# Supplementary Information (SI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2024

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Ti1d
_database_code_depnum_ccdc_archive 'CCDC 2377764'
loop_
_audit_author_name
_audit_author_address
'Marc Schmidtmann'
;Carl von Ossietzky Universitaet Oldenburg
Germany
;
_audit_update_record             
;
2024-08-15 deposited with the CCDC.	2024-09-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/3
_shelx_SHELXL_version_number     2019/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_structural     Ti(C15H19)(C24H28N3OS)
_chemical_formula_sum            'C39 H47 N3 O S Ti'
_chemical_formula_weight         653.75

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'
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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   12.0547(3)
_cell_length_b                   11.8933(3)
_cell_length_c                   22.4765(5)
_cell_angle_alpha                90
_cell_angle_beta                 101.8642(12)
_cell_angle_gamma                90
_cell_volume                     3153.62(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9817
_cell_measurement_theta_min      4.02
_cell_measurement_theta_max      74.46

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_F_000             1392
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.060
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.030
_exptl_absorpt_coefficient_mu    3.200
_shelx_estimated_absorpt_T_min   0.831
_shelx_estimated_absorpt_T_max   0.910
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9074
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'I\mS microfocus'
_diffrn_measurement_device_type  'Bruker Photon III CPAD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            54536
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         3.871
_diffrn_reflns_theta_max         74.469
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             6406
_reflns_number_gt                5846
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT V8.40B'
_computing_data_reduction        'Bruker SAINT V8.40B'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0450P)²+1.5500P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6406
_refine_ls_number_parameters     415
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0315
_refine_ls_wR_factor_ref         0.0847
_refine_ls_wR_factor_gt          0.0818
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.037
_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_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 0.43312(2) 0.27064(2) 0.20105(2) 0.01346(8) Uani 1 1 d . . . . .
S1 S 0.16057(3) 0.61272(3) 0.09507(2) 0.02391(10) Uani 1 1 d . . . . .
O1 O 0.54884(8) 0.32759(9) 0.16220(4) 0.0164(2) Uani 1 1 d . . . . .
N1 N 0.31649(10) 0.31827(10) 0.12586(5) 0.0158(2) Uani 1 1 d . . . . .
N2 N 0.29106(10) 0.43310(11) 0.11498(6) 0.0178(3) Uani 1 1 d . . . . .
H2 H 0.3443(18) 0.4817(19) 0.1168(10) 0.031(5) Uiso 1 1 d . . . . .
N3 N 0.10265(11) 0.39547(13) 0.09645(7) 0.0260(3) Uani 1 1 d . . . . .
H3 H 0.1264(18) 0.3259(19) 0.1056(9) 0.031(5) Uiso 1 1 d . . . . .
C1 C 0.46961(12) 0.45613(12) 0.24821(6) 0.0162(3) Uani 1 1 d . . . . .
C2 C 0.54145(13) 0.37691(12) 0.28441(6) 0.0183(3) Uani 1 1 d . . . . .
H2A H 0.621880 0.376237 0.291279 0.022 Uiso 1 1 calc R U . . .
C3 C 0.47404(14) 0.29925(13) 0.30858(6) 0.0214(3) Uani 1 1 d . . . . .
H3A H 0.501191 0.238809 0.335251 0.026 Uiso 1 1 calc R U . . .
C4 C 0.35961(14) 0.32696(13) 0.28629(7) 0.0217(3) Uani 1 1 d . . . . .
H4 H 0.295805 0.288001 0.294737 0.026 Uiso 1 1 calc R U . . .
C5 C 0.35657(12) 0.42306(13) 0.24908(7) 0.0187(3) Uani 1 1 d . . . . .
H5 H 0.289892 0.459658 0.228068 0.022 Uiso 1 1 calc R U . . .
C6 C 0.50446(11) 0.55682(12) 0.21560(6) 0.0155(3) Uani 1 1 d . . . . .
H6 H 0.482573 0.541370 0.170990 0.019 Uiso 1 1 calc R U . . .
C7 C 0.44005(12) 0.66368(12) 0.22844(6) 0.0177(3) Uani 1 1 d . . . . .
H7 H 0.356791 0.647929 0.219832 0.021 Uiso 1 1 calc R U . . .
C8 C 0.46444(13) 0.75988(13) 0.18750(7) 0.0209(3) Uani 1 1 d . . . . .
H8A H 0.423019 0.828277 0.195483 0.025 Uiso 1 1 calc R U . . .
H8B H 0.438035 0.738899 0.144277 0.025 Uiso 1 1 calc R U . . .
C9 C 0.59233(13) 0.78386(13) 0.20025(7) 0.0212(3) Uani 1 1 d . . . . .
H9 H 0.608487 0.845713 0.173111 0.025 Uiso 1 1 calc R U . . .
