#------------------------------------------------------------------------------ #$Date: 2020-10-06 11:56:53 +0300 (Tue, 06 Oct 2020) $ #$Revision: 257552 $ #$URL: file:///home/coder/svn-repositories/cod/cif/7/70/52/7705234.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_7705234 loop_ _publ_author_name 'Sha, Fanrui' 'Shimizu, Emily A.' 'Slocumb, Hannah S.' 'Towell, Sydney E.' 'Zhen, Yi' 'Porter, Hanna Z.' 'Takase, Michael K.' 'Johnson, Adam R.' _publ_section_title ; Catalytic intramolecular hydroamination of aminoallenes using titanium and tantalum complexes of sterically encumbered chiral sulfonamides. ; _journal_issue 35 _journal_name_full 'Dalton transactions (Cambridge, England : 2003)' _journal_page_first 12418 _journal_page_last 12431 _journal_paper_doi 10.1039/d0dt02557g _journal_volume 49 _journal_year 2020 _chemical_absolute_configuration ad _chemical_formula_sum 'C42 H48 F6 N4 O3 S Ti' _chemical_formula_weight 850.80 _space_group_crystal_system orthorhombic _space_group_IT_number 19 _space_group_name_Hall 'P 2ac 2ab' _space_group_name_H-M_alt 'P 21 21 21' _atom_sites_solution_hydrogens mixed _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _audit_creation_method SHELXL-2018/3 _audit_update_record ; 2019-12-06 deposited with the CCDC. 2020-08-21 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 8.1293(8) _cell_length_b 21.067(2) _cell_length_c 24.630(2) _cell_measurement_reflns_used 9715 _cell_measurement_temperature 100(2) _cell_measurement_theta_max 74.33 _cell_measurement_theta_min 2.76 _cell_volume 4218.1(7) _computing_cell_refinement 'SAINT v8.38A (Bruker-AXS, 2013)' _computing_data_collection 'APEX3 v2017.3-0 (Bruker-AXS, 2017)' _computing_data_reduction 'SAINT v8.38A (Bruker-AXS, 2013)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _computing_structure_refinement 'SHELXL-2018/3 (Sheldrick, 2018)' _computing_structure_solution 'SHELXS-2013/1 (Sheldrick, 2013)' _diffrn_ambient_temperature 100(2) _diffrn_detector_area_resol_mean 7.69 _diffrn_measured_fraction_theta_full 1.000 _diffrn_measured_fraction_theta_max 0.999 _diffrn_measurement_device_type 'Bruker D8 VENTURE Kappa Duo PHOTON II CPAD' _diffrn_measurement_method '\f and \w scans' _diffrn_radiation_type CuK\a _diffrn_radiation_wavelength 1.54178 _diffrn_reflns_av_R_equivalents 0.0479 _diffrn_reflns_av_unetI/netI 0.0378 _diffrn_reflns_Laue_measured_fraction_full 1.000 _diffrn_reflns_Laue_measured_fraction_max 0.999 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_number 52021 _diffrn_reflns_point_group_measured_fraction_full 0.990 _diffrn_reflns_point_group_measured_fraction_max 0.986 _diffrn_reflns_theta_full 67.679 _diffrn_reflns_theta_max 74.427 _diffrn_reflns_theta_min 2.760 _diffrn_source 'I\mS HB micro-focus sealed tube' _exptl_absorpt_coefficient_mu 2.776 _exptl_absorpt_correction_T_max 0.7538 _exptl_absorpt_correction_T_min 0.6025 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS-2016/2 (Sheldrick, 2014)' _exptl_crystal_colour colourless _exptl_crystal_density_diffrn 1.340 _exptl_crystal_density_method 'not measured' _exptl_crystal_description Block _exptl_crystal_F_000 1776 _exptl_crystal_size_max 0.300 _exptl_crystal_size_mid 0.250 _exptl_crystal_size_min 0.150 _refine_diff_density_max 0.487 _refine_diff_density_min -0.219 _refine_diff_density_rms 0.044 _refine_ls_abs_structure_details ; Flack x determined using 3313 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). ; _refine_ls_abs_structure_Flack 0.056(3) _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_hydrogen_treatment mixed _refine_ls_matrix_type full _refine_ls_number_parameters 580 _refine_ls_number_reflns 8503 _refine_ls_number_restraints 272 _refine_ls_restrained_S_all 1.131 _refine_ls_R_factor_all 0.0349 _refine_ls_R_factor_gt 0.0326 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0418P)^2^+1.1839P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0828 _refine_ls_wR_factor_ref 0.0847 _reflns_Friedel_coverage 0.758 _reflns_Friedel_fraction_full 0.977 _reflns_Friedel_fraction_max 0.969 _reflns_number_gt 8079 _reflns_number_total 8503 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d0dt02557g2.cif _cod_data_source_block V19228 _cod_depositor_comments 'Adding full bibliography for 7705232--7705236.cif.' _cod_database_code 7705234 _shelx_shelxl_version_number 2018/3 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelx_estimated_absorpt_t_min 0.490 _shelx_estimated_absorpt_t_max 0.681 _shelx_res_file ; TITL V19228 in P2(1)2(1)2(1) V19228.res created by SHELXL-2018/3 at 09:50:50 on 06-Jun-2019 CELL 1.54178 8.12930 21.06700 24.63000 90.0000 90.0000 90.0000 ZERR 4.00 0.00080 0.00200 0.00200 0.0000 0.0000 0.0000 LATT -1 SYMM 0.5-X, -Y, 0.5+Z SYMM -X, 0.5+Y, 0.5-Z SYMM 0.5+X, 0.5-Y, -Z SFAC C H N O F S TI UNIT 168 192 16 12 24 4 4 TEMP -173 SIZE 0.15 0.25 0.30 ACTA WPDB -2 CONF L.S. 10 BOND $H FMAP 2 PLAN 20 dfix 0.91 n2 h2n rigu c47 > f3a c48 > f6a EQIV $1 x-1, y, z HTAB HTAB N2 S1_$1 HTAB N2 O3_$1 HTAB C51 O1 HTAB C52 N3 WGHT 0.041800 1.183900 FVAR 0.13349 0.56123 0.51702 TI1 7 0.398183 0.522001 0.661379 11.00000 0.01429 0.02785 = 0.01535 -0.00494 0.00018 -0.00058 O1 4 0.331964 0.553691 0.593154 11.00000 0.01593 0.02598 = 0.01924 -0.00218 0.00231 0.00109 C1 1 0.436062 0.559501 0.547083 11.00000 0.01645 0.02051 = 0.01926 -0.00079 0.00031 0.00023 C11 1 0.527732 0.623418 0.549978 11.00000 0.02477 0.02015 = 0.02179 -0.00129 -0.00029 -0.00110 C12 1 0.697849 0.630255 0.547595 11.00000 0.02652 0.02415 = 0.02839 -0.00047 -0.00093 -0.00314 AFIX 43 H12 2 0.765119 0.593602 0.544146 11.00000 -1.20000 AFIX 0 C13 1 0.771150 0.689965 0.550185 11.00000 0.03034 0.03427 = 0.04034 0.00127 -0.00210 -0.00904 AFIX 43 H13 2 0.887455 0.693689 0.548192 11.00000 -1.20000 AFIX 0 C14 1 0.675150 0.743934 0.555654 11.00000 0.04895 0.02347 = 0.04775 -0.00155 -0.00314 -0.01062 AFIX 43 H14 2 0.725075 0.784649 0.557497 11.00000 -1.20000 AFIX 0 C15 1 0.507042 0.737989 0.558383 11.00000 0.04699 0.02170 = 0.05087 -0.00216 0.00286 0.00110 AFIX 43 H15 2 0.440589 0.774760 0.562559 11.00000 -1.20000 AFIX 0 C16 1 0.433436 0.678462 0.555073 11.00000 0.03014 0.02647 = 0.04252 -0.00253 0.00200 0.00279 AFIX 43 H16 2 0.316933 0.675241 0.556304 11.00000 -1.20000 AFIX 0 C21 1 0.331148 0.559537 0.495555 11.00000 0.02221 0.02128 = 0.02035 0.00113 -0.00106 0.00090 C22 1 0.162955 0.547281 0.498061 11.00000 0.02152 0.03910 = 0.02276 0.00258 -0.00195 -0.00026 AFIX 43 H22 2 0.112550 0.538417 0.532024 11.00000 -1.20000 AFIX 0 C23 1 0.068567 0.547992 0.450919 11.00000 0.02314 0.05517 = 0.03037 0.00155 -0.00659 -0.00374 AFIX 43 H23 2 -0.046124 0.539675 0.452954 11.00000 -1.20000 AFIX 0 C24 1 0.140440 0.560749 0.400905 11.00000 0.03448 0.04758 = 0.02454 0.00355 -0.00936 0.00135 AFIX 43 H24 2 0.075347 0.561276 0.368875 11.00000 -1.20000 AFIX 0 C25 1 0.308335 0.572729 0.398136 11.00000 0.03574 0.03443 = 0.02159 0.00614 0.00004 -0.00043 AFIX 43 H25 2 0.358842 0.581302 0.364136 11.00000 -1.20000 AFIX 0 C26 1 0.401909 0.572112 0.445278 11.00000 0.02410 0.02546 = 0.02508 0.00208 0.00024 -0.00004 AFIX 43 H26 2 0.516578 0.580446 0.443157 11.00000 -1.20000 AFIX 0 C2 1 0.554422 0.501539 0.550003 11.00000 0.01810 0.01936 = 0.01517 -0.00167 0.00168 -0.00240 AFIX 13 H2 2 0.657122 0.511005 0.529173 11.00000 -1.20000 AFIX 0 N1 3 0.593211 0.496886 0.608760 11.00000 0.01410 0.02229 = 0.01566 -0.00203 0.00050 0.00005 S1 6 0.767200 0.473329 0.627480 11.00000 0.01438 0.02153 = 0.01906 -0.00231 -0.00085 -0.00064 O2 4 0.773673 0.475927 0.686082 11.00000 0.02464 0.03187 = 0.02024 -0.00330 -0.00475 0.00317 O3 4 0.901550 0.502924 0.598087 11.00000 0.01507 0.02321 = 0.03036 -0.00185 0.00148 -0.00209 C41 1 0.787614 0.390747 0.611454 11.00000 0.01814 0.02237 = 0.01944 0.00080 -0.00209 -0.00048 C42 1 0.906339 0.370564 0.574859 11.00000 0.01635 0.02511 = 0.02098 0.00187 -0.00148 -0.00057 AFIX 43 H42 2 0.974751 0.400423 0.556815 11.00000 -1.20000 AFIX 0 same c43 c47 f2 f3 f1 f1 f2 f3 C43 1 0.923462 0.306225 0.565077 11.00000 0.02427 0.02448 = 0.02637 -0.00232 0.00118 0.00159 C47 1 1.056484 0.284517 0.526639 11.00000 0.03659 0.02987 = 0.04545 -0.00944 0.01404 -0.00192 PART 1 F1 5 1.120317 0.327059 0.497642 21.00000 0.08412 0.02469 = 0.09731 0.00017 0.07045 -0.00068 F2 5 1.019851 0.233746 0.499902 21.00000 0.04569 0.06556 = 0.07331 -0.05131 0.02535 -0.01808 F3 5 1.188474 0.262131 0.558129 21.00000 0.03637 0.11236 = 0.07123 -0.01643 0.00319 0.03356 PART 2 F1A 5 1.029619 0.316219 0.476756 -21.00000 0.09338 0.09274 = 0.04944 0.02502 0.04254 0.04881 F2A 5 1.048693 0.227177 0.512111 -21.00000 0.11869 0.01411 = 0.13482 -0.00515 0.08907 0.00102 F3A 5 1.199004 0.302201 0.538636 -21.00000 0.03200 0.12012 = 0.09165 -0.06265 0.01965 -0.01117 PART 0 C44 1 0.825428 0.261870 0.590831 11.00000 0.02989 0.02327 = 0.03459 0.00204 0.00062 0.00118 AFIX 43 H44 2 0.839031 0.217840 0.583814 11.00000 -1.20000 AFIX 0 same c43 > f3a C45 1 0.707358 0.282769 0.626948 11.00000 0.03068 0.02678 = 0.03537 0.00491 0.00610 -0.00346 C48 1 0.601606 0.235090 0.656684 11.00000 0.04873 0.03153 = 0.06006 0.00524 0.02533 -0.00570 PART 1 F4 5 0.581046 0.183511 0.629073 31.00000 0.07575 0.03707 = 0.07896 0.00702 -0.01053 -0.03405 F5 5 0.628553 0.231985 0.706800 31.00000 0.24199 0.17434 = 0.04902 0.01726 0.02121 -0.15670 F6 5 0.440656 0.255094 0.652963 31.00000 0.06121 0.03894 = 0.29447 0.04279 0.09545 0.00401 PART 2 F4A 5 0.590045 0.179466 0.632067 -31.00000 0.05053 0.03080 = 0.06806 0.00027 0.03697 -0.00692 F5A 5 0.692653 0.212027 0.700971 -31.00000 0.06732 0.04665 = 0.03082 0.02045 0.00151 -0.01720 F6A 5 0.469030 0.255800 0.675941 -31.00000 0.07607 0.04309 = 0.13821 0.02979 0.08130 0.01168 PART 0 C46 1 0.686587 0.347340 0.637720 11.00000 0.02318 0.02835 = 0.02861 0.00239 0.00658 -0.00111 AFIX 43 H46 2 0.604859 0.361330 0.662557 11.00000 -1.20000 AFIX 0 C3 1 0.475892 0.439539 0.528381 11.00000 0.02063 