(9) . . ? C32 C29 N10 108.3(11) . . ? C31A C29 N10 107.7(11) . . ? C30A C29 N10 107.1(10) . . ? C30 C29 N10 111.8(9) . . ? C32 C29 C31 111.9(11) . . ? C31A C29 C31 32.5(10) . . ? C30A C29 C31 85.2(11) . . ? C30 C29 C31 107.8(10) . . ? N10 C29 C31 103.2(11) . . ? C32 C29 C32A 33.1(12) . . ? C31A C29 C32A 110.3(12) . . ? C30A C29 C32A 107.9(12) . . ? C30 C29 C32A 83.0(12) . . ? N10 C29 C32A 110.2(14) . . ? C31 C29 C32A 137.8(15) . . ? Cl20 C50 Cl21 112(2) . . ? Cl24 C50A Cl25 106.8(18) . . ? Cl23 C51 Cl22 104(3) . . ? Cl27 C51A Cl26 120(3) . . ? C62 C61 C60 113(2) . . ? C62 C62 C61 103(3) 7_566 . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.693 _refine_diff_density_min -0.393 _refine_diff_density_rms 0.125 #============================================================================ data_12 _database_code_depnum_ccdc_archive 'CCDC 604781' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H32 Li N5 O S Si' _chemical_formula_weight 413.59 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pna21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-x+1/2, y+1/2, z+1/2' 'x+1/2, -y+1/2, z' _cell_length_a 19.185(2) _cell_length_b 8.806(3) _cell_length_c 14.696(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2482.8(9) _cell_formula_units_Z 4 _cell_measurement_temperature 290(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 2 _cell_measurement_theta_max 20 _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.106 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 888 _exptl_absorpt_coefficient_mu 0.195 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 290(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'four circle diffractometer Nonius-Mach3' _diffrn_measurement_method '\w/2\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% ? _diffrn_reflns_number 6226 _diffrn_reflns_av_R_equivalents 0.0441 _diffrn_reflns_av_sigmaI/netI 0.1449 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 27.99 _reflns_number_total 5992 _reflns_number_gt 2460 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius (control program)' _computing_cell_refinement 'Nonius (control program)' _computing_data_reduction 'XRAY80 (Stewart, 1976)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1046P)^2^+0.2502P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.13(19) _refine_ls_number_reflns 5992 _refine_ls_number_parameters 257 _refine_ls_number_restraints 16 _refine_ls_R_factor_all 0.2360 _refine_ls_R_factor_gt 0.0769 _refine_ls_wR_factor_ref 0.2391 _refine_ls_wR_factor_gt 0.1852 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.019 _refine_ls_shift/su_max 0.044 _refine_ls_shift/su_mean 0.003 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Si1 Si -0.48236(9) 0.7450(2) -0.18139(14) 0.0605(5) Uani 1 1 d . . . S1 S -0.82089(10) 1.0974(2) -0.2259(2) 0.1157(10) Uani 1 1 d . . . N1 N -0.7258(3) 