C10 C 0.65627(13) 0.67698(13) 0.18856(7) 0.0208(3) Uani 1 1 d . . . . .
H10A H 0.738654 0.692592 0.196149 0.025 Uiso 1 1 calc R U . . .
H10B H 0.631474 0.653782 0.145574 0.025 Uiso 1 1 calc R U . . .
C11 C 0.63297(12) 0.58144(13) 0.23053(6) 0.0166(3) Uani 1 1 d . . . . .
H11 H 0.675674 0.512563 0.223043 0.020 Uiso 1 1 calc R U . . .
C12 C 0.47901(13) 0.69822(13) 0.29532(7) 0.0196(3) Uani 1 1 d . . . . .
H12A H 0.463410 0.636572 0.322039 0.023 Uiso 1 1 calc R U . . .
H12B H 0.436493 0.765562 0.303757 0.023 Uiso 1 1 calc R U . . .
C13 C 0.63113(14) 0.81908(13) 0.26691(7) 0.0227(3) Uani 1 1 d . . . . .
H13A H 0.590423 0.888050 0.274745 0.027 Uiso 1 1 calc R U . . .
H13B H 0.713341 0.835749 0.275506 0.027 Uiso 1 1 calc R U . . .
C14 C 0.67200(12) 0.61901(13) 0.29703(6) 0.0186(3) Uani 1 1 d . . . . .
H14A H 0.658407 0.557889 0.324563 0.022 Uiso 1 1 calc R U . . .
H14B H 0.754286 0.635311 0.305457 0.022 Uiso 1 1 calc R U . . .
C15 C 0.60684(13) 0.72413(13) 0.30863(7) 0.0195(3) Uani 1 1 d . . . . .
H15 H 0.631768 0.747653 0.352043 0.023 Uiso 1 1 calc R U . . .
C16 C 0.38118(12) 0.10994(12) 0.13963(6) 0.0147(3) Uani 1 1 d . . . . .
C17 C 0.32814(12) 0.10219(12) 0.19071(6) 0.0168(3) Uani 1 1 d . . . . .
H17 H 0.248863 0.105377 0.189182 0.020 Uiso 1 1 calc R U . . .
C18 C 0.41222(13) 0.08909(12) 0.24351(7) 0.0187(3) Uani 1 1 d . . . . .
H18 H 0.400056 0.079647 0.283649 0.022 Uiso 1 1 calc R U . . .
C19 C 0.51879(12) 0.09251(12) 0.22606(7) 0.0183(3) Uani 1 1 d . . . . .
H19 H 0.590922 0.089357 0.252729 0.022 Uiso 1 1 calc R U . . .
C20 C 0.49875(12) 0.10142(12) 0.16200(7) 0.0168(3) Uani 1 1 d . . . . .
H20 H 0.555217 0.101630 0.138094 0.020 Uiso 1 1 calc R U . . .
C21 C 0.32355(11) 0.13625(12) 0.07458(6) 0.0148(3) Uani 1 1 d . . . . .
C22 C 0.37644(12) 0.06456(12) 0.02955(6) 0.0171(3) Uani 1 1 d . . . . .
H22 H 0.458679 0.083570 0.034733 0.021 Uiso 1 1 calc R U . . .
C23 C 0.31685(13) 0.08598(13) -0.03694(6) 0.0205(3) Uani 1 1 d . . . . .
H23A H 0.324263 0.166290 -0.047042 0.025 Uiso 1 1 calc R U . . .
H23B H 0.353411 0.040489 -0.064409 0.025 Uiso 1 1 calc R U . . .
C24 C 0.19108(13) 0.05468(14) -0.04631(7) 0.0234(3) Uani 1 1 d . . . . .
H24 H 0.152736 0.070343 -0.089345 0.028 Uiso 1 1 calc R U . . .
C25 C 0.13649(12) 0.12620(14) -0.00313(7) 0.0216(3) Uani 1 1 d . . . . .
H25A H 0.054960 0.107479 -0.008832 0.026 Uiso 1 1 calc R U . . .
H25B H 0.143078 0.206898 -0.012648 0.026 Uiso 1 1 calc R U . . .
C26 C 0.19578(12) 0.10363(13) 0.06332(6) 0.0178(3) Uani 1 1 d . . . . .
H26 H 0.157868 0.148825 0.090949 0.021 Uiso 1 1 calc R U . . .
C27 C 0.36426(13) -0.06136(13) 0.04300(7) 0.0205(3) Uani 1 1 d . . . . .
H27A H 0.401202 -0.106755 0.015655 0.025 Uiso 1 1 calc R U . . .
H27B H 0.402605 -0.077664 0.085445 0.025 Uiso 1 1 calc R U . . .
C28 C 0.18062(14) -0.07065(14) -0.03259(7) 0.0249(3) Uani 1 1 d . . . . .
H28A H 0.216897 -0.116052 -0.060216 0.030 Uiso 1 1 calc R U . . .
