Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_2 _database_code_CSD 157350 _journal_coden_Cambridge 182 loop_ _publ_author_name _publ_author_address 'Lutz H. Gade' ; Laboratoire de Chimie Organometallique et de Catalyse (UMR 7513) Institut LeBel Universite Louis Pasteur 4, rue Blaise Pascal 67070 Strasbourg France ; 'Christian H. Galka' ; Institut für Anorganische Chemie der Universität Würzburg Am Hubland 97074 Würzburg Germany ; _publ_contact_author ; Prof. Dr. Lutz H. Gade Laboratoire de Chimie Organometallique et de Catalyse (UMR 7513) Institut LeBel Universite Louis Pasteur 4, rue Blaise Pascal 67070 Strasbourg France ; _publ_contact_author_phone '0033 388 415 325' _publ_contact_author_fax '0033 388 416 045' _publ_contact_author_email 'gade@chimie.u-strasbg.fr' _publ_requested_journal 'Chem. Commun.' _publ_requested_coeditor_name 'Christian H. Galka' _publ_contact_letter ; Please consider this CIF submission for publication in "Chem. Commun." ; _publ_section_title ; First Structural Characterization of a Mixed Valent Thallium(I/III) Amide Bearing a Butylthallium(III) Unit Stabilized by a Tripodal Amido Ligand ; _publ_section_abstract ; Lithiation of the tripodal amine HC{SiMe2NH(p-Tol)}3 in the presence of TlCl yielded the Tl(I/III) mixed valent complex [HC{SiMe2N(p-Tol)}3(Tl-C4H9)(Tl)] (2); an X-ray diffraction study established the central butylthallium(III) unit coordinated by the amido tripod in which two of the amido functions are additionally bridged by the Tl(I) atom. ; _publ_section_exptl_prep ; "Crystals grown from n-pentane at -30_C" ; _publ_section_exptl_refinement ; One half of a disordered solvent molecule (pentane) was found in the asymetric unit and refined with isotropic displacement parameters. Due to the special position of C1S no hydrogen atoms could be calculated. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C34.50 H55 N3 Si3 Tl2' _chemical_formula_weight 1004.83 _chemical_melting_point ? _chemical_compound_source ? 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' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Si' 'Si' 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Tl' 'Tl' -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 1 2/c 1' _symmetry_Int_Tables_number 15 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 21.346(6) _cell_length_b 14.4015(13) _cell_length_c 26.384(10) _cell_angle_alpha 90.00 _cell_angle_beta 107.869(14) _cell_angle_gamma 90.00 _cell_volume 7719(4) _cell_formula_units_Z 8 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 10 _cell_measurement_theta_max 15 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.6 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.729 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3896 _exptl_absorpt_coefficient_mu 8.459 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.3611 _exptl_absorpt_correction_T_max 0.9991 _exptl_absorpt_process_details ; empirical absorption correction by psi-scans from 10 reflections with chi-angles near 90 degrees ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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 'CAD4 (Enraf-Nonius)' _diffrn_measurement_method 'Omega/Theta scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 1.6 _diffrn_reflns_number 7684 _diffrn_reflns_av_R_equivalents 0.0423 _diffrn_reflns_av_sigmaI/netI 0.0412 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 1 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 2 _diffrn_reflns_theta_min 2.00 _diffrn_reflns_theta_max 24.99 _reflns_number_total 6781 _reflns_number_gt 5138 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 (Enraf-Nonius)' _computing_cell_refinement 'CAD4 (Enraf-Nonius)' _computing_data_reduction 'BEGIN (SDP)' _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. Distance of Q1 to closest atoms [length]: TL1 0.88, C40 1.36, H40B 1.83, H40A 2.03. Q1 could not be refined for a special atom type. ; _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^)+(0.0653P)^2^+88.4538P] 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 refxyz _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6781 _refine_ls_number_parameters 382 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0693 _refine_ls_R_factor_gt 0.0471 _refine_ls_wR_factor_ref 0.1287 _refine_ls_wR_factor_gt 0.1108 _refine_ls_goodness_of_fit_ref 1.069 _refine_ls_restrained_S_all 1.069 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Tl1 Tl 0.088458(16) 0.07274(2) 0.164450(13) 0.02358(12) Uani 1 1 d . . . Tl2 Tl 0.092153(18) -0.07015(3) 0.266090(15) 0.03608(13) Uani 1 1 d . . . C1 C 0.1894(4) -0.0817(6) 0.1405(4) 0.0253(19) Uani 1 1 d . . . H1 H 0.2216 -0.1256 0.1327 0.030 Uiso 1 1 calc . . . Si1 Si 0.16144(13) -0.00396(17) 0.08014(10) 0.0280(6) Uani 1 1 d . . . C2 C 0.0967(6) -0.0597(8) 0.0238(4) 0.048(3) Uani 1 1 d . . . H2A H 0.0559 -0.0658 0.0332 0.072 Uiso 1 1 calc R . . H2B H 0.1117 -0.1214 0.0168 0.072 Uiso 1 1 calc R . . H2C H 0.0886 -0.0212 -0.0082 0.072 Uiso 1 1 calc R . . C3 C 0.2324(6) 0.0205(8) 0.0546(5) 0.050(3) Uani 1 1 d . . . H3A H 0.2174 0.0586 0.0223 0.075 Uiso 1 1 calc R . . H3B H 0.2503 -0.0382 0.0462 0.075 Uiso 1 1 calc R . . H3C H 0.2667 0.0539 0.0818 0.075 Uiso 1 1 calc R . . Si2 Si 0.23778(12) -0.01833(18) 0.20261(10) 0.0281(6) Uani 1 1 d . . . C4 C 0.2869(6) 0.0797(8) 0.1894(5) 0.048(3) Uani 1 1 d . . . H4A H 0.2572 0.1275 0.1687 0.071 Uiso 1 1 calc R . . H4B H 0.3155 0.0572 0.1692 0.071 Uiso 1 1 calc R . . H4C H 0.3139 0.1063 0.2232 0.071 Uiso 1 1 calc R . . C5 C 0.3024(5) -0.0964(8) 0.2476(5) 0.049(3) Uani 1 1 d . . . H5A H 0.3289 -0.0608 0.2784 0.074 Uiso 1 1 calc R . . H5B H 0.3309 -0.1210 0.2279 0.074 Uiso 1 1 calc R . . H5C H 0.2808 -0.1480 0.2599 0.074 Uiso 1 1 calc R . . Si3 Si 0.12318(12) -0.15803(16) 0.15128(10) 0.0257(5) Uani 1 1 d . . . C6 C 0.1576(5) -0.2347(8) 0.2108(5) 0.046(3) Uani 1 1 d . . . H6A H 0.1788 -0.1962 0.2421 0.069 Uiso 1 1 calc R . . H6B H 0.1902 -0.2770 0.2042 0.069 Uiso 1 1 calc R . . H6C H 0.1220 -0.2708 0.2174 0.069 Uiso 1 1 calc R . . C7 C 0.0903(5) -0.2462(7) 0.0972(4) 0.039(2) Uani 1 1 d . . . H7A