0.02061 = 0.01820 0.00017 0.00060 -0.00319 AFIX 23 H3A 2 0.513465 0.403662 0.551187 11.00000 -1.20000 H3B 2 0.354916 0.442632 0.532166 11.00000 -1.20000 AFIX 0 C31 1 0.517026 0.425162 0.469479 11.00000 0.03246 0.01632 = 0.01898 -0.00005 -0.00066 -0.00090 C32 1 0.395139 0.415638 0.431025 11.00000 0.03791 0.02564 = 0.02159 0.00226 -0.00386 -0.01059 AFIX 43 H32 2 0.282963 0.419600 0.441293 11.00000 -1.20000 AFIX 0 C33 1 0.434231 0.400405 0.377755 11.00000 0.06342 0.03236 = 0.01888 0.00122 -0.00788 -0.01738 AFIX 43 H33 2 0.349032 0.394098 0.351913 11.00000 -1.20000 AFIX 0 C34 1 0.597889 0.394347 0.362110 11.00000 0.07270 0.03663 = 0.01533 -0.00317 0.00444 -0.00063 AFIX 43 H34 2 0.624879 0.383468 0.325754 11.00000 -1.20000 AFIX 0 C35 1 0.721196 0.404311 0.399986 11.00000 0.04983 0.04659 = 0.02385 -0.00149 0.00987 0.01332 AFIX 43 H35 2 0.833333 0.400709 0.389576 11.00000 -1.20000 AFIX 0 C36 1 0.680640 0.419601 0.453295 11.00000 0.03671 0.03402 = 0.01957 -0.00189 -0.00053 0.00907 AFIX 43 H36 2 0.765832 0.426354 0.479057 11.00000 -1.20000 AFIX 0 N2 3 0.147319 0.556655 0.681766 11.00000 0.01679 0.03353 = 0.02678 -0.00968 0.00263 -0.00075 H2N 2 0.083772 0.535518 0.657726 11.00000 -1.20000 C51 1 0.122673 0.624620 0.671423 11.00000 0.02888 0.03745 = 0.06825 -0.01305 0.01680 0.00609 AFIX 137 H51A 2 0.008638 0.636102 0.679795 11.00000 -1.50000 H51B 2 0.145567 0.633794 0.633155 11.00000 -1.50000 H51C 2 0.197360 0.649333 0.694415 11.00000 -1.50000 AFIX 0 C52 1 0.094696 0.540161 0.737580 11.00000 0.02326 0.07604 = 0.02258 -0.01392 0.00532 0.00511 AFIX 137 H52A 2 0.166887 0.561257 0.763845 11.00000 -1.50000 H52B 2 0.101303 0.494083 0.742586 11.00000 -1.50000 H52C 2 -0.018923 0.554230 0.743241 11.00000 -1.50000 AFIX 0 N3 3 0.340787 0.439552 0.687257 11.00000 0.01975 0.03427 = 0.01956 0.00365 0.00157 -0.00215 C53 1 0.376196 0.405661 0.737543 11.00000 0.03339 0.04647 = 0.02351 0.00618 -0.00202 -0.00349 AFIX 137 H53A 2 0.280196 0.407732 0.761544 11.00000 -1.50000 H53B 2 0.470873 0.425282 0.755571 11.00000 -1.50000 H53C 2 0.401313 0.361194 0.729307 11.00000 -1.50000 AFIX 0 C54 1 0.224358 0.405671 0.653898 11.00000 0.02976 0.03551 = 0.02539 0.00342 -0.00277 -0.00360 AFIX 137 H54A 2 0.269825 0.364102 0.644217 11.00000 -1.50000 H54B 2 0.202645 0.430033 0.620768 11.00000 -1.50000 H54C 2 0.121497 0.399858 0.674043 11.00000 -1.50000 AFIX 0 N4 3 0.506201 0.574941 0.711235 11.00000 0.02000 0.04269 = 0.02482 -0.01394 -0.00030 -0.00142 C55 1 0.536566 0.558750 0.768107 11.00000 0.03785 0.05475 = 0.02691 -0.01442 -0.00876 0.00516 AFIX 137 H55A 2 0.651834 0.546202 0.772638 11.00000 -1.50000 H55B 2 0.464908 0.523484 0.778779 11.00000 -1.50000 H55C 2 0.513300 0.595715 0.791009 11.00000 -1.50000 AFIX 0 C56 1 0.591075 0.632112 0.695372 11.00000 0.03666 0.05179 = 0.03698 -0.01633 0.00496 -0.01316 AFIX 137 H56A 2 0.549429 0.667963 0.716677 11.00000 -1.50000 H56B 2 0.572247 0.640165 0.656680 11.00000 -1.50000 H56C 2 0.709231 0.627064 0.701979 11.00000 -1.50000 AFIX 0 C1T 1 0.019768 0.798923 0.712671 11.00000 0.03897 0.04090 = 0.04875 -0.00300 -0.00375 0.00909 C2T 1 0.018767 0.779837 0.659191 11.00000 0.04766 0.03789 = 0.04448 -0.00240 -0.00483 0.00071 AFIX 43 H2T 2 -0.051669 0.746033 0.648645 11.00000 -1.20000 AFIX 0 C3T 1 0.116763 0.808231 0.620444 11.00000 0.05829 0.05017 = 0.04868 0.00508 -0.00114 0.01463 AFIX 43 H3T 2 0.118306 0.792613 0.584264 11.00000 -1.20000 AFIX 0 C4T 1 0.213245 0.859999 0.635017 11.00000 0.03764 0.06311 = 0.07168 0.02119 0.00422 0.00268 AFIX 43 H4T 2 0.283172 0.879533 0.609019 11.00000 -1.20000 AFIX 0 C5T 1 0.206818 0.882585 0.686963 11.00000 0.03537 0.06217 = 0.07845 0.00765 -0.02060 -0.00936 AFIX 43 H5T 2 0.267483 0.919507 0.696419 11.00000 -1.20000 AFIX 0 C6T 1 0.111796 0.851889 0.726379 11.00000 0.04572 0.05531 = 0.04827 -0.00841 -0.00779 0.00150 AFIX 43 H6T 2 0.110386 0.867393 0.762596 11.00000 -1.20000 AFIX 0 C7T 1 -0.081744 0.763766 0.753936 11.00000 0.08383 0.04527 = 0.06328 0.00455 0.03113 0.01841 AFIX 137 H7T1 2 -0.075566 0.785768 0.788934 11.00000 -1.50000 H7T2 2 -0.039321 0.720477 0.757952 11.00000 -1.50000 H7T3 2 -0.196483 0.762148 0.741809 11.00000 -1.50000 AFIX 0 HKLF 4 REM V19228 in P2(1)2(1)2(1) REM wR2 = 0.084745, GooF = S = 1.03711, Restrained GooF = 1.13094 for all data REM R1 = 0.032643 for 8079 Fo > 4sig(Fo) and 0.034914 for all 8503 data REM 580 parameters refined using 272 restraints END WGHT 0.0418 1.1840 REM Instructions for potential hydrogen bonds HTAB N2 S1_$1 HTAB N2 O3_$1 HTAB C51 O1 HTAB C52 N3 HTAB C53 F6A REM Highest difference peak 0.487, deepest hole -0.219, 1-sigma level 0.044 Q1 1 -0.1402 0.7629 0.6881 11.00000 0.05 0.49 Q2 1 0.1166 0.8213 0.6870 11.00000 0.05 0.42 Q3 1 0.3984 0.5598 0.6530 11.00000 0.05 0.40 Q4 1 0.1272 0.8038 0.7417 11.00000 0.05 0.39 Q5 1 0.0234 0.7838 0.7714 11.00000 0.05 0.33 Q6 1 0.7795 0.4221 0.6165 11.00000 0.05 0.26 Q7 1 0.5255 0.6596 0.6787 11.00000 0.05 0.24 Q8 1 0.3478 0.4785 