H28B H 0.099641 -0.092070 -0.039274 0.030 Uiso 1 1 calc R U . . .
C29 C 0.18263(12) -0.02246(13) 0.07624(7) 0.0202(3) Uani 1 1 d . . . . .
H29A H 0.218476 -0.039071 0.119038 0.024 Uiso 1 1 calc R U . . .
H29B H 0.101158 -0.041677 0.070118 0.024 Uiso 1 1 calc R U . . .
C30 C 0.23855(13) -0.09380(13) 0.03363(7) 0.0219(3) Uani 1 1 d . . . . .
H30 H 0.231596 -0.175369 0.043021 0.026 Uiso 1 1 calc R U . . .
C31 C 0.33897(12) 0.26687(12) 0.06871(6) 0.0156(3) Uani 1 1 d . . . . .
H31 H 0.278378 0.293719 0.034348 0.019 Uiso 1 1 calc R U . . .
C32 C 0.45280(12) 0.30711(12) 0.05638(6) 0.0156(3) Uani 1 1 d . . . . .
C33 C 0.54891(12) 0.33127(12) 0.10237(6) 0.0154(3) Uani 1 1 d . . . . .
C34 C 0.64925(12) 0.36897(13) 0.08625(7) 0.0196(3) Uani 1 1 d . . . . .
H34 H 0.713919 0.383634 0.117343 0.024 Uiso 1 1 calc R U . . .
C35 C 0.65598(13) 0.38519(13) 0.02621(7) 0.0222(3) Uani 1 1 d . . . . .
H35 H 0.725440 0.407402 0.016013 0.027 Uiso 1 1 calc R U . . .
C36 C 0.55989(14) 0.36860(14) -0.01905(7) 0.0224(3) Uani 1 1 d . . . . .
H36 H 0.562437 0.381971 -0.060420 0.027 Uiso 1 1 calc R U . . .
C37 C 0.46079(13) 0.33259(13) -0.00355(7) 0.0198(3) Uani 1 1 d . . . . .
H37 H 0.395032 0.324698 -0.034839 0.024 Uiso 1 1 calc R U . . .
C38 C 0.18415(12) 0.47252(13) 0.10207(6) 0.0185(3) Uani 1 1 d . . . . .
C39 C -0.01816(13) 0.41996(18) 0.08120(9) 0.0344(4) Uani 1 1 d . . . . .
H39A H -0.032780 0.477773 0.049489 0.052 Uiso 1 1 calc R U . . .
H39B H -0.043089 0.447167 0.117475 0.052 Uiso 1 1 calc R U . . .
H39C H -0.059958 0.351416 0.066380 0.052 Uiso 1 1 calc R U . . .


_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 O1 1.9152(10) . ?
Ti1 N1 2.0437(12) . ?
Ti1 C17 2.3555(14) . ?
Ti1 C16 2.3654(14) . ?
Ti1 C4 2.3669(15) . ?
Ti1 C19 2.3732(15) . ?
Ti1 C3 2.3897(14) . ?
Ti1 C5 2.3902(15) . ?
Ti1 C20 2.3941(15) . ?
Ti1 C18 2.3949(15) . ?
Ti1 C2 2.4099(14) . ?
Ti1 C1 2.4479(14) . ?
S1 C38 1.6934(16) . ?
O1 C33 1.3455(17) . ?
N1 N2 1.4100(17) . ?
N1 C31 1.4968(18) . ?
N2 C38 1.3458(19) . ?
N2 H2 0.86(2) . ?
N3 C38 1.330(2) . ?
N3 C39 1.455(2) . ?
N3 H3 0.89(2) . ?
C1 C2 1.418(2) . ?
C1 C5 1.422(2) . ?
C1 C6 1.508(2) . ?
C2 C3 1.411(2) . ?
C2 H2A 0.9500 . ?
C3 C4 1.407(2) . ?
C3 H3A 0.9500 . ?
C4 C5 1.412(2) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 C11 1.5441(18) . ?
C6 C7 1.547(2) . ?
C6 H6 1.0000 . ?
C7 C8 1.534(2) . ?
C7 C12 1.536(2) . ?
C7 H7 1.0000 . ?
C8 C9 1.536(2) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C13 1.533(2) . ?
C9 C10 1.537(2) . ?
C9 H9 1.0000 . ?
C10 C11 1.539(2) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C14 1.5380(19) . ?
C11 H11 1.0000 . ?
C12 C15 1.539(2) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 C15 1.534(2) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 C15 1.527(2) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15 1.0000 . ?
C16 C20 1.4067(19) . ?
C16 C17 1.427(2) . ?
C16 C21 1.5166(19) . ?
C17 C18 1.402(2) . ?
C17 H17 0.9500 . ?
C18 C19 1.419(2) . ?
C18 H18 0.9500 . ?