H 0.0650 -0.2932 0.1094 0.058 Uiso 1 1 calc R . . H7B H 0.1270 -0.2760 0.0886 0.058 Uiso 1 1 calc R . . H7C H 0.0617 -0.2153 0.0654 0.058 Uiso 1 1 calc R . . N1 N 0.1326(4) 0.0958(5) 0.1022(3) 0.0282(17) Uani 1 1 d . . . C10 C 0.1236(4) 0.1831(6) 0.0782(4) 0.029(2) Uani 1 1 d . . . C11 C 0.1108(6) 0.1966(8) 0.0239(4) 0.044(3) Uani 1 1 d . . . H11 H 0.1083 0.1443 0.0014 0.053 Uiso 1 1 calc R . . C12 C 0.1017(6) 0.2848(8) 0.0018(4) 0.047(3) Uani 1 1 d . . . H12 H 0.0929 0.2915 -0.0356 0.056 Uiso 1 1 calc R . . C13 C 0.1052(5) 0.3638(7) 0.0329(4) 0.038(2) Uani 1 1 d . . . C14 C 0.1189(5) 0.3515(7) 0.0867(4) 0.034(2) Uani 1 1 d . . . H14 H 0.1221 0.4043 0.1090 0.041 Uiso 1 1 calc R . . C15 C 0.1281(4) 0.2637(6) 0.1094(4) 0.031(2) Uani 1 1 d . . . H15 H 0.1377 0.2577 0.1469 0.037 Uiso 1 1 calc R . . C16 C 0.0941(7) 0.4584(9) 0.0080(6) 0.061(4) Uani 1 1 d . . . H16A H 0.0882 0.5036 0.0339 0.092 Uiso 1 1 calc R . . H16B H 0.0545 0.4574 -0.0231 0.092 Uiso 1 1 calc R . . H16C H 0.1322 0.4761 -0.0032 0.092 Uiso 1 1 calc R . . N2 N 0.1807(4) 0.0229(5) 0.2315(3) 0.0249(16) Uani 1 1 d . . . C20 C 0.2007(4) 0.0703(7) 0.2816(4) 0.028(2) Uani 1 1 d . . . C21 C 0.1777(5) 0.1585(6) 0.2888(4) 0.030(2) Uani 1 1 d . . . H21 H 0.1520 0.1921 0.2585 0.036 Uiso 1 1 calc R . . C22 C 0.1915(5) 0.1985(7) 0.3387(4) 0.036(2) Uani 1 1 d . . . H22 H 0.1740 0.2583 0.3415 0.043 Uiso 1 1 calc R . . C23 C 0.2297(5) 0.1548(8) 0.3849(4) 0.038(2) Uani 1 1 d . . . C24 C 0.2519(5) 0.0680(8) 0.3770(4) 0.045(3) Uani 1 1 d . . . H24 H 0.2787 0.0355 0.4072 0.054 Uiso 1 1 calc R . . C25 C 0.2378(5) 0.0253(7) 0.3281(4) 0.040(2) Uani 1 1 d . . . H25 H 0.2536 -0.0358 0.3259 0.048 Uiso 1 1 calc R . . C26 C 0.2431(6) 0.1973(10) 0.4385(4) 0.058(3) Uani 1 1 d . . . H26A H 0.2124 0.1720 0.4560 0.087 Uiso 1 1 calc R . . H26B H 0.2374 0.2648 0.4348 0.087 Uiso 1 1 calc R . . H26C H 0.2884 0.1832 0.4600 0.087 Uiso 1 1 calc R . . N3 N 0.0615(4) -0.0842(5) 0.1584(3) 0.0261(17) Uani 1 1 d . . . C30 C -0.0042(5) -0.1116(6) 0.1433(4) 0.027(2) Uani 1 1 d . . . C31 C -0.0234(5) -0.1977(6) 0.1585(4) 0.032(2) Uani 1 1 d . . . H31 H 0.0091 -0.2391 0.1793 0.039 Uiso 1 1 calc R . . C32 C -0.0902(5) -0.2233(7) 0.1433(4) 0.040(2) Uani 1 1 d . . . H32 H -0.1019 -0.2823 0.1538 0.048 Uiso 1 1 calc R . . C33 C -0.1392(4) -0.1654(7) 0.1136(4) 0.032(2) Uani 1 1 d . . . C34 C -0.1203(4) -0.0784(7) 0.1000(4) 0.030(2) Uani 1 1 d . . . H34 H -0.1532 -0.0362 0.0808 0.036 Uiso 1 1 calc R . . C35 C -0.0548(4) -0.0523(6) 0.1138(3) 0.0240(19) Uani 1 1 d . . . H35 H -0.0438 0.0069 0.1031 0.029 Uiso 1 1 calc R . . C36 C -0.2106(5) -0.1970(9) 0.0946(6) 0.056(3) Uani 1 1 d . . . H36A H -0.2394 -0.1445 0.0955 0.084 Uiso 1 1 calc R . . H36B H -0.2172 -0.2466 0.1178 0.084 Uiso 1 1 calc R . . H36C H -0.2211 -0.2203 0.0580 0.084 Uiso 1 1 calc R . . C40 C 0.0158(5) 0.1522(7) 0.1897(4) 0.037(2) Uani 1 1 d . . . H40A H -0.0217 0.1110 0.1885 0.044 Uiso 1 1 calc R . . H40B H 0.0360 0.1716 0.2272 0.044 Uiso 1 1 calc R . . C41 C -0.0105(5) 0.2388(7) 0.1559(4) 0.038(2) Uani 1 1 d . . . H41A H -0.0421 0.2705 0.1709 0.046 Uiso 1 1 calc R . . H41B H 0.0267 0.2819 0.1593 0.046 Uiso 1 1 calc R . . C42 C -0.0442(5) 0.2207(7) 0.0976(4) 0.041(2) Uani 1 1 d . . . H42A H -0.0815 0.1778 0.0940 0.050 Uiso 1 1 calc R . . H42B H -0.0127 0.1894 0.0824 0.050 Uiso 1 1 calc R . . C43 C -0.0697(7) 0.3075(9) 0.0654(6) 0.067(4) Uani 1 1 d . . . H43A H -0.1029 0.3371 0.0787 0.100 Uiso 1 1 calc R . . H43B H -0.0896 0.2907 0.0279 0.100 Uiso 1 1 calc R . . H43C H -0.0332 0.3507 0.0688 0.100 Uiso 1 1 calc R . . C1S C 0.0000 -0.455(3) 0.2500 0.164(15) Uiso 1 2 d S . . C2S C 0.0019(18) -0.501(3) 0.2944(13) 0.236(18) Uiso 1 1 d . A -1 H2S1 H -0.0268 -0.5560 0.2823 0.284 Uiso 1 1 calc R A -1 H2S2 H 0.0473 -0.5258 0.3083 0.284 Uiso 1 1 calc R A -1 C3S C -0.0120(14) -0.471(2) 0.3352(11) 0.164(11) Uiso 1 1 d . A -1 H3S1 H 0.0266 -0.4766 0.3668 0.246 Uiso 1 1 calc R A -1 H3S2 H -0.0486 -0.5067 0.3403 0.246 Uiso 1 1 calc R A -1 H3S3 H -0.0248 -0.4051 0.3297 0.246 Uiso 1 1 calc R A -1 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 Tl1 0.03019(19) 0.02444(19) 0.0189(2) 0.00127(14) 0.01156(14) 0.00023(14) Tl2 0.0382(2) 0.0481(3) 0.0253(2) 0.00615(17) 0.01481(17) -0.00830(17) C1 0.029(4) 0.028(5) 0.024(5) -0.001(4) 0.016(4) -0.003(4) Si1 0.0400(14) 0.0268(12) 0.0220(13) -0.0024(11) 0.0165(11) -0.0041(11) C2 0.064(7) 0.056(7) 0.020(6) 0.004(5) 0.008(5) -0.012(6) C3 0.072(8) 0.044(6) 0.055(8) -0.007(6) 0.053(7) -0.001(6) Si2 0.0269(12) 0.0323(14) 0.0251(14) -0.0055(11) 0.0081(11) -0.0014(11) C4 0.043(6) 0.059(7) 0.043(7) -0.011(6) 0.018(5) -0.020(5) C5 0.036(6) 0.063(7) 0.039(7) -0.018(6) -0.003(5) 0.011(5) Si3 0.0285(12) 0.0214(12) 0.0299(14) 0.0019(11) 0.0131(11) 0.0008(10) C6 0.034(5) 0.042(6) 0.063(8) 0.012(6) 0.019(5) 0.006(5) C7 0.050(6) 0.026(5) 0.052(7) -0.014(5) 0.033(5) -0.009(4) N1 0.047(5) 0.025(4) 0.022(4) 0.004(3) 0.024(4) 0.004(3) C10 0.030(5) 0.029(5) 0.034(6) 0.002(4) 0.016(4) 0.001(4) C11 0.065(7) 0.040(6) 0.029(6) 0.005(5) 0.015(5) 0.006(5) C12 0.066(7) 0.045(6) 0.031(6) 0.014(5) 0.017(5) 0.007(6) C13 0.042(6) 0.031(5) 0.038(6) 0.021(5) 0.009(5) -0.002(4) C14 0.039(5) 0.026(5) 0.041(6) -0.002(4) 0.018(5) -0.002(4) C15 0.033(5) 0.033(5) 0.029(5) 0.005(4) 0.013(4) -0.001(4) C16 0.069(8) 0.054(7) 0.062(9) 0.027(7) 0.023(7) 0.011(6) N2 0.034(4) 0.033(4) 0.011(4) -0.001(3) 0.011(3) 0.001(3) C20 0.028(5) 0.040(5) 0.019(5) -0.001(4) 0.013(4) -0.008(4) C21 0.039(5) 0.024(5) 0.027(5) 0.002(4) 0.010(4) -0.003(4) C22 0.043(6) 0.041(6) 0.028(6) -0.009(5) 0.019(5) -0.002(5) C23 0.037(5) 0.050(6) 0.031(6) -0.018(5) 0.017(5) -0.015(5) C24 0.041(6) 0.069(8) 0.019(5) 0.003(5) 0.001(4) -0.002(6) C25 0.044(6) 0.037(6) 0.033(6) -0.006(5) 0.004(5) 0.000(5) C26 0.055(7) 0.093(10) 0.026(6) -0.026(6) 0.012(5) -0.019(7) N3 0.028(4) 0.020(4) 0.036(5) 0.000(3) 0.018(3) -0.002(3) C30 0.039(5) 0.024(4) 0.023(5) -0.003(4) 0.018(4) -0.005(4) C31 0.033(5) 0.029(5) 0.042(6) 0.006(4) 0.023(5) 0.002(4) C32 0.041(6) 0.033(5) 0.052(7) 0.000(5) 0.020(5) -0.014(5) C33 0.026(5) 0.039(5) 0.031(5) -0.007(4) 0.009(4) -0.007(4) C34 0.028(5) 