0.8726(8) -0.2689(5) 0.097(2) Uani 1 1 d . A . N11 N -0.5147(2) 0.6602(5) -0.3598(3) 0.0497(12) Uani 1 1 d . . . N12 N -0.5704(2) 0.7519(7) -0.3714(4) 0.0646(13) Uani 1 1 d . A . N21 N -0.5578(2) 0.4902(5) -0.2462(3) 0.0481(11) Uani 1 1 d . . . N22 N -0.6187(2) 0.5492(5) -0.2127(3) 0.0484(11) Uani 1 1 d . A . C1 C -0.5023(3) 0.5938(7) -0.2715(4) 0.0453(14) Uani 1 1 d . . . H1 H -0.4601 0.5322 -0.2774 0.054 Uiso 1 1 calc R . . C2 C -0.4542(6) 0.6409(11) -0.0779(6) 0.118(3) Uani 1 1 d . . . H2A H -0.4172 0.5721 -0.0933 0.177 Uiso 1 1 calc R . . H2B H -0.4928 0.5846 -0.0537 0.177 Uiso 1 1 calc R . . H2C H -0.4379 0.7120 -0.0331 0.177 Uiso 1 1 calc R . . C3 C -0.4094(3) 0.8553(7) -0.2324(5) 0.0748(19) Uani 1 1 d . . . H3A H -0.3989 0.9410 -0.1944 0.112 Uiso 1 1 calc R . . H3B H -0.4226 0.8901 -0.2918 0.112 Uiso 1 1 calc R . . H3C H -0.3689 0.7916 -0.2372 0.112 Uiso 1 1 calc R . . C4 C -0.5568(4) 0.8728(8) -0.1538(6) 0.097(3) Uani 1 1 d . . . H4A H -0.5936 0.8147 -0.1264 0.145 Uiso 1 1 calc R . . H4B H -0.5736 0.9195 -0.2086 0.145 Uiso 1 1 calc R . . H4C H -0.5416 0.9500 -0.1121 0.145 Uiso 1 1 calc R . . C5 C -0.7651(3) 0.9655(8) -0.2511(5) 0.0710(19) Uani 1 1 d . . . C13 C -0.5627(4) 0.8091(9) -0.4547(6) 0.081(2) Uani 1 1 d . . . C14 C -0.5030(4) 0.7584(10) -0.4936(5) 0.084(2) Uani 1 1 d . . . H14 H -0.4864 0.7853 -0.5509 0.101 Uiso 1 1 calc R . . C15 C -0.4718(3) 0.6627(8) -0.4352(5) 0.0652(17) Uani 1 1 d . . . C16 C -0.4067(4) 0.5690(9) -0.4390(5) 0.091(2) Uani 1 1 d . . . H16A H -0.3754 0.6011 -0.3918 0.136 Uiso 1 1 calc R . . H16B H -0.3848 0.5818 -0.4972 0.136 Uiso 1 1 calc R . . H16C H -0.4183 0.4639 -0.4303 0.136 Uiso 1 1 calc R . . C17 C -0.6168(5) 0.9137(12) -0.4918(7) 0.132(4) Uani 1 1 d . . . H17A H -0.6418 0.8637 -0.5398 0.198 Uiso 1 1 calc R . . H17B H -0.5949 1.0035 -0.5152 0.198 Uiso 1 1 calc R . . H17C H -0.6487 0.9412 -0.4442 0.198 Uiso 1 1 calc R . . C23 C -0.6572(3) 0.4297(7) -0.1911(4) 0.0528(14) Uani 1 1 d . . . C24 C -0.6229(3) 0.2964(7) -0.2111(5) 0.0650(19) Uani 1 1 d . . . H24 H -0.6392 0.1981 -0.2018 0.078 Uiso 1 1 calc R . . C25 C -0.5599(3) 0.3380(7) -0.2475(4) 0.0581(15) Uani 1 1 d . . . C26 C -0.5001(4) 0.2441(8) -0.2814(6) 0.093(3) Uani 1 1 d . . . H26A H -0.4921 0.2660 -0.3445 0.140 Uiso 1 1 calc R . . H26B H -0.5109 0.1383 -0.2744 0.140 Uiso 1 1 calc R . . H26C H -0.4590 0.2678 -0.2470 0.140 Uiso 1 1 calc R . . C27 C -0.7293(3) 0.4532(9) -0.1526(5) 0.078(2) Uani 1 1 d . . . H27A H -0.7272 0.4508 -0.0874 0.117 Uiso 1 1 calc R . . H27B H -0.7596 0.3739 -0.1738 0.117 Uiso 1 1 calc R . . H27C H -0.7470 0.5497 -0.1722 0.117 Uiso 1 1 calc R . . Li1 Li -0.6635(6) 0.7087(13) -0.3028(8) 0.073(3) Uani 1 1 d . . . O1 O -0.7180(5) 0.5642(13) -0.3816(7) 0.045(4) Uiso 0.456(18) 1 d PDU A 1 C31 C -0.6794(7) 0.4724(18) -0.4474(11) 0.073(5) Uiso 0.456(18) 1 d PDU A 1 H31A H -0.6393 0.4243 -0.4196 0.087 Uiso 