C19 C20 1.414(2) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C21 C22 1.5567(19) . ?
C21 C26 1.5578(18) . ?
C21 C31 1.573(2) . ?
C22 C23 1.5403(19) . ?
C22 C27 1.541(2) . ?
C22 H22 1.0000 . ?
C23 C24 1.533(2) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C28 1.533(2) . ?
C24 C25 1.537(2) . ?
C24 H24 1.0000 . ?
C25 C26 1.541(2) . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C26 C29 1.542(2) . ?
C26 H26 1.0000 . ?
C27 C30 1.536(2) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C28 C30 1.533(2) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 C30 1.535(2) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30 1.0000 . ?
C31 C32 1.5313(19) . ?
C31 H31 1.0000 . ?
C32 C37 1.403(2) . ?
C32 C33 1.415(2) . ?
C33 C34 1.406(2) . ?
C34 C35 1.382(2) . ?
C34 H34 0.9500 . ?
C35 C36 1.390(2) . ?
C35 H35 0.9500 . ?
C36 C37 1.380(2) . ?
C36 H36 0.9500 . ?
C37 H37 0.9500 . ?
C39 H39A 0.9800 . ?
C39 H39B 0.9800 . ?
C39 H39C 0.9800 . ?

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
O1 Ti1 N1 88.09(5) . . ?
O1 Ti1 C17 133.06(5) . . ?
N1 Ti1 C17 83.68(5) . . ?
O1 Ti1 C16 98.62(5) . . ?
N1 Ti1 C16 71.75(5) . . ?
C17 Ti1 C16 35.20(5) . . ?
O1 Ti1 C4 134.26(5) . . ?
N1 Ti1 C4 106.41(5) . . ?
C17 Ti1 C4 92.16(5) . . ?
C16 Ti1 C4 127.07(5) . . ?
O1 Ti1 C19 95.82(5) . . ?
N1 Ti1 C19 129.44(5) . . ?
C17 Ti1 C19 57.51(5) . . ?
C16 Ti1 C19 57.80(5) . . ?
C4 Ti1 C19 106.14(5) . . ?
O1 Ti1 C3 113.11(5) . . ?
N1 Ti1 C3 139.53(5) . . ?
C17 Ti1 C3 102.47(5) . . ?
C16 Ti1 C3 132.86(5) . . ?
C4 Ti1 C3 34.39(6) . . ?
C19 Ti1 C3 84.16(5) . . ?
O1 Ti1 C5 108.83(5) . . ?
N1 Ti1 C5 84.23(5) . . ?
C17 Ti1 C5 116.12(5) . . ?
C16 Ti1 C5 142.75(5) . . ?
C4 Ti1 C5 34.54(5) . . ?
C19 Ti1 C5 139.43(5) . . ?
C3 Ti1 C5 56.89(5) . . ?
O1 Ti1 C20 78.67(5) . . ?
N1 Ti1 C20 98.79(5) . . ?
C17 Ti1 C20 57.33(5) . . ?
C16 Ti1 C20 34.38(5) . . ?
C4 Ti1 C20 137.86(5) . . ?
C19 Ti1 C20 34.51(5) . . ?
C3 Ti1 C20 118.38(5) . . ?
C5 Ti1 C20 172.09(5) . . ?
O1 Ti1 C18 130.29(5) . . ?
N1 Ti1 C18 117.94(5) . . ?
C17 Ti1 C18 34.31(5) . . ?
C16 Ti1 C18 57.81(5) . . ?
C4 Ti1 C18 81.09(5) . . ?
C19 Ti1 C18 34.62(5) . . ?
C3 Ti1 C18 75.05(5) . . ?
C5 Ti1 C18 114.95(5) . . ?
C20 Ti1 C18 57.18(5) . . ?
O1 Ti1 C2 80.79(5) . . ?
N1 Ti1 C2 131.93(5) . . ?
C17 Ti1 C2 135.81(5) . . ?
C16 Ti1 C2 156.02(5) . . ?
C4 Ti1 C2 57.00(5) . . ?
C19 Ti1 C2 98.29(5) . . ?
C3 Ti1 C2 34.18(5) . . ?
C5 Ti1 C2 56.55(5) . . ?
C20 Ti1 C2 123.97(5) . . ?
C18 Ti1 C2 104.34(5) . . ?
O1 Ti1 C1 78.22(5) . . ?
N1 Ti1 C1 98.05(5) . . ?
C17 Ti1 C1 148.68(5) . . ?
C16 Ti1 C1 169.52(5) . . ?
C4 Ti1 C1 57.20(5) . . ?
C19 Ti1 C1 132.16(5) . . ?
C3 Ti1 C1 56.80(5) . . ?
C5 Ti1 C1 34.16(5) . . ?
C20 Ti1 C1 150.78(5) . . ?
C18 Ti1 C1 131.63(5) . . ?