0.6866 11.00000 0.05 0.24 Q9 1 0.2579 0.8414 0.6626 11.00000 0.05 0.22 Q10 1 0.3631 0.5240 0.6182 11.00000 0.05 0.22 Q11 1 -0.0345 0.8163 0.6684 11.00000 0.05 0.22 Q12 1 0.5067 0.5885 0.5470 11.00000 0.05 0.20 Q13 1 0.9808 0.2760 0.4733 11.00000 0.05 0.19 Q14 1 0.5041 0.2232 0.6386 11.00000 0.05 0.19 Q15 1 0.4954 0.5426 0.6908 11.00000 0.05 0.18 Q16 1 0.7292 0.3800 0.6111 11.00000 0.05 0.18 Q17 1 0.5272 0.4643 0.5394 11.00000 0.05 0.18 Q18 1 0.1206 0.5466 0.4255 11.00000 0.05 0.17 Q19 1 0.3619 0.4428 0.7502 11.00000 0.05 0.17 Q20 1 0.2140 0.9432 0.6660 11.00000 0.05 0.17 ; _shelx_res_checksum 43778 loop_ _space_group_symop_operation_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' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.39818(5) 0.52200(2) 0.66138(2) 0.01916(11) Uani 1 1 d . . . . . O1 O 0.3320(2) 0.55369(9) 0.59315(7) 0.0204(4) Uani 1 1 d . . . . . C1 C 0.4361(3) 0.55950(11) 0.54708(10) 0.0187(5) Uani 1 1 d . . . . . C11 C 0.5277(3) 0.62342(12) 0.54998(11) 0.0222(5) Uani 1 1 d . . . . . C12 C 0.6978(4) 0.63025(13) 0.54760(11) 0.0264(6) Uani 1 1 d . . . . . H12 H 0.765119 0.593602 0.544146 0.032 Uiso 1 1 calc R U . . . C13 C 0.7711(4) 0.68996(15) 0.55018(13) 0.0350(6) Uani 1 1 d . . . . . H13 H 0.887455 0.693689 0.548192 0.042 Uiso 1 1 calc R U . . . C14 C 0.6751(5) 0.74393(15) 0.55565(15) 0.0401(8) Uani 1 1 d . . . . . H14 H 0.725075 0.784649 0.557497 0.048 Uiso 1 1 calc R U . . . C15 C 0.5070(5) 0.73799(14) 0.55838(15) 0.0399(8) Uani 1 1 d . . . . . H15 H 0.440589 0.774760 0.562559 0.048 Uiso 1 1 calc R U . . . C16 C 0.4334(4) 0.67846(14) 0.55507(13) 0.0330(6) Uani 1 1 d . . . . . H16 H 0.316933 0.675241 0.556304 0.040 Uiso 1 1 calc R U . . . C21 C 0.3311(3) 0.55954(12) 0.49555(10) 0.0213(5) Uani 1 1 d . . . . . C22 C 0.1630(3) 0.54728(14) 0.49806(11) 0.0278(6) Uani 1 1 d . . . . . H22 H 0.112550 0.538417 0.532024 0.033 Uiso 1 1 calc R U . . . C23 C 0.0686(4) 0.54799(17) 0.45092(12) 0.0362(7) Uani 1 1 d . . . . . H23 H -0.046124 0.539675 0.452954 0.043 Uiso 1 1 calc R U . . . C24 C 0.1404(4) 0.56075(16) 0.40091(12) 0.0355(7) Uani 1 1 d . . . . . H24 H 0.075347 0.561276 0.368875 0.043 Uiso 1 1 calc R U . . . C25 C 0.3083(4) 0.57273(14) 0.39814(12) 0.0306(6) Uani 1 1 d . . . . . H25 H 0.358842 0.581302 0.364136 0.037 Uiso 1 1 calc R U . . . C26 C 0.4019(4) 0.57211(12) 0.44528(11) 0.0249(5) Uani 1 1 d . . . . . H26 H 0.516578 0.580446 0.443157 0.030 Uiso 1 1 calc R U . . . C2 C 0.5544(3) 0.50154(11) 0.55000(9) 0.0175(5) Uani 1 1 d . . . . . H2 H 0.657122 0.511005 0.529173 0.021 Uiso 1 1 calc R U . . . N1 N 0.5932(3) 0.49689(10) 0.60876(7) 0.0174(4) Uani 1 1 d . . . . . S1 S 0.76720(7) 0.47333(3) 0.62748(2) 0.01832(13) Uani 1 1 d . . . . . O2 O 0.7737(2) 0.47593(10) 0.68608(7) 0.0256(4) Uani 1 1 d . . . . . O3 O 0.9016(2) 0.50292(8) 0.59809(7) 0.0229(4) Uani 1 1 d . . . . . C41 C 0.7876(3) 0.39075(12) 0.61145(10) 0.0200(5) Uani 1 1 d . . . . . C42 C 0.9063(3) 0.37056(12) 0.57486(10) 0.0208(5) Uani 1 1 d . . . . . H42 H 0.974751 0.400423 0.556815 0.025 Uiso 1 1 calc R U . . . C43 C 0.9235(3) 0.30623(13) 0.56508(11) 0.0250(5) Uani 1 1 d D . . . . C47 C 1.0565(4) 0.28452(15) 0.52664(14) 0.0373(7) Uani 1 1 d D . . . . F1 F 1.1203(13) 0.3271(2) 0.4976(5) 0.069(4) Uani 0.56(2) 1 d D . P A 1 F2 F 1.0199(13) 0.2337(4) 0.4999(5) 0.062(3) Uani 0.56(2) 1 d D . P A 1 F3 F 1.1885(9) 0.2621(6) 0.5581(3) 0.073(3) Uani 0.56(2) 1 d D . P A 1 F1A F 1.030(2) 0.3162(7) 0.4768(4) 0.079(4) Uani 0.44(2) 1 d D . P A 2 F2A F 1.049(2) 0.2272(4) 0.5121(7) 0.089(5) Uani 0.44(2) 1 d D . P A 2 F3A F 1.1990(8) 0.3022(8) 0.5386(6) 0.081(6) Uani 0.44(2) 1 d D . P A 2 C44 C 0.8254(4) 0.26187(13) 0.59083(12) 0.0292(6) Uani 1 1 d . . . . . H44 H 0.839031 0.217840 0.583814 0.035 Uiso 1 1 calc R U . . . C45 C 0.7074(4) 0.28277(14) 0.62695(13) 0.0309(6) Uani 1 1 d D . . . . C48 C 0.6016(5) 0.23509(15) 0.65668(16) 0.0468(8) Uani 1 1 d D . . . . F4 F 0.5810(17) 0.1835(6) 0.6291(6) 0.064(4) Uani 0.52(3) 1 d D . P B 1 F5 F 0.629(4) 0.2320(13) 0.7068(4) 0.155(9) Uani 0.52(3) 1 d D . P B 1 F6 F 0.4407(16) 0.2551(8) 0.6530(13) 0.132(7) Uani 0.52(3) 1 d D . P B 1 F4A F 0.5900(15) 0.1795(6) 0.6321(6) 0.050(3) Uani 0.48(3) 1 d D . P B 2 F5A F 0.6927(11) 0.2120(4) 0.7010(3) 0.048(3) Uani 0.48(3) 1 d D . P B 2 F6A F 0.4690(19) 0.2558(9) 0.6759(7) 0.086(4) Uani 0.48(3) 1 d D . P B 2 C46 C 0.6866(3) 0.34734(13) 0.63772(12) 0.0267(6) Uani 1 1 d . . . . . H46 H 0.604859 0.361330 0.662557 0.032 Uiso 1 1 calc R U . . . C3 C 0.4759(3) 0.43954(12) 0.52838(10) 0.0198(5) Uani 1 1 d . . . . . H3A H 0.513465 0.403662 0.551187 0.024 Uiso 1 1 calc R U . . . H3B H 0.354916 0.442632 0.532166 0.024 Uiso 1 1 calc R U . . . C31 C 0.5170(4) 0.42516(12) 0.46948(10) 0.0226(5) Uani 1 1 d . . . . . C32 C 0.3951(4) 0.41564(13) 0.43103(11) 0.0284(6) Uani 1 1 d . . . . . H32 H 0.282963 0.419600 0.441293 0.034 Uiso 1 1 calc R U . . . C33 C 0.4342(5) 0.40040(14) 0.37776(12) 0.0382(8) Uani 