0.043(5) 0.024(5) 0.006(4) 0.013(4) -0.002(4) C35 0.032(5) 0.021(4) 0.021(5) 0.005(4) 0.012(4) -0.004(4) C36 0.030(5) 0.058(7) 0.080(10) -0.008(7) 0.017(6) -0.018(5) C40 0.033(5) 0.042(6) 0.042(6) -0.017(5) 0.023(5) -0.001(4) C41 0.040(6) 0.032(5) 0.045(6) -0.006(5) 0.016(5) 0.003(4) C42 0.043(6) 0.040(6) 0.042(6) 0.001(5) 0.014(5) 0.008(5) C43 0.072(8) 0.048(7) 0.073(10) 0.022(7) 0.011(7) 0.019(7) _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 Tl1 N1 2.155(7) . ? Tl1 C40 2.188(9) . ? Tl1 N2 2.321(7) . ? Tl1 N3 2.326(7) . ? Tl1 Si1 3.274(3) . ? Tl1 Si2 3.305(3) . ? Tl1 Tl2 3.3620(9) . ? Tl2 N2 2.694(7) . ? Tl2 N3 2.721(8) . ? Tl2 Tl2 3.7615(13) 2 ? C1 Si3 1.879(9) . ? C1 Si2 1.883(9) . ? C1 Si1 1.888(9) . ? Si1 N1 1.733(8) . ? Si1 C3 1.870(10) . ? Si1 C2 1.872(11) . ? Si2 N2 1.728(8) . ? Si2 C4 1.855(11) . ? Si2 C5 1.890(11) . ? Si3 N3 1.747(7) . ? Si3 C6 1.876(11) . ? Si3 C7 1.877(10) . ? N1 C10 1.395(11) . ? C10 C11 1.388(14) . ? C10 C15 1.408(13) . ? C11 C12 1.386(15) . ? C12 C13 1.392(15) . ? C13 C14 1.370(14) . ? C13 C16 1.501(14) . ? C14 C15 1.388(13) . ? N2 C20 1.431(11) . ? C20 C21 1.396(13) . ? C20 C25 1.399(14) . ? C21 C22 1.383(13) . ? C22 C23 1.393(15) . ? C23 C24 1.375(15) . ? C23 C26 1.486(13) . ? C24 C25 1.377(14) . ? N3 C30 1.391(11) . ? C30 C31 1.402(12) . ? C30 C35 1.410(13) . ? C31 C32 1.408(13) . ? C32 C33 1.379(14) . ? C33 C34 1.397(13) . ? C33 C36 1.519(12) . ? C34 C35 1.385(12) . ? C40 C41 1.536(14) . ? C41 C42 1.509(14) . ? C42 C43 1.515(15) . ? C1S C2S 1.34(4) 2 ? C1S C2S 1.34(4) . ? C2S C3S 1.28(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Tl1 C40 131.9(3) . . ? N1 Tl1 N2 99.3(3) . . ? C40 Tl1 N2 116.4(3) . . ? N1 Tl1 N3 104.7(3) . . ? C40 Tl1 N3 110.2(3) . . ? N2 Tl1 N3 83.5(3) . . ? N1 Tl1 Si1 28.8(2) . . ? C40 Tl1 Si1 155.8(3) . . ? N2 Tl1 Si1 86.80(18) . . ? N3 Tl1 Si1 77.57(19) . . ? N1 Tl1 Si2 71.8(2) . . ? C40 Tl1 Si2 145.3(3) . . ? N2 Tl1 Si2 29.72(18) . . ? N3 Tl1 Si2 80.25(18) . . ? Si1 Tl1 Si2 57.16(7) . . ? N1 Tl1 Tl2 142.5(2) . . ? C40 Tl1 Tl2 85.6(3) . . ? N2 Tl1 Tl2 52.83(18) . . ? N3 Tl1 Tl2 53.5(2) . . ? Si1 Tl1 Tl2 115.83(5) . . ? Si2 Tl1 Tl2 74.32(5) . . ? N2 Tl2 N3 69.7(2) . . ? N2 Tl2 Tl1 43.34(15) . . ? N3 Tl2 Tl1 43.40(15) . . ? N2 Tl2 Tl2 135.85(15) . 2 ? N3 Tl2 Tl2 82.20(15) . 2 ? Tl1 Tl2 Tl2 93.040(17) . 2 ? Si3 C1 Si2 112.9(5) . . ? Si3 C1 Si1 114.6(5) . . ? Si2 C1 Si1 113.2(5) . . ? N1 Si1 C3 112.0(4) . . ? N1 Si1 C2 111.8(5) . . ? C3 Si1 C2 106.1(5) . . ? N1 Si1 C1 105.1(4) . . ? C3 Si1 C1 109.5(5) . . ? C2 Si1 C1 112.4(4) . . ? N1 Si1 Tl1 36.8(2) . . ? C3 Si1 Tl1 142.0(4) . . ? C2 Si1 Tl1 107.2(4) . . ? C1 Si1 Tl1 73.8(3) . . ? N2 Si2 C4 109.7(5) . . ? N2 Si2 C1 106.1(4) . . ? C4 Si2 C1 113.3(5) . . ? N2 Si2 C5 113.8(5) . . ? C4 Si2 C5 103.1(6) . . ? C1 Si2 C5 110.9(4) . . ? N2 Si2 Tl1 41.7(2) . . ? C4 Si2 Tl1 100.9(4) . . ? C1 Si2 Tl1 73.0(3) . . ? C5 Si2 Tl1 151.3(4) . . ? N3 Si3 C6 112.5(4) . . ? N3 Si3 C7 112.0(4) . . ? C6 Si3 C7 101.4(5) . . ? N3 Si3 C1 106.7(4) . . ? C6 Si3 C1 110.5(4) . . ? C7 Si3 C1 113.8(4) . . ? C10 