C2 Ti1 C1 33.93(5) . . ?
C33 O1 Ti1 128.12(9) . . ?
N2 N1 C31 108.54(11) . . ?
N2 N1 Ti1 120.00(9) . . ?
C31 N1 Ti1 112.42(8) . . ?
C38 N2 N1 122.63(13) . . ?
C38 N2 H2 116.7(14) . . ?
N1 N2 H2 120.7(14) . . ?
C38 N3 C39 124.63(15) . . ?
C38 N3 H3 115.1(14) . . ?
C39 N3 H3 120.1(14) . . ?
C2 C1 C5 106.39(13) . . ?
C2 C1 C6 127.47(13) . . ?
C5 C1 C6 126.14(13) . . ?
C2 C1 Ti1 71.57(8) . . ?
C5 C1 Ti1 70.69(8) . . ?
C6 C1 Ti1 123.26(9) . . ?
C3 C2 C1 108.90(13) . . ?
C3 C2 Ti1 72.13(8) . . ?
C1 C2 Ti1 74.51(8) . . ?
C3 C2 H2A 125.5 . . ?
C1 C2 H2A 125.5 . . ?
Ti1 C2 H2A 119.6 . . ?
C4 C3 C2 108.04(14) . . ?
C4 C3 Ti1 71.92(8) . . ?
C2 C3 Ti1 73.69(8) . . ?
C4 C3 H3A 126.0 . . ?
C2 C3 H3A 126.0 . . ?
Ti1 C3 H3A 120.2 . . ?
C3 C4 C5 107.74(13) . . ?
C3 C4 Ti1 73.69(9) . . ?
C5 C4 Ti1 73.64(8) . . ?
C3 C4 H4 126.1 . . ?
C5 C4 H4 126.1 . . ?
Ti1 C4 H4 118.5 . . ?
C4 C5 C1 108.89(13) . . ?
C4 C5 Ti1 71.83(9) . . ?
C1 C5 Ti1 75.14(8) . . ?
C4 C5 H5 125.6 . . ?
C1 C5 H5 125.6 . . ?
Ti1 C5 H5 119.3 . . ?
C1 C6 C11 114.34(12) . . ?
C1 C6 C7 111.16(12) . . ?
C11 C6 C7 108.86(12) . . ?
C1 C6 H6 107.4 . . ?
C11 C6 H6 107.4 . . ?
C7 C6 H6 107.4 . . ?
C8 C7 C12 109.26(12) . . ?
C8 C7 C6 109.59(12) . . ?
C12 C7 C6 109.76(12) . . ?
C8 C7 H7 109.4 . . ?
C12 C7 H7 109.4 . . ?
C6 C7 H7 109.4 . . ?
C7 C8 C9 109.59(12) . . ?
C7 C8 H8A 109.8 . . ?
C9 C8 H8A 109.8 . . ?
C7 C8 H8B 109.8 . . ?
C9 C8 H8B 109.8 . . ?
H8A C8 H8B 108.2 . . ?
C13 C9 C8 109.03(13) . . ?
C13 C9 C10 109.27(12) . . ?
C8 C9 C10 109.51(12) . . ?
C13 C9 H9 109.7 . . ?
C8 C9 H9 109.7 . . ?
C10 C9 H9 109.7 . . ?
C9 C10 C11 110.16(12) . . ?
C9 C10 H10A 109.6 . . ?
C11 C10 H10A 109.6 . . ?
C9 C10 H10B 109.6 . . ?
C11 C10 H10B 109.6 . . ?
H10A C10 H10B 108.1 . . ?
C14 C11 C10 108.85(12) . . ?
C14 C11 C6 111.05(12) . . ?
C10 C11 C6 107.95(11) . . ?
C14 C11 H11 109.7 . . ?
C10 C11 H11 109.7 . . ?
C6 C11 H11 109.7 . . ?
C7 C12 C15 109.65(12) . . ?
C7 C12 H12A 109.7 . . ?
C15 C12 H12A 109.7 . . ?
C7 C12 H12B 109.7 . . ?
C15 C12 H12B 109.7 . . ?
H12A C12 H12B 108.2 . . ?
C9 C13 C15 109.76(12) . . ?
C9 C13 H13A 109.7 . . ?
C15 C13 H13A 109.7 . . ?
C9 C13 H13B 109.7 . . ?
C15 C13 H13B 109.7 . . ?
H13A C13 H13B 108.2 . . ?
C15 C14 C11 109.79(12) . . ?
C15 C14 H14A 109.7 . . ?
C11 C14 H14A 109.7 . . ?
C15 C14 H14B 109.7 . . ?
C11 C14 H14B 109.7 . . ?
H14A C14 H14B 108.2 . . ?
C14 C15 C13 109.19(13) . . ?
C14 C15 C12 109.41(12) . . ?
C13 C15 C12 109.74(12) . . ?