1 1 d . . . . . H33 H 0.349032 0.394098 0.351913 0.046 Uiso 1 1 calc R U . . . C34 C 0.5979(5) 0.39435(15) 0.36211(11) 0.0416(8) Uani 1 1 d . . . . . H34 H 0.624879 0.383468 0.325754 0.050 Uiso 1 1 calc R U . . . C35 C 0.7212(5) 0.40431(17) 0.39999(13) 0.0401(8) Uani 1 1 d . . . . . H35 H 0.833333 0.400709 0.389576 0.048 Uiso 1 1 calc R U . . . C36 C 0.6806(4) 0.41960(14) 0.45329(11) 0.0301(6) Uani 1 1 d . . . . . H36 H 0.765832 0.426354 0.479057 0.036 Uiso 1 1 calc R U . . . N2 N 0.1473(3) 0.55665(12) 0.68177(10) 0.0257(5) Uani 1 1 d D . . . . H2N H 0.084(4) 0.5355(15) 0.6577(12) 0.031 Uiso 1 1 d D U . . . C51 C 0.1227(4) 0.62462(16) 0.67142(17) 0.0449(8) Uani 1 1 d . . . . . H51A H 0.008638 0.636102 0.679795 0.067 Uiso 1 1 calc R U . . . H51B H 0.145567 0.633794 0.633155 0.067 Uiso 1 1 calc R U . . . H51C H 0.197360 0.649333 0.694415 0.067 Uiso 1 1 calc R U . . . C52 C 0.0947(4) 0.54016(19) 0.73758(11) 0.0406(8) Uani 1 1 d . . . . . H52A H 0.166887 0.561257 0.763845 0.061 Uiso 1 1 calc R U . . . H52B H 0.101303 0.494083 0.742586 0.061 Uiso 1 1 calc R U . . . H52C H -0.018923 0.554230 0.743241 0.061 Uiso 1 1 calc R U . . . N3 N 0.3408(3) 0.43955(12) 0.68726(9) 0.0245(5) Uani 1 1 d . . . . . C53 C 0.3762(4) 0.40566(16) 0.73754(12) 0.0345(7) Uani 1 1 d . . . . . H53A H 0.280196 0.407732 0.761544 0.052 Uiso 1 1 calc R U . . . H53B H 0.470873 0.425282 0.755571 0.052 Uiso 1 1 calc R U . . . H53C H 0.401313 0.361194 0.729307 0.052 Uiso 1 1 calc R U . . . C54 C 0.2244(4) 0.40567(14) 0.65390(12) 0.0302(6) Uani 1 1 d . . . . . H54A H 0.269825 0.364102 0.644217 0.045 Uiso 1 1 calc R U . . . H54B H 0.202645 0.430033 0.620768 0.045 Uiso 1 1 calc R U . . . H54C H 0.121497 0.399858 0.674043 0.045 Uiso 1 1 calc R U . . . N4 N 0.5062(3) 0.57494(13) 0.71124(10) 0.0292(5) Uani 1 1 d . . . . . C55 C 0.5366(4) 0.55875(18) 0.76811(12) 0.0398(7) Uani 1 1 d . . . . . H55A H 0.651834 0.546202 0.772638 0.060 Uiso 1 1 calc R U . . . H55B H 0.464908 0.523484 0.778779 0.060 Uiso 1 1 calc R U . . . H55C H 0.513300 0.595715 0.791009 0.060 Uiso 1 1 calc R U . . . C56 C 0.5911(5) 0.63211(17) 0.69537(13) 0.0418(8) Uani 1 1 d . . . . . H56A H 0.549429 0.667963 0.716677 0.063 Uiso 1 1 calc R U . . . H56B H 0.572247 0.640165 0.656680 0.063 Uiso 1 1 calc R U . . . H56C H 0.709231 0.627064 0.701979 0.063 Uiso 1 1 calc R U . . . C1T C 0.0198(5) 0.79892(17) 0.71267(15) 0.0429(8) Uani 1 1 d . . . . . C2T C 0.0188(5) 0.77984(16) 0.65919(15) 0.0433(7) Uani 1 1 d . . . . . H2T H -0.051669 0.746033 0.648645 0.052 Uiso 1 1 calc R U . . . C3T C 0.1168(6) 0.80823(19) 0.62044(17) 0.0524(9) Uani 1 1 d . . . . . H3T H 0.118306 0.792613 0.584264 0.063 Uiso 1 1 calc R U . . . C4T C 0.2132(5) 0.8600(2) 0.6350(2) 0.0575(11) Uani 1 1 d . . . . . H4T H 0.283172 0.879533 0.609019 0.069 Uiso 1 1 calc R U . . . C5T C 0.2068(5) 0.8826(2) 0.6870(2) 0.0587(11) Uani 1 1 d . . . . . H5T H 0.267483 0.919507 0.696419 0.070 Uiso 1 1 calc R U . . . C6T C 0.1118(5) 0.85189(19) 0.72638(16) 0.0498(9) Uani 1 1 d . . . . . H6T H 0.110386 0.867393 0.762596 0.060 Uiso 1 1 calc R U . . . C7T C -0.0817(7) 0.7638(2) 0.75394(18) 0.0641(12) Uani 1 1 d . . . . . H7T1 H -0.075566 0.785768 0.788934 0.096 Uiso 1 1 calc R U . . . H7T2 H -0.039321 0.720477 0.757952 0.096 Uiso 1 1 calc R U . . . H7T3 H -0.196483 0.762148 0.741809 0.096 Uiso 1 1 calc R U . . . 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 0.01429(19) 0.0279(2) 0.01535(19) -0.00494(17) 0.00018(16) -0.00058(18) O1 0.0159(8) 0.0260(9) 0.0192(8) -0.0022(7) 0.0023(7) 0.0011(7) C1 0.0165(11) 0.0205(11) 0.0193(11) -0.0008(9) 0.0003(9) 0.0002(9) C11 0.0248(13) 0.0202(12) 0.0218(12) -0.0013(10) -0.0003(10) -0.0011(10) C12 0.0265(14) 0.0241(12) 0.0284(13) -0.0005(10) -0.0009(11) -0.0031(11) C13 0.0303(15) 0.0343(15) 0.0403(16) 0.0013(13) -0.0021(13) -0.0090(13) C14 0.0490(19) 0.0235(14) 0.0477(19) -0.0015(13) -0.0031(16) -0.0106(13) C15 0.0470(19) 0.0217(13) 0.051(2) -0.0022(13) 0.0029(16) 0.0011(13) C16 0.0301(16) 0.0265(13) 0.0425(16) -0.0025(12) 0.0020(13) 0.0028(12) C21 0.0222(12) 0.0213(12) 0.0204(12) 0.0011(9) -0.0011(10) 0.0009(10) C22 0.0215(12) 0.0391(15) 0.0228(12) 0.0026(11) -0.0019(10) -0.0003(11) C23 0.0231(14) 0.0552(19) 0.0304(14) 0.0016(13) -0.0066(12) -0.0037(13) C24 0.0345(16) 0.0476(18) 0.0245(13) 0.0036(12) -0.0094(12) 0.0014(13) C25 0.0357(15) 0.0344(14) 0.0216(13) 0.0061(11) 0.0000(12) -0.0004(12) C26 0.0241(12) 0.0255(12) 0.0251(12) 0.0021(10) 0.0002(11) 0.0000(11) C2 0.0181(11) 0.0194(10) 0.0152(11) -0.0017(9) 0.0017(9) -0.0024(9) N1 0.0141(9) 0.0223(9) 0.0157(9) -0.0020(7) 0.0005(8) 0.0001(8) S1 0.0144(3) 0.0215(3) 0.0191(3) -0.0023(2) -0.0009(2) -0.0006(2) O2 0.0246(9) 0.0319(9) 0.0202(8) -0.0033(8) -0.0048(7) 0.0032(9) O3 0.0151(8) 0.0232(8) 0.0304(9) -0.0019(7) 0.0015(8) -0.0021(7) C41 0.0181(11) 0.0224(11) 0.0194(11) 0.0008(9) -0.0021(9) -0.0005(10) C42 0.0163(11) 0.0251(12) 0.0210(11) 0.0019(9) -0.0015(10) -0.0006(10) C43 