N1 Si1 127.5(6) . . ? C10 N1 Tl1 117.0(6) . . ? Si1 N1 Tl1 114.3(4) . . ? C11 C10 N1 123.4(9) . . ? C11 C10 C15 116.5(9) . . ? N1 C10 C15 120.1(8) . . ? C12 C11 C10 121.3(10) . . ? C11 C12 C13 121.7(10) . . ? C14 C13 C12 117.5(9) . . ? C14 C13 C16 121.8(11) . . ? C12 C13 C16 120.7(10) . . ? C13 C14 C15 121.4(10) . . ? C14 C15 C10 121.6(9) . . ? C20 N2 Si2 121.4(6) . . ? C20 N2 Tl1 119.9(6) . . ? Si2 N2 Tl1 108.5(3) . . ? C20 N2 Tl2 88.0(5) . . ? Si2 N2 Tl2 129.9(4) . . ? Tl1 N2 Tl2 83.8(2) . . ? C21 C20 C25 115.6(9) . . ? C21 C20 N2 122.8(8) . . ? C25 C20 N2 121.1(9) . . ? C22 C21 C20 121.8(9) . . ? C21 C22 C23 122.8(9) . . ? C24 C23 C22 114.5(9) . . ? C24 C23 C26 123.0(11) . . ? C22 C23 C26 122.5(10) . . ? C23 C24 C25 124.2(10) . . ? C24 C25 C20 121.1(10) . . ? C30 N3 Si3 121.6(6) . . ? C30 N3 Tl1 120.1(6) . . ? Si3 N3 Tl1 114.8(3) . . ? C30 N3 Tl2 102.6(5) . . ? Si3 N3 Tl2 102.1(3) . . ? Tl1 N3 Tl2 83.1(2) . . ? N3 C30 C31 121.7(9) . . ? N3 C30 C35 121.3(8) . . ? C31 C30 C35 116.9(8) . . ? C30 C31 C32 120.7(9) . . ? C33 C32 C31 122.0(9) . . ? C32 C33 C34 117.3(8) . . ? C32 C33 C36 121.1(9) . . ? C34 C33 C36 121.5(9) . . ? C35 C34 C33 121.7(9) . . ? C34 C35 C30 121.4(8) . . ? C41 C40 Tl1 114.6(7) . . ? C42 C41 C40 115.3(8) . . ? C41 C42 C43 114.0(10) . . ? C2S C1S C2S 120(5) 2 . ? C3S C2S C1S 128(4) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 Tl1 Tl2 N2 49.0(4) . . . . ? C40 Tl1 Tl2 N2 -128.2(3) . . . . ? N3 Tl1 Tl2 N2 112.6(3) . . . . ? Si1 Tl1 Tl2 N2 63.6(2) . . . . ? Si2 Tl1 Tl2 N2 23.2(2) . . . . ? N1 Tl1 Tl2 N3 -63.5(4) . . . . ? C40 Tl1 Tl2 N3 119.2(3) . . . . ? N2 Tl1 Tl2 N3 -112.6(3) . . . . ? Si1 Tl1 Tl2 N3 -49.0(2) . . . . ? Si2 Tl1 Tl2 N3 -89.4(2) . . . . ? N1 Tl1 Tl2 Tl2 -138.8(4) . . . 2 ? C40 Tl1 Tl2 Tl2 43.9(3) . . . 2 ? N2 Tl1 Tl2 Tl2 172.1(2) . . . 2 ? N3 Tl1 Tl2 Tl2 -75.3(2) . . . 2 ? Si1 Tl1 Tl2 Tl2 -124.28(5) . . . 2 ? Si2 Tl1 Tl2 Tl2 -164.66(5) . . . 2 ? Si3 C1 Si1 N1 87.7(5) . . . . ? Si2 C1 Si1 N1 -43.8(5) . . . . ? Si3 C1 Si1 C3 -151.8(5) . . . . ? Si2 C1 Si1 C3 76.8(6) . . . . ? Si3 C1 Si1 C2 -34.2(7) . . . . ? Si2 C1 Si1 C2 -165.6(5) . . . . ? Si3 C1 Si1 Tl1 68.1(4) . . . . ? Si2 C1 Si1 Tl1 -63.3(4) . . . . ? C40 Tl1 Si1 N1 48.3(8) . . . . ? N2 Tl1 Si1 N1 -115.9(5) . . . . ? N3 Tl1 Si1 N1 160.1(5) . . . . ? Si2 Tl1 Si1 N1 -113.6(5) . . . . ? Tl2 Tl1 Si1 N1 -161.5(5) . . . . ? N1 Tl1 Si1 C3 46.3(8) . . . . ? C40 Tl1 Si1 C3 94.6(9) . . . . ? N2 Tl1 Si1 C3 -69.6(7) . . . . ? N3 Tl1 Si1 C3 -153.6(7) . . . . ? Si2 Tl1 Si1 C3 -67.3(7) . . . . ? Tl2 Tl1 Si1 C3 -115.2(7) . . . . ? N1 Tl1 Si1 C2 -103.6(6) . . . . ? C40 Tl1 Si1 C2 -55.3(7) . . . . ? N2 Tl1 Si1 C2 140.5(4) . . . . ? N3 Tl1 Si1 C2 56.5(4) . . . . ? Si2 Tl1 Si1 C2 142.8(4) . . . . ? Tl2 Tl1 Si1 C2 94.9(4) . . . . ? N1 Tl1 Si1 C1 147.4(5) . . . . ? C40 Tl1 Si1 C1 -164.3(7) . . . . ? N2 Tl1 Si1 C1 31.5(3) . . . . ? N3 Tl1 Si1 C1 -52.5(3) . . . . ? Si2 Tl1 Si1 C1 33.8(3) . . . . ? Tl2 Tl1 Si1 C1 -14.1(3) . . . . ? Si3 C1 Si2 N2 -43.8(6) . . . . ? Si1 C1 Si2 N2 88.4(5) . . . . ? Si3 C1 Si2 C4 -164.3(5) . . . . ? Si1 C1 Si2 C4 -32.0(7) . . . . ? Si3 C1 Si2 C5 80.3(6) . . . . ? Si1 C1 Si2 C5 -147.4(5) . . . . ? Si3 C1 Si2 Tl1 -69.5(4) . . . . ? Si1 C1 Si2 Tl1 62.7(4) . . . . ? N1 Tl1 Si2 N2 156.9(4) . . . . ? C40 Tl1 Si2 N2 17.6(6) . . . . ? N3 Tl1 Si2 N2 -93.9(4) . . . . ? Si1 Tl1 Si2 N2 -175.3(4) . . . . ? Tl2 Tl1 Si2 N2 -39.3(4) . . . . ? N1 Tl1 Si2 C4 49.4(4) . . . . ? C40 Tl1 Si2 C4 -89.9(6) . . . . ? N2 Tl1 Si2 C4 -107.5(5) . . . . ? N3 Tl1 Si2 C4 158.6(4) . . . . ? Si1 Tl1 Si2 C4 77.2(4) . . . . ? Tl2 Tl1 Si2 C4 -146.8(4) . . . . ? N1 Tl1 Si2 C1 -61.9(4) . . . . ? C40 Tl1 Si2 C1 158.8(6) . . . . ? N2 Tl1 Si2 C1 141.2(5) . . . . ? N3 Tl1 Si2 C1 47.3(3) . . . . ? Si1 Tl1 Si2 C1 -34.1(3) . . . . ? Tl2 Tl1 Si2 C1 101.9(3) . . . . ? N1 Tl1 Si2 C5 -164.5(8) . . . . ? C40 Tl1 Si2 C5 56.2(9) . . . . ? N2 Tl1 Si2 C5 38.5(8) . . . . ? N3 Tl1 Si2 C5 -55.4(8) . . . . ? Si1 Tl1 Si2 C5 -136.8(8) . . . . ? Tl2 Tl1 Si2 C5 -0.7(7) . . . . ? Si2 C1 Si3 N3 72.2(5) . . . . ? Si1 C1 Si3 N3 -59.4(6) . . . . ? Si2 C1 Si3 C6 -50.5(6) . . . . ? Si1 C1 Si3 C6 178.0(5) . . . . ? Si2 C1 Si3 C7 -163.8(5) . . . . ? Si1 C1 Si3 C7 64.7(6) . . . . ? C3 Si1 N1 C10 41.9(10) . . . . ? C2 Si1 N1 C10 -77.0(9) . . . . ? C1 Si1 N1 C10 160.8(8) . . . . ? Tl1 Si1 N1 C10 -166.8(11) . . . . ? C3 Si1 N1 Tl1 -151.3(5) . . . . ? C2 Si1 N1 Tl1 89.8(5) . . . . ? C1 Si1 N1 Tl1 -32.4(5) . . . . ? C40 Tl1 N1 C10 12.5(9) . . . . ? N2 Tl1 N1 C10 -126.2(7) . . . . ? N3 Tl1 N1 C10 148.2(7) . . . . ? Si1 Tl1 N1 C10 168.3(10) . . . . ? Si2 Tl1 N1 C10 -137.5(7) . . . . ? Tl2 Tl1 N1 C10 -163.7(5) . . . . ? C40 Tl1 N1 Si1 -155.8(4) . . . . ? N2 Tl1 N1 Si1 65.5(5) . . . . ? N3 Tl1 N1 Si1 -20.1(5) . . . . ? Si2 Tl1 N1 Si1 54.2(4) . . . . ? Tl2 Tl1 N1 Si1 28.0(7) . . . . ? Si1 N1 C10 C11 27.0(14) . . . . ? Tl1 N1 C10 C11 -139.5(8) . . . . ? Si1 N1 C10 C15 -152.1(7) . . . . ? Tl1 N1 C10 C15 41.4(11) . . . . ? N1 C10 C11 C12 179.5(10) . . . . ? C15 C10 C11 C12 -1.4(16) . . . . ? C10 C11 C12 C13 0.3(18) . . . . ? C11 C12 C13 C14 0.9(17) . . . . ? C11 C12 C13 C16 -179.0(11) . . . . ? C12 C13 C14 C15 -0.9(15) . . . . ? C16 C13 C14 C15 179.0(10) . . . . ? C13 C14 C15 C10 -0.2(15) . . . . ? C11 C10 C15 C14 1.3(14) . . . . ? N1 C10 C15 C14 -179.5(9) . . . . ? C4 Si2 N2 C20 -61.0(8) . . . . ? C1 Si2 N2 C20 176.2(7) . . . . ? C5 Si2 N2 C20 53.9(8) . . . . ? Tl1 Si2 N2 C20 -145.2(9) . . . . ? C4 Si2 N2 Tl1 84.2(5) . . . . ? C1 Si2 N2 Tl1 -38.6(5) . . . . ? C5 Si2 N2 Tl1 -160.9(4) . . . . ? C4 Si2 N2 Tl2 -178.2(5) . . . . ? C1 Si2 N2 Tl2 59.0(5) . . . . ? C5 Si2 N2 Tl2 -63.3(6) . . . . ? Tl1 Si2 N2 Tl2 97.6(5) . . . . ? N1 Tl1 N2 C20 123.6(6) . . . . ? C40 Tl1 N2 C20 -23.1(7) . . . . ? N3 Tl1 N2 C20 -132.4(6) . . . . ? Si1 Tl1 N2 C20 149.7(6) . . . . ? Si2 Tl1 N2 C20 145.8(8) . . . . ? Tl2 Tl1 N2 C20 -84.1(6) . . . . ? N1 Tl1 N2 Si2 -22.1(4) . . . . ? C40 Tl1 N2 Si2 -168.9(4) . . . . ? N3 Tl1 N2 Si2 81.8(4) . . . . ? Si1 Tl1 N2 Si2 3.9(3) . . . . ? Tl2 Tl1 N2 Si2 130.1(4) . . . . ? N1 Tl1 N2 Tl2 -152.2(2) . . . . ? C40 Tl1 N2 Tl2 61.0(4) . . . . ? N3 Tl1 