C14 C15 H15 109.5 . . ?
C13 C15 H15 109.5 . . ?
C12 C15 H15 109.5 . . ?
C20 C16 C17 107.02(12) . . ?
C20 C16 C21 125.99(13) . . ?
C17 C16 C21 126.63(13) . . ?
C20 C16 Ti1 73.93(8) . . ?
C17 C16 Ti1 72.02(8) . . ?
C21 C16 Ti1 114.19(9) . . ?
C18 C17 C16 108.83(13) . . ?
C18 C17 Ti1 74.38(8) . . ?
C16 C17 Ti1 72.78(8) . . ?
C18 C17 H17 125.6 . . ?
C16 C17 H17 125.6 . . ?
Ti1 C17 H17 119.1 . . ?
C17 C18 C19 107.52(13) . . ?
C17 C18 Ti1 71.30(8) . . ?
C19 C18 Ti1 71.86(8) . . ?
C17 C18 H18 126.2 . . ?
C19 C18 H18 126.2 . . ?
Ti1 C18 H18 122.3 . . ?
C20 C19 C18 107.99(13) . . ?
C20 C19 Ti1 73.56(8) . . ?
C18 C19 Ti1 73.53(8) . . ?
C20 C19 H19 126.0 . . ?
C18 C19 H19 126.0 . . ?
Ti1 C19 H19 118.8 . . ?
C16 C20 C19 108.54(13) . . ?
C16 C20 Ti1 71.70(8) . . ?
C19 C20 Ti1 71.94(8) . . ?
C16 C20 H20 125.7 . . ?
C19 C20 H20 125.7 . . ?
Ti1 C20 H20 122.3 . . ?
C16 C21 C22 110.25(12) . . ?
C16 C21 C26 110.29(11) . . ?
C22 C21 C26 106.34(11) . . ?
C16 C21 C31 104.24(11) . . ?
C22 C21 C31 114.52(12) . . ?
C26 C21 C31 111.24(11) . . ?
C23 C22 C27 107.87(12) . . ?
C23 C22 C21 111.63(12) . . ?
C27 C22 C21 109.66(12) . . ?
C23 C22 H22 109.2 . . ?
C27 C22 H22 109.2 . . ?
C21 C22 H22 109.2 . . ?
C24 C23 C22 110.11(12) . . ?
C24 C23 H23A 109.6 . . ?
C22 C23 H23A 109.6 . . ?
C24 C23 H23B 109.6 . . ?
C22 C23 H23B 109.6 . . ?
H23A C23 H23B 108.2 . . ?
C28 C24 C23 109.17(13) . . ?
C28 C24 C25 110.35(13) . . ?
C23 C24 C25 108.58(12) . . ?
C28 C24 H24 109.6 . . ?
C23 C24 H24 109.6 . . ?
C25 C24 H24 109.6 . . ?
C24 C25 C26 110.01(12) . . ?
C24 C25 H25A 109.7 . . ?
C26 C25 H25A 109.7 . . ?
C24 C25 H25B 109.7 . . ?
C26 C25 H25B 109.7 . . ?
H25A C25 H25B 108.2 . . ?
C25 C26 C29 107.87(12) . . ?
C25 C26 C21 111.10(12) . . ?
C29 C26 C21 110.37(12) . . ?
C25 C26 H26 109.2 . . ?
C29 C26 H26 109.2 . . ?
C21 C26 H26 109.2 . . ?
C30 C27 C22 110.39(13) . . ?
C30 C27 H27A 109.6 . . ?
C22 C27 H27A 109.6 . . ?
C30 C27 H27B 109.6 . . ?
C22 C27 H27B 109.6 . . ?
H27A C27 H27B 108.1 . . ?
C24 C28 C30 109.28(12) . . ?
C24 C28 H28A 109.8 . . ?
C30 C28 H28A 109.8 . . ?
C24 C28 H28B 109.8 . . ?
C30 C28 H28B 109.8 . . ?
H28A C28 H28B 108.3 . . ?
C30 C29 C26 110.16(12) . . ?
C30 C29 H29A 109.6 . . ?
C26 C29 H29A 109.6 . . ?
C30 C29 H29B 109.6 . . ?
C26 C29 H29B 109.6 . . ?
H29A C29 H29B 108.1 . . ?
C28 C30 C29 109.61(13) . . ?
C28 C30 C27 109.12(13) . . ?
C29 C30 C27 108.85(12) . . ?
C28 C30 H30 109.7 . . ?
C29 C30 H30 109.7 . . ?
C27 C30 H30 109.7 . . ?
N1 C31 C32 110.78(11) . . ?
N1 C31 C21 106.61(11) . . ?
C32 C31 C21 116.71(12) . . ?
N1 C31 H31 107.5 . . ?
C32 C31 H31 107.5 . . ?
C21 C31 H31 107.5 . . ?
C37 C32 C33 116.75(13) . . ?