0.0243(14) 0.0245(12) 0.0264(12) -0.0023(10) 0.0012(11) 0.0016(10) C47 0.0366(16) 0.0299(14) 0.0454(17) -0.0094(13) 0.0140(14) -0.0019(13) F1 0.084(7) 0.0247(19) 0.097(7) 0.000(2) 0.070(6) -0.001(3) F2 0.046(3) 0.066(5) 0.073(4) -0.051(4) 0.025(3) -0.018(3) F3 0.036(3) 0.112(7) 0.071(4) -0.016(4) 0.003(2) 0.034(3) F1A 0.093(8) 0.093(6) 0.049(4) 0.025(4) 0.043(4) 0.049(6) F2A 0.119(11) 0.014(3) 0.135(11) -0.005(4) 0.089(8) 0.001(4) F3A 0.032(3) 0.120(11) 0.092(8) -0.063(9) 0.020(4) -0.011(4) C44 0.0299(14) 0.0233(13) 0.0346(15) 0.0020(11) 0.0006(12) 0.0012(11) C45 0.0307(15) 0.0268(13) 0.0354(15) 0.0049(12) 0.0061(12) -0.0035(12) C48 0.0487(19) 0.0315(15) 0.060(2) 0.0052(15) 0.0253(19) -0.0057(15) F4 0.076(7) 0.037(5) 0.079(6) 0.007(4) -0.011(5) -0.034(4) F5 0.242(19) 0.174(15) 0.049(4) 0.017(6) 0.021(8) -0.157(14) F6 0.061(5) 0.039(4) 0.29(2) 0.043(10) 0.095(8) 0.004(4) F4A 0.051(5) 0.031(4) 0.068(6) 0.000(4) 0.037(5) -0.007(4) F5A 0.067(4) 0.047(4) 0.031(3) 0.020(2) 0.002(2) -0.017(3) F6A 0.076(6) 0.043(4) 0.138(9) 0.030(5) 0.081(6) 0.012(5) C46 0.0232(13) 0.0283(13) 0.0286(13) 0.0024(11) 0.0066(11) -0.0011(11) C3 0.0206(12) 0.0206(11) 0.0182(11) 0.0002(9) 0.0006(9) -0.0032(10) C31 0.0325(14) 0.0163(11) 0.0190(12) 0.0000(9) -0.0007(10) -0.0009(10) C32 0.0379(15) 0.0256(12) 0.0216(12) 0.0023(10) -0.0039(12) -0.0106(12) C33 0.063(2) 0.0324(14) 0.0189(13) 0.0012(11) -0.0079(14) -0.0174(15) C34 0.073(2) 0.0366(16) 0.0153(12) -0.0032(11) 0.0044(15) -0.0006(17) C35 0.050(2) 0.0466(18) 0.0239(14) -0.0015(13) 0.0099(14) 0.0133(16) C36 0.0367(15) 0.0340(14) 0.0196(13) -0.0019(11) -0.0005(11) 0.0091(12) N2 0.0168(11) 0.0335(12) 0.0268(11) -0.0097(9) 0.0026(9) -0.0007(9) C51 0.0289(16) 0.0374(16) 0.068(2) -0.0131(16) 0.0168(16) 0.0061(13) C52 0.0233(14) 0.076(2) 0.0226(13) -0.0139(14) 0.0053(12) 0.0051(15) N3 0.0197(10) 0.0343(12) 0.0196(10) 0.0036(9) 0.0016(8) -0.0022(9) C53 0.0334(16) 0.0465(17) 0.0235(13) 0.0062(12) -0.0020(12) -0.0035(14) C54 0.0298(14) 0.0355(14) 0.0254(13) 0.0034(11) -0.0028(12) -0.0036(12) N4 0.0200(11) 0.0427(14) 0.0248(12) -0.0139(10) -0.0003(9) -0.0014(10) C55 0.0379(17) 0.055(2) 0.0269(15) -0.0144(14) -0.0088(13) 0.0052(15) C56 0.0367(17) 0.0518(19) 0.0370(16) -0.0163(14) 0.0050(14) -0.0132(16) C1T 0.0390(18) 0.0409(17) 0.049(2) -0.0030(15) -0.0038(15) 0.0091(15) C2T 0.0477(19) 0.0379(16) 0.0445(18) -0.0024(15) -0.0048(16) 0.0007(15) C3T 0.058(2) 0.050(2) 0.049(2) 0.0051(17) -0.0011(19) 0.0146(19) C4T 0.038(2) 0.063(2) 0.072(3) 0.021(2) 0.0042(19) 0.0027(18) C5T 0.035(2) 0.062(2) 0.078(3) 0.008(2) -0.021(2) -0.0094(18) C6T 0.046(2) 0.055(2) 0.048(2) -0.0084(17) -0.0078(18) 0.0015(18) C7T 0.084(3) 0.045(2) 0.063(2) 0.0046(18) 0.031(2) 0.018(2) loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 N4 Ti1 O1 120.39(10) . . ? N4 Ti1 N3 115.90(11) . . ? O1 Ti1 N3 123.36(9) . . ? N4 Ti1 N1 101.47(9) . . ? O1 Ti1 N1 75.91(8) . . ? N3 Ti1 N1 99.22(9) . . ? N4 Ti1 N2 94.95(10) . . ? O1 Ti1 N2 79.82(8) . . ? N3 Ti1 N2 89.95(10) . . ? N1 Ti1 N2 155.24(9) . . ? C1 O1 Ti1 124.88(15) . . ? O1 C1 C21 109.31(19) . . ? O1 C1 C11 109.05(19) . . ? C21 C1 C11 107.9(2) . . ? O1 C1 C2 105.29(19) . . ? C21 C1 C2 112.6(2) . . ? C11 C1 C2 112.6(2) . . ? C12 C11 C16 117.6(3) . . ? C12 C11 C1 124.7(2) . . ? C16 C11 C1 117.7(2) . . ? C11 C12 C13 121.1(3) . . ? C11 C12 H12 119.5 . . ? C13 C12 H12 119.5 . . ? C14 C13 C12 120.3(3) . . ? C14 C13 H13 119.9 . . ? C12 C13 H13 119.9 . . ? C15 C14 C13 119.4(3) . . ? C15 C14 H14 120.3 . . ? C13 C14 H14 120.3 . . ? C14 C15 C16 120.5(3) . . ? C14 C15 H15 119.8 . . ? C16 C15 H15 119.8 . . ? C15 C16 C11 121.2(3) . . ? C15 C16 H16 119.4 . . ? C11 C16 H16 119.4 . . ? C26 C21 C22 118.7(3) . . ? C26 C21 C1 120.6(2) . . ? C22 C21 C1 120.7(2) . . ? C23 C22 C21 120.1(3) . . ? C23 C22 H22 119.9 . . ? C21 C22 H22 119.9 . . ? C24 C23 C22 120.7(3) . . ? C24 C23 H23 119.7 . . ? C22 C23 H23 119.7 . . ? C23 C24 C25 119.4(3) . . ? C23 C24 H24 120.3 . . ? C25 C24 H24 120.3 . . ? C26 C25 C24 119.7(3) . . ? C26 C25 H25 120.2 . . ? C24 C25 H25 120.2 . . ? C25 C26 C21 121.3(3) . . ? C25 C26 H26 119.3 . . ? C21 C26 H26 119.3 . . ? N1 C2 C3 111.54(19) . . ? N1 C2 C1 103.19(18) . . ? C3 C2 C1 113.0(2) . . ? N1 C2 H2 109.6 . . ? C3 C2 H2 109.6 . . ? C1 C2 H2 109.6 . . ? C2 N1 S1 119.94(16) . . ? C2 N1 Ti1 114.94(15) . . ? S1 N1 Ti1 125.11(11) . . ? O2 S1 O3 117.04(11) . . ? O2 S1 N1 108.33(11) . . ? O3 S1 N1 113.34(11) . . ? O2 S1 C41 104.68(12) . . ? O3 S1 C41 103.74(11) . . ? N1 S1 C41 109.03(11) . . ? C42 C41 C46 120.8(2) . . ? C42 C41 S1 120.3(2) . . ? C46 C41 S1 118.8(2) . . ? C43 C42 C41 118.9(2) . . ? C43 C42 H42 120.5 . . ? C41 C42 H42 120.5 . . ? C44 C43 C42 121.6(3) . . ? C44 C43 C47 119.8(2) . . ? C42 C43 C47 118.6(3) . . ? F3A C47 F2A 113.5(9) . . ? F1 C47 F2 113.3(7) . . ? F1 C47 F3 103.7(5) . . ? F2 C47 F3 100.3(6) . . ? F3A C47 F1A 102.0(7) . . ? F2A C47 F1A 101.4(9) . . ? F3A C47 C43 115.2(4) . . ? F1 C47 