0.456(18) 1 calc PR A 1 H31B H -0.6643 0.5328 -0.4989 0.087 Uiso 0.456(18) 1 calc PR A 1 C32 C -0.7342(11) 0.355(3) -0.476(2) 0.132(12) Uiso 0.456(18) 1 d PDU A 1 H32A H -0.7326 0.3366 -0.5406 0.176 Uiso 0.456(18) 1 calc PR A 1 H32B H -0.7272 0.2598 -0.4437 0.176 Uiso 0.456(18) 1 calc PR A 1 C33 C -0.8021(10) 0.427(3) -0.4487(18) 0.134(10) Uiso 0.456(18) 1 d PDU A 1 H33A H -0.8324 0.4358 -0.5012 0.161 Uiso 0.456(18) 1 calc PR A 1 H33B H -0.8254 0.3654 -0.4031 0.161 Uiso 0.456(18) 1 calc PR A 1 C34 C -0.7859(9) 0.577(2) -0.4121(16) 0.104(7) Uiso 0.456(18) 1 d PDU A 1 H34A H -0.7897 0.6537 -0.4589 0.125 Uiso 0.456(18) 1 calc PR A 1 H34B H -0.8171 0.6021 -0.3625 0.125 Uiso 0.456(18) 1 calc PR A 1 O1A O -0.7109(7) 0.5991(14) -0.3970(9) 0.087(5) Uiso 0.544(18) 1 d PDU A 2 C31A C -0.7089(14) 0.4272(19) -0.4055(17) 0.142(8) Uiso 0.544(18) 1 d PDU A 2 H31C H -0.6621 0.3944 -0.4212 0.170 Uiso 0.544(18) 1 calc PR A 2 H31D H -0.7215 0.3811 -0.3479 0.170 Uiso 0.544(18) 1 calc PR A 2 C32A C -0.7603(18) 0.377(3) -0.480(3) 0.143(13) Uiso 0.544(18) 1 d PDU A 2 H32C H -0.7361 0.3440 -0.5343 0.232 Uiso 0.544(18) 1 calc PR A 2 H32D H -0.7903 0.2955 -0.4585 0.232 Uiso 0.544(18) 1 calc PR A 2 C33A C -0.7996(10) 0.517(3) -0.4954(16) 0.139(8) Uiso 0.544(18) 1 d PDU A 2 H33C H -0.8018 0.5382 -0.5602 0.167 Uiso 0.544(18) 1 calc PR A 2 H33D H -0.8469 0.5053 -0.4731 0.167 Uiso 0.544(18) 1 calc PR A 2 C34A C -0.7666(11) 0.641(2) -0.4495(15) 0.132(8) Uiso 0.544(18) 1 d PDU A 2 H34C H -0.7511 0.7140 -0.4944 0.158 Uiso 0.544(18) 1 calc PR A 2 H34D H -0.8008 0.6907 -0.4111 0.158 Uiso 0.544(18) 1 calc PR A 2 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 Si1 0.0599(9) 0.0608(9) 0.0608(9) -0.0050(10) 0.0027(10) -0.0120(9) S1 0.0659(11) 0.0869(13) 0.194(3) -0.0531(16) -0.0072(14) 0.0053(11) N1 0.070(4) 0.101(5) 0.121(6) 0.003(4) 0.001(4) 0.032(4) N11 0.045(3) 0.059(3) 0.045(3) 0.012(2) 0.002(2) 0.001(2) N12 0.055(3) 0.068(3) 0.071(3) 0.017(3) 0.000(3) 0.001(3) N21 0.045(2) 0.047(3) 0.053(3) -0.002(2) 0.005(2) -0.001(2) N22 0.041(2) 0.054(3) 0.051(3) -0.004(2) 0.003(2) 0.001(2) C1 0.036(3) 0.048(3) 0.052(3) -0.001(3) 0.001(2) 0.007(2) C2 0.153(9) 0.120(7) 0.081(6) -0.003(5) -0.015(6) -0.019(7) C3 0.061(4) 0.072(4) 0.092(5) -0.015(4) 0.005(4) -0.012(3) C4 0.083(5) 0.073(5) 0.135(7) -0.033(5) 0.038(5) -0.009(4) C5 0.051(4) 0.073(4) 0.089(5) -0.012(4) -0.001(4) -0.017(4) C13 0.068(5) 0.090(5) 0.084(6) 0.029(4) 0.005(4) -0.008(4) C14 0.089(5) 0.105(5) 0.057(4) 0.020(4) 0.009(4) -0.022(5) C15 0.057(4) 0.080(5) 0.059(4) 0.001(4) 0.007(3) -0.017(4) C16 0.080(5) 0.111(6) 0.081(5) 0.002(5) 0.035(4) 0.016(5) C17 0.100(6) 0.179(10) 0.117(7) 0.088(7) -0.007(6) 0.025(7) C23 0.040(3) 0.058(4) 0.061(4) 0.012(3) -0.009(3) -0.006(3) C24 0.052(4) 0.057(4) 0.085(5) 0.011(3) -0.002(3) -0.018(3) C25 0.056(4) 0.054(4) 0.065(4) -0.008(4) -0.006(3) 0.007(3) C26 