C37 C32 C31 118.82(12) . . ?
C33 C32 C31 124.13(12) . . ?
O1 C33 C34 116.45(12) . . ?
O1 C33 C32 123.71(13) . . ?
C34 C33 C32 119.69(13) . . ?
C35 C34 C33 121.51(14) . . ?
C35 C34 H34 119.2 . . ?
C33 C34 H34 119.2 . . ?
C34 C35 C36 119.19(14) . . ?
C34 C35 H35 120.4 . . ?
C36 C35 H35 120.4 . . ?
C37 C36 C35 119.60(14) . . ?
C37 C36 H36 120.2 . . ?
C35 C36 H36 120.2 . . ?
C36 C37 C32 122.92(14) . . ?
C36 C37 H37 118.5 . . ?
C32 C37 H37 118.5 . . ?
N3 C38 N2 115.87(14) . . ?
N3 C38 S1 124.25(12) . . ?
N2 C38 S1 119.87(12) . . ?
N3 C39 H39A 109.5 . . ?
N3 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
N3 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?

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
C31 N1 N2 C38 98.66(15) . . . . ?
Ti1 N1 N2 C38 -130.19(12) . . . . ?
C5 C1 C2 C3 -1.90(16) . . . . ?
C6 C1 C2 C3 177.35(13) . . . . ?
Ti1 C1 C2 C3 -64.43(10) . . . . ?
C5 C1 C2 Ti1 62.53(10) . . . . ?
C6 C1 C2 Ti1 -118.22(14) . . . . ?
C1 C2 C3 C4 1.79(17) . . . . ?
Ti1 C2 C3 C4 -64.19(10) . . . . ?
C1 C2 C3 Ti1 65.98(10) . . . . ?
C2 C3 C4 C5 -0.95(17) . . . . ?
Ti1 C3 C4 C5 -66.31(10) . . . . ?
C2 C3 C4 Ti1 65.35(10) . . . . ?
C3 C4 C5 C1 -0.23(17) . . . . ?
Ti1 C4 C5 C1 -66.58(10) . . . . ?
C3 C4 C5 Ti1 66.34(10) . . . . ?
C2 C1 C5 C4 1.31(16) . . . . ?
C6 C1 C5 C4 -177.95(13) . . . . ?
Ti1 C1 C5 C4 64.42(10) . . . . ?
C2 C1 C5 Ti1 -63.11(10) . . . . ?
C6 C1 C5 Ti1 117.63(14) . . . . ?
C2 C1 C6 C11 -7.7(2) . . . . ?
C5 C1 C6 C11 171.41(13) . . . . ?
Ti1 C1 C6 C11 -99.20(13) . . . . ?
C2 C1 C6 C7 -131.45(14) . . . . ?
C5 C1 C6 C7 47.65(18) . . . . ?
Ti1 C1 C6 C7 137.04(10) . . . . ?
C1 C6 C7 C8 -171.78(11) . . . . ?
C11 C6 C7 C8 61.39(14) . . . . ?
C1 C6 C7 C12 68.22(15) . . . . ?
C11 C6 C7 C12 -58.60(15) . . . . ?
C12 C7 C8 C9 60.62(16) . . . . ?
C6 C7 C8 C9 -59.68(16) . . . . ?
C7 C8 C9 C13 -60.82(16) . . . . ?
C7 C8 C9 C10 58.69(16) . . . . ?
C13 C9 C10 C11 59.21(16) . . . . ?
C8 C9 C10 C11 -60.15(15) . . . . ?
C9 C10 C11 C14 -59.28(15) . . . . ?
C9 C10 C11 C6 61.35(15) . . . . ?
C1 C6 C11 C14 -67.21(16) . . . . ?
C7 C6 C11 C14 57.77(15) . . . . ?
C1 C6 C11 C10 173.54(12) . . . . ?
C7 C6 C11 C10 -61.48(14) . . . . ?
C8 C7 C12 C15 -59.49(16) . . . . ?
C6 C7 C12 C15 60.70(16) . . . . ?
C8 C9 C13 C15 60.12(16) . . . . ?
C10 C9 C13 C15 -59.53(16) . . . . ?
C10 C11 C14 C15 60.10(15) . . . . ?
C6 C11 C14 C15 -58.61(16) . . . . ?
C11 C14 C15 C13 -60.87(15) . . . . ?
C11 C14 C15 C12 59.26(15) . . . . ?
C9 C13 C15 C14 60.52(16) . . . . ?
C9 C13 C15 C12 -59.40(16) . . . . ?
C7 C12 C15 C14 -60.80(16) . . . . ?
C7 C12 C15 C13 58.99(16) . . . . ?
C20 C16 C17 C18 -0.02(16) . . . . ?
C21 C16 C17 C18 -173.39(13) . . . . ?
Ti1 C16 C17 C18 -66.21(10) . . . . ?