C43 115.9(3) . . ? F2A C47 C43 115.6(8) . . ? F2 C47 C43 114.0(6) . . ? F3 C47 C43 107.6(4) . . ? F1A C47 C43 106.9(4) . . ? C45 C44 C43 118.7(3) . . ? C45 C44 H44 120.6 . . ? C43 C44 H44 120.6 . . ? C44 C45 C46 121.1(3) . . ? C44 C45 C48 119.7(3) . . ? C46 C45 C48 119.1(3) . . ? F5 C48 F4 119.7(15) . . ? F6A C48 F4A 114.8(11) . . ? F5 C48 F6 104.3(11) . . ? F4 C48 F6 95.7(13) . . ? F6A C48 F5A 106.2(9) . . ? F4A C48 F5A 95.0(9) . . ? F5 C48 C45 114.3(6) . . ? F6A C48 C45 116.1(9) . . ? F4 C48 C45 112.2(7) . . ? F4A C48 C45 114.0(6) . . ? F6 C48 C45 107.7(8) . . ? F5A C48 C45 107.8(5) . . ? C41 C46 C45 118.8(3) . . ? C41 C46 H46 120.6 . . ? C45 C46 H46 120.6 . . ? C31 C3 C2 113.9(2) . . ? C31 C3 H3A 108.8 . . ? C2 C3 H3A 108.8 . . ? C31 C3 H3B 108.8 . . ? C2 C3 H3B 108.8 . . ? H3A C3 H3B 107.7 . . ? C32 C31 C36 118.4(3) . . ? C32 C31 C3 121.6(3) . . ? C36 C31 C3 120.0(2) . . ? C31 C32 C33 121.1(3) . . ? C31 C32 H32 119.5 . . ? C33 C32 H32 119.5 . . ? C32 C33 C34 120.1(3) . . ? C32 C33 H33 119.9 . . ? C34 C33 H33 119.9 . . ? C35 C34 C33 119.4(3) . . ? C35 C34 H34 120.3 . . ? C33 C34 H34 120.3 . . ? C34 C35 C36 119.9(3) . . ? C34 C35 H35 120.0 . . ? C36 C35 H35 120.0 . . ? C35 C36 C31 121.0(3) . . ? C35 C36 H36 119.5 . . ? C31 C36 H36 119.5 . . ? C51 N2 C52 110.5(3) . . ? C51 N2 Ti1 113.97(18) . . ? C52 N2 Ti1 113.42(19) . . ? C51 N2 H2N 107(2) . . ? C52 N2 H2N 109(2) . . ? Ti1 N2 H2N 102(2) . . ? N2 C51 H51A 109.5 . . ? N2 C51 H51B 109.5 . . ? H51A C51 H51B 109.5 . . ? N2 C51 H51C 109.5 . . ? H51A C51 H51C 109.5 . . ? H51B C51 H51C 109.5 . . ? N2 C52 H52A 109.5 . . ? N2 C52 H52B 109.5 . . ? H52A C52 H52B 109.5 . . ? N2 C52 H52C 109.5 . . ? H52A C52 H52C 109.5 . . ? H52B C52 H52C 109.5 . . ? C54 N3 C53 111.8(2) . . ? C54 N3 Ti1 114.88(18) . . ? C53 N3 Ti1 132.9(2) . . ? N3 C53 H53A 109.5 . . ? N3 C53 H53B 109.5 . . ? H53A C53 H53B 109.5 . . ? N3 C53 H53C 109.5 . . ? H53A C53 H53C 109.5 . . ? H53B C53 H53C 109.5 . . ? N3 C54 H54A 109.5 . . ? N3 C54 H54B 109.5 . . ? H54A C54 H54B 109.5 . . ? N3 C54 H54C 109.5 . . ? H54A C54 H54C 109.5 . . ? H54B C54 H54C 109.5 . . ? C56 N4 C55 111.9(3) . . ? C56 N4 Ti1 122.9(2) . . ? C55 N4 Ti1 124.5(2) . . ? N4 C55 H55A 109.5 . . ? N4 C55 H55B 109.5 . . ? H55A C55 H55B 109.5 . . ? N4 C55 H55C 109.5 . . ? H55A C55 H55C 109.5 . . ? H55B C55 H55C 109.5 . . ? N4 C56 H56A 109.5 . . ? N4 C56 H56B 109.5 . . ? H56A C56 H56B 109.5 . . ? N4 C56 H56C 109.5 . . ? H56A C56 H56C 109.5 . . ? H56B C56 H56C 109.5 . . ? C2T C1T C6T 118.1(4) . . ? C2T C1T C7T 120.0(4) . . ? C6T C1T C7T 121.9(4) . . ? C1T C2T C3T 122.1(4) . . ? C1T C2T H2T 118.9 . . ? C3T C2T H2T 118.9 . . ? C2T C3T C4T 119.2(4) . . ? C2T C3T H3T 120.4 . . ? C4T C3T H3T 120.4 . . ? C5T C4T C3T 119.6(4) . . ? C5T C4T H4T 120.2 . . ? C3T C4T H4T 120.2 . . ? C4T C5T C6T 120.7(4) . . ? C4T C5T H5T 119.7 . . ? C6T C5T H5T 119.7 . . ? C1T C6T C5T 120.1(4) . . ? C1T C6T H6T 120.0 . . ? C5T C6T H6T 120.0 . . ? C1T C7T H7T1 109.5 . . ? C1T C7T H7T2 109.5 . . ? H7T1 C7T H7T2 109.5 . . ? C1T C7T H7T3 109.5 . . ? H7T1 C7T H7T3 109.5 . . ? H7T2 C7T H7T3 109.5 . . ? 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 N4 1.877(2) . ? Ti1 O1 1.8866(18) . ? Ti1 N3 1.908(2) . ? Ti1 N1 2.115(2) . ? Ti1 N2 2.224(2) . ? O1 C1 1.421(3) . ? C1 C21 1.529(3) . ? C1 C11 1.541(3) . ? C1 C2 1.556(3) . ? C11 C12 1.392(4) . ? C11 C16 1.396(4) . ? C12 C13 1.393(4) . ? C12 H12 0.9500 . ? C13 C14 1.386(5) . ? C13 H13 0.9500 . ? C14 C15 1.374(5) . ? C14 H14 0.9500 . ? C15 C16 1.392(4) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C21 C26 1.391(4) . ? C21 C22 1.393(4) . ? C22 C23 1.392(4) . ? C22 H22 0.9500 . ? C23 C24 1.390(4) . ? C23 H23 0.9500 . ? C24 C25 1.390(4) . ? C24 H24 0.9500 . ? C25 C26 1.388(4) . ? C25 H25 0.9500 . ? C26 H26 0.9500 . ? C2 N1 1.484(3) . ? C2 C3 1.548(3) . ? C2 H2 1.0000 . ? N1 S1 1.568(2) . ? S1 O2 1.4454(18) . ? S1 O3 1.4511(19) . ? S1 C41 1.792(3) . ? C41 C42 1.387(4) . ? C41 C46 1.389(4) . ? C42 C43 1.384(4) . ? C42 H42 0.9500 . ? C43 C44 1.382(4) . ? C43 C47 1.508(4) . ? C47 F3A 1.252(7) . ? C47 F1 1.258(6) . ? C47 F2A 1.261(10) . ? C47 F2 1.291(7) . ? C47 F3 1.405(6) . ? C47 F1A 1.415(7) . ? C44 C45 1.381(4) . ? C44 H44 0.9500 . ? C45 C46 1.396(4) . ? C45 C48 1.511(4) . ? C48 F5 1.255(10) . ? C48 F6A 1.256(11) . ? C48 F4 1.293(10) . ? C48 F4A 1.323(10) . ? C48 F6 1.378(13) . ? C48 F5A 1.405(8) . ? C46 H46 0.9500 . ? C3 C31 1.519(3) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C31 C32 1.385(4) . ? C31 C36 1.393(4) . ? C32 C33 1.388(4) . ? C32 H32 0.9500 . ? C33 C34 1.391(6) . ? C33 H33 0.9500 . ? C34 C35 1.385(5) . ? C34 H34 0.9500 . ? C35 C36 1.392(4) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? N2 C51 1.468(4) . ? N2 C52 1.481(4) . ? N2 H2N 0.90(2) . ? C51 H51A 0.9800 . ? C51 H51B 0.9800 . ? C51 H51C 0.9800 . ? C52 H52A 0.9800 . ? C52 H52B 0.9800 . ? C52 H52C 0.9800 . ? N3 C54 1.442(4) . ? N3 C53 1.458(4) . ? C53 H53A 0.9800 . ? C53 H53B 0.9800 . ? C53 H53C 0.9800 . ? C54 H54A 0.9800 . ? C54 H54B 0.9800 . ? C54 H54C 0.9800 . ? N4 C56 1.442(4) . ? N4 C55 1.463(4) . ? C55 H55A 0.9800 . ? C55 H55B 0.9800 . ? C55 H55C 0.9800 . ? C56 H56A 0.9800 . ? C56 H56B 0.9800 . ? C56 H56C 0.9800 . ? C1T C2T 1.377(5) . ? C1T C6T 1.385(6) . ? C1T C7T 1.504(6) . ? C2T C3T 1.380(6) . ? C2T H2T 0.9500 . ? C3T C4T 1.390(6) . ? C3T H3T 0.9500 . ? C4T C5T 1.366(7) . ? C4T H4T 0.9500 . ? C5T C6T 1.399(6) . ? C5T H5T 0.9500 . ? C6T H6T 0.9500 . ? C7T H7T1 0.9800 . ? C7T H7T2 0.9800 . ? C7T H7T3 0.9800 . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag N2 H2N S1 0.90(2) 2.98(3) 3.797(2) 151(3) 1_455 yes N2 H2N O3 0.90(2) 2.20(2) 3.086(3) 168(3) 1_455 yes C51 H51B O1 0.98 2.47 2.974(4) 111.4 . yes C52 H52B N3 0.98 2.64 3.167(4) 114.0 . yes 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 N4 Ti1 O1 C1 82.1(2) . . . . ? N3 Ti1 O1 C1 -104.92(19) . . . . ? N1 Ti1 O1 C1 -13.05(17) . . . . ? N2 Ti1 O1 C1 171.93(19) . . . . ? Ti1 O1 C1 C21 156.41(16) . . . . ? Ti1 O1 C1 C11 -85.8(2) . . . . ? Ti1 O1 C1 C2 35.3(2) . . . . ? O1 C1 C11 C12 125.3(3) . . . . ? C21 C1 C11 C12 -116.1(3) . . . . ? C2 C1 C11 C12 8.8(4) . . . . ? O1 C1 C11 C16 -55.1(3) . . . . ? C21 C1 C11 C16 63.6(3) . . . . ? C2 C1 C11 C16 -171.6(2) . . . . ? C16 C11 C12 C13 0.0(5) . . . . ? C1 C11 C12 C13 179.6(3) . . . . ? C11 C12 C13 C14 0.5(5) . . . . ? C12 C13 C14 C15 -0.1(5) . . . . ? C13 C14 C15 C16 -0.7(6) . . . . ? C14 C15 C16 C11 1.2(5) . . . . ? C12 C11 C16 C15 -0.8(5) . . . . ? C1 C11 C16 C15 179.5(3) . . . . ? O1 C1 C21 C26 172.5(2) . . . . ? C11 C1 C21 C26 54.0(3) . . . . ? C2 C1 C21 C26 -70.9(3) . . . . ? O1 C1 C21 C22 -7.2(3) . . . . ? C11 C1 C21 C22 -125.7(3) . . . . ? C2 C1 C21 C22 109.4(3) . . . . ? C26 C21 C22 C23 -0.3(4) . . . . ? C1 C21 C22 C23 179.4(3) . . . . ? C21 C22 C23 C24 0.1(5) . . . . ? C22 C23 C24 C25 0.2(5) . . . . ? C23 C24 C25 C26 -0.3(5) . . . . ? C24 C25 C26 C21 0.2(4) . . . . ? C22 C21 C26 C25 0.1(4) . . . . ? C1 C21 C26 C25 -179.6(2) . . . . ? O1 C1 C2 N1 -40.1(2) . . . . ? C21 C1 C2 N1 -159.1(2) . . . . ? C11 C1 C2 N1 78.6(2) . . . . ? O1 C1 C2 C3 80.5(2) . . . . ? C21 C1 C2 C3 -38.5(3) . . . . ? C11 C1 C2 C3 -160.8(2) . . . . ? C3 C2 N1 S1 91.6(2) . . . . ? C1 C2 N1 S1 -146.75(16) . . . . ? C3 C2 N1 Ti1 -87.1(2) . . . . ? C1 C2 N1 Ti1 34.5(2) . . . . ? C2 N1 S1 O2 177.64(18) . . . . ? Ti1 N1 S1 O2 -3.73(18) . . . . ? C2 N1 S1 O3 46.0(2) . . . . ? Ti1 N1 S1 O3 -135.37(13) . . . . ? C2 N1 S1 C41 -69.0(2) . . . . ? Ti1 N1 S1 C41 109.63(14) . . . . ? O2 S1 C41 C42 -127.4(2) . . . . ? O3 S1 C41 C42 -4.2(2) . . . . ? N1 S1 C41 C42 116.9(2) . . . . ? O2 S1 C41 C46 50.4(2) . . . . ? O3 S1 C41 C46 173.6(2) . . . . ? N1 S1 C41 C46 -65.4(2) . . . . ? C46 C41 C42 C43 -0.4(4) . . . . ? S1 C41 C42 C43 177.3(2) . . . . ? C41 C42 C43 C44 0.0(4) . . . . ? C41 C42 C43 C47 -178.0(3) . . . . ? C44 C43 C47 F3A -121.9(11) . . . . ? C42 C43 C47 F3A 56.2(11) . . . . ? C44 C43 C47 F1 167.8(8) . . . . ? C42 C43 C47 F1 -14.2(9) . . . . ? C44 C43 C47 F2A 13.6(12) . . . . ? C42 C43 C47 F2A -168.4(11) . . . . ? C44 C43 C47 F2 33.6(8) . . . . ? C42 C43 C47 F2 -148.3(7) . . . . ? C44 C43 C47 F3 -76.7(7) . . . . ? C42 C43 C47 F3 101.3(7) . . . . ? C44 C43 C47 F1A 125.6(10) . . . . ? C42 C43 C47 F1A -56.3(10) . . . . ? C42 C43 C44 C45 0.3(4) . . . . ? C47 C43 C44 C45 178.3(3) . . . . ? C43 C44 C45 C46 -0.2(5) . . . . ? C43 C44 C45 C48 -178.4(3) . . . . ? C44 C45 C48 F5 112(2) . . . . ? C46 C45 C48 F5 -67(2) . . . . ? C44 C45 C48 F6A -159.9(11) . . . . ? C46 C45 C48 F6A 21.8(12) . . . . ? C44 C45 C48 F4 -28.9(9) . . . . ? C46 C45 C48 F4 152.8(9) . . . . ? C44 C45 C48 F4A -23.0(9) . . . . ? C46 C45 C48 F4A 158.7(9) . . . . ? C44 C45 C48 F6 -133.0(14) . . . . ? C46 C45 C48 F6 48.8(14) . . . . ? C44 C45 C48 F5A 81.1(5) . . . . ? C46 C45 C48 F5A -97.2(5) . . . . ? C42 C41 C46 C45 0.5(4) . . . . ? S1 C41 C46 C45 -177.3(2) . . . . ? C44 C45 C46 C41 -0.2(5) . . . . ? C48 C45 C46 C41 178.1(3) . . . . ? N1 C2 C3 C31 -148.1(2) . . . . ? C1 C2 C3 C31 96.1(3) . . . . ? C2 C3 C31 C32 -124.4(3) . . . . ? C2 C3 C31 C36 57.3(3) . . . . ? C36 C31 C32 C33 0.5(4) . . . . ? C3 C31 C32 C33 -177.8(2) . . . . ? C31 C32 C33 C34 0.1(4) . . . . ? C32 C33 C34 C35 -0.7(5) . . . . ? C33 C34 C35 C36 0.7(5) . . . . ? C34 C35 C36 C31 0.0(5) . . . . ? C32 C31 C36 C35 -0.6(4) . . . . ? C3 C31 C36 C35 177.8(3) . . . . ? O1 Ti1 N4 C56 -21.3(3) . . . . ? N3 Ti1 N4 C56 165.3(2) . . . . ? N1 Ti1 N4 C56 59.0(3) . . . . ? N2 Ti1 N4 C56 -102.4(3) . . . . ? O1 Ti1 N4 C55 168.7(2) . . . . ? N3 Ti1 N4 C55 -4.7(3) . . . . ? N1 Ti1 N4 C55 -111.0(2) . . . . ? N2 Ti1 N4 C55 87.6(2) . . . . ? C6T C1T C2T C3T 5.7(6) . . . . ? C7T C1T C2T C3T -176.3(4) . . . . ? C1T C2T C3T C4T -3.5(6) . . . . ? C2T C3T C4T C5T -1.3(6) . . . . ? C3T C4T C5T C6T 3.8(6) . . . . ? C2T C1T C6T C5T -3.1(6) . . . . ? C7T C1T C6T C5T 178.9(4) . . . . ? C4T C5T C6T C1T -1.6(6) . . . . ?