0.079(5) 0.058(4) 0.143(8) -0.005(5) 0.017(5) 0.003(4) C27 0.048(3) 0.105(6) 0.080(5) 0.009(4) 0.010(3) 0.000(4) Li1 0.061(6) 0.089(8) 0.069(6) 0.004(6) -0.002(6) 0.013(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Si1 C2 1.857(10) . ? Si1 C3 1.862(7) . ? Si1 C4 1.863(7) . ? Si1 C1 1.917(6) . ? S1 C5 1.622(8) . ? N1 C5 1.143(8) . ? N1 Li1 1.939(13) . ? N11 N12 1.350(6) . ? N11 C15 1.380(7) . ? N11 C1 1.443(7) . ? N12 C13 1.332(9) . ? N12 Li1 2.086(12) . ? N21 C25 1.340(7) . ? N21 N22 1.371(6) . ? N21 C1 1.450(7) . ? N22 C23 1.324(6) . ? N22 Li1 2.113(12) . ? C13 C14 1.356(10) . ? C13 C17 1.492(10) . ? C14 C15 1.344(10) . ? C15 C16 1.497(9) . ? C23 C24 1.378(8) . ? C23 C27 1.509(8) . ? C24 C25 1.372(8) . ? C25 C26 1.501(9) . ? Li1 O1A 1.916(16) . ? Li1 O1 2.012(15) . ? O1 C34 1.381(15) . ? O1 C31 1.462(14) . ? C31 C32 1.530(15) . ? C32 C33 1.500(17) . ? C33 C34 1.457(16) . ? O1A C34A 1.369(15) . ? O1A C31A 1.520(16) . ? C31A C32A 1.536(19) . ? C32A C33A 1.47(2) . ? C33A C34A 1.428(17) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 Si1 C3 111.6(4) . . ? C2 Si1 C4 110.1(5) . . ? C3 Si1 C4 110.5(3) . . ? C2 Si1 C1 106.3(4) . . ? C3 Si1 C1 103.6(3) . . ? C4 Si1 C1 114.6(3) . . ? C5 N1 Li1 176.6(7) . . ? N12 N11 C15 111.2(5) . . ? N12 N11 C1 119.1(4) . . ? C15 N11 C1 129.0(5) . . ? C13 N12 N11 104.7(5) . . ? C13 N12 Li1 127.5(5) . . ? N11 N12 Li1 120.5(5) . . ? C25 N21 N22 110.9(5) . . ? C25 N21 C1 130.5(5) . . ? N22 N21 C1 118.6(4) . . ? C23 N22 N21 105.1(4) . . ? C23 N22 Li1 116.8(5) . . ? N21 N22 Li1 111.9(4) . . ? N11 C1 N21 111.4(4) . . ? N11 C1 Si1 111.9(4) . . ? N21 C1 Si1 114.0(4) . . ? N1 C5 S1 179.9(9) . . ? N12 C13 C14 110.9(6) . . ? N12 C13 C17 119.4(7) . . ? C14 C13 C17 129.6(7) . . ? C15 C14 C13 108.2(6) . . ? C14 C15 N11 104.9(6) . . ? C14 C15 C16 133.9(7) . . ? N11 C15 C16 121.2(6) . . ? N22 C23 C24 111.1(5) . . ? N22 C23 C27 119.5(6) . . ? C24 C23 C27 129.4(6) . . ? C25 C24 C23 106.0(5) . . ? N21 C25 C24 106.8(5) . . ? N21 C25 C26 122.1(6) . . ? C24 C25 C26 131.0(6) . . ? O1A Li1 N1 105.6(6) . . ? O1A Li1 O1 11.5(6) . . ? N1 Li1 O1 107.4(6) . . ? O1A Li1 N12 98.5(7) . . ? N1 Li1 N12 121.1(6) . . ? O1 Li1 N12 106.4(6) . . ? O1A Li1 N22 108.1(7) . . ? N1 Li1 N22 125.8(6) . . ? O1 Li1 N22 98.7(6) . . ? N12 Li1 N22 94.3(5) . . ? C34 O1 C31 107.8(10) . . ? C34 O1 Li1 128.8(9) . . ? C31 O1 Li1 117.9(9) . . ? O1 C31 C32 101.8(12) . . ? C33 C32 C31 103.9(13) . . ? C34 C33 C32 107.0(14) . . ? O1 C34 C33 104.5(14) . . ? C34A O1A C31A 103.9(11) . . ? C34A O1A Li1 130.0(11) . . ? C31A O1A Li1 123.3(11) . . ? C32A C31A O1A 109.3(14) . . ? C33A C32A C31A 101.4(15) . . ? C34A C33A C32A 109.9(15) . . ? O1A C34A C33A 114.1(14) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.99 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.208 _refine_diff_density_min -0.220 _refine_diff_density_rms 0.047