N2 Tl2 -48.3(2) . . . . ? Si1 Tl1 N2 Tl2 -126.16(15) . . . . ? Si2 Tl1 N2 Tl2 -130.1(4) . . . . ? N3 Tl2 N2 C20 162.9(5) . . . . ? Tl1 Tl2 N2 C20 120.4(6) . . . . ? Tl2 Tl2 N2 C20 109.1(5) 2 . . . ? N3 Tl2 N2 Si2 -66.5(5) . . . . ? Tl1 Tl2 N2 Si2 -109.1(5) . . . . ? Tl2 Tl2 N2 Si2 -120.4(4) 2 . . . ? N3 Tl2 N2 Tl1 42.6(2) . . . . ? Tl2 Tl2 N2 Tl1 -11.3(3) 2 . . . ? Si2 N2 C20 C21 125.3(8) . . . . ? Tl1 N2 C20 C21 -16.1(11) . . . . ? Tl2 N2 C20 C21 -97.8(8) . . . . ? Si2 N2 C20 C25 -63.3(11) . . . . ? Tl1 N2 C20 C25 155.3(7) . . . . ? Tl2 N2 C20 C25 73.6(8) . . . . ? C25 C20 C21 C22 0.4(14) . . . . ? N2 C20 C21 C22 172.3(8) . . . . ? C20 C21 C22 C23 1.1(15) . . . . ? C21 C22 C23 C24 -0.9(14) . . . . ? C21 C22 C23 C26 -178.7(9) . . . . ? C22 C23 C24 C25 -0.8(16) . . . . ? C26 C23 C24 C25 177.0(11) . . . . ? C23 C24 C25 C20 2.3(17) . . . . ? C21 C20 C25 C24 -2.0(14) . . . . ? N2 C20 C25 C24 -174.1(9) . . . . ? C6 Si3 N3 C30 -88.1(8) . . . . ? C7 Si3 N3 C30 25.4(9) . . . . ? C1 Si3 N3 C30 150.6(7) . . . . ? C6 Si3 N3 Tl1 113.0(5) . . . . ? C7 Si3 N3 Tl1 -133.5(5) . . . . ? C1 Si3 N3 Tl1 -8.3(5) . . . . ? C6 Si3 N3 Tl2 25.1(5) . . . . ? C7 Si3 N3 Tl2 138.5(4) . . . . ? C1 Si3 N3 Tl2 -96.3(4) . . . . ? N1 Tl1 N3 C30 -113.7(7) . . . . ? C40 Tl1 N3 C30 32.6(8) . . . . ? N2 Tl1 N3 C30 148.4(7) . . . . ? Si1 Tl1 N3 C30 -123.5(7) . . . . ? Si2 Tl1 N3 C30 178.2(7) . . . . ? Tl2 Tl1 N3 C30 100.6(7) . . . . ? N1 Tl1 N3 Si3 45.5(5) . . . . ? C40 Tl1 N3 Si3 -168.1(4) . . . . ? N2 Tl1 N3 Si3 -52.4(4) . . . . ? Si1 Tl1 N3 Si3 35.8(4) . . . . ? Si2 Tl1 N3 Si3 -22.5(4) . . . . ? Tl2 Tl1 N3 Si3 -100.2(4) . . . . ? N1 Tl1 N3 Tl2 145.7(2) . . . . ? C40 Tl1 N3 Tl2 -68.0(3) . . . . ? N2 Tl1 N3 Tl2 47.8(2) . . . . ? Si1 Tl1 N3 Tl2 135.93(17) . . . . ? Si2 Tl1 N3 Tl2 77.64(14) . . . . ? N2 Tl2 N3 C30 -161.9(6) . . . . ? Tl1 Tl2 N3 C30 -119.4(6) . . . . ? Tl2 Tl2 N3 C30 -16.5(5) 2 . . . ? N2 Tl2 N3 Si3 71.5(3) . . . . ? Tl1 Tl2 N3 Si3 114.0(4) . . . . ? Tl2 Tl2 N3 Si3 -143.2(3) 2 . . . ? N2 Tl2 N3 Tl1 -42.5(2) . . . . ? Tl2 Tl2 N3 Tl1 102.87(16) 2 . . . ? Si3 N3 C30 C31 47.8(12) . . . . ? Tl1 N3 C30 C31 -154.4(7) . . . . ? Tl2 N3 C30 C31 -65.1(9) . . . . ? Si3 N3 C30 C35 -134.8(8) . . . . ? Tl1 N3 C30 C35 23.0(11) . . . . ? Tl2 N3 C30 C35 112.3(8) . . . . ? N3 C30 C31 C32 179.3(9) . . . . ? C35 C30 C31 C32 1.7(14) . . . . ? C30 C31 C32 C33 -0.7(16) . . . . ? C31 C32 C33 C34 -1.4(16) . . . . ? C31 C32 C33 C36 175.9(10) . . . . ? C32 C33 C34 C35 2.5(15) . . . . ? C36 C33 C34 C35 -174.8(10) . . . . ? C33 C34 C35 C30 -1.5(14) . . . . ? N3 C30 C35 C34 -178.2(8) . . . . ? C31 C30 C35 C34 -0.7(13) . . . . ? N1 Tl1 C40 C41 2.3(9) . . . . ? N2 Tl1 C40 C41 135.7(7) . . . . ? N3 Tl1 C40 C41 -131.6(7) . . . . ? Si1 Tl1 C40 C41 -26.6(12) . . . . ? Si2 Tl1 C40 C41 126.0(6) . . . . ? Tl2 Tl1 C40 C41 -180.0(7) . . . . ? Tl1 C40 C41 C42 59.4(10) . . . . ? C40 C41 C42 C43 179.9(10) . . . . ? C2S C1S C2S C3S -161(5) 2 . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 2.214 _refine_diff_density_min -2.920 _refine_diff_density_rms 0.220