C20 C16 C17 Ti1 66.19(10) . . . . ?
C21 C16 C17 Ti1 -107.19(14) . . . . ?
C16 C17 C18 C19 2.00(17) . . . . ?
Ti1 C17 C18 C19 -63.16(10) . . . . ?
C16 C17 C18 Ti1 65.16(10) . . . . ?
C17 C18 C19 C20 -3.23(17) . . . . ?
Ti1 C18 C19 C20 -66.02(10) . . . . ?
C17 C18 C19 Ti1 62.80(10) . . . . ?
C17 C16 C20 C19 -2.00(16) . . . . ?
C21 C16 C20 C19 171.44(13) . . . . ?
Ti1 C16 C20 C19 62.91(10) . . . . ?
C17 C16 C20 Ti1 -64.90(10) . . . . ?
C21 C16 C20 Ti1 108.53(14) . . . . ?
C18 C19 C20 C16 3.25(17) . . . . ?
Ti1 C19 C20 C16 -62.75(10) . . . . ?
C18 C19 C20 Ti1 66.00(10) . . . . ?
C20 C16 C21 C22 45.97(19) . . . . ?
C17 C16 C21 C22 -141.86(14) . . . . ?
Ti1 C16 C21 C22 133.17(10) . . . . ?
C20 C16 C21 C26 163.12(14) . . . . ?
C17 C16 C21 C26 -24.7(2) . . . . ?
Ti1 C16 C21 C26 -109.68(11) . . . . ?
C20 C16 C21 C31 -77.39(17) . . . . ?
C17 C16 C21 C31 94.77(16) . . . . ?
Ti1 C16 C21 C31 9.81(13) . . . . ?
C16 C21 C22 C23 177.89(12) . . . . ?
C26 C21 C22 C23 58.32(15) . . . . ?
C31 C21 C22 C23 -64.95(15) . . . . ?
C16 C21 C22 C27 58.40(15) . . . . ?
C26 C21 C22 C27 -61.17(14) . . . . ?
C31 C21 C22 C27 175.56(11) . . . . ?
C27 C22 C23 C24 60.06(16) . . . . ?
C21 C22 C23 C24 -60.48(16) . . . . ?
C22 C23 C24 C28 -61.16(16) . . . . ?
C22 C23 C24 C25 59.19(16) . . . . ?
C28 C24 C25 C26 59.85(16) . . . . ?
C23 C24 C25 C26 -59.77(16) . . . . ?
C24 C25 C26 C29 -59.75(15) . . . . ?
C24 C25 C26 C21 61.35(16) . . . . ?
C16 C21 C26 C25 -178.19(12) . . . . ?
C22 C21 C26 C25 -58.64(15) . . . . ?
C31 C21 C26 C25 66.66(15) . . . . ?
C16 C21 C26 C29 -58.57(15) . . . . ?
C22 C21 C26 C29 60.97(14) . . . . ?
C31 C21 C26 C29 -173.73(11) . . . . ?
C23 C22 C27 C30 -59.81(15) . . . . ?
C21 C22 C27 C30 61.96(15) . . . . ?
C23 C24 C28 C30 60.55(16) . . . . ?
C25 C24 C28 C30 -58.71(17) . . . . ?
C25 C26 C29 C30 60.61(15) . . . . ?
C21 C26 C29 C30 -60.95(15) . . . . ?
C24 C28 C30 C29 59.01(17) . . . . ?
C24 C28 C30 C27 -60.10(17) . . . . ?
C26 C29 C30 C28 -60.96(15) . . . . ?
C26 C29 C30 C27 58.31(16) . . . . ?
C22 C27 C30 C28 60.48(16) . . . . ?
C22 C27 C30 C29 -59.10(16) . . . . ?
N2 N1 C31 C32 71.86(13) . . . . ?
Ti1 N1 C31 C32 -63.27(13) . . . . ?
N2 N1 C31 C21 -160.19(10) . . . . ?
Ti1 N1 C31 C21 64.67(11) . . . . ?
C16 C21 C31 N1 -42.44(13) . . . . ?
C22 C21 C31 N1 -162.99(11) . . . . ?
C26 C21 C31 N1 76.41(13) . . . . ?
C16 C21 C31 C32 81.93(14) . . . . ?
C22 C21 C31 C32 -38.62(16) . . . . ?
C26 C21 C31 C32 -159.22(11) . . . . ?
N1 C31 C32 C37 -139.72(13) . . . . ?
C21 C31 C32 C37 98.06(16) . . . . ?
N1 C31 C32 C33 33.75(19) . . . . ?
C21 C31 C32 C33 -88.47(17) . . . . ?
Ti1 O1 C33 C34 -174.79(10) . . . . ?
Ti1 O1 C33 C32 9.7(2) . . . . ?
C37 C32 C33 O1 169.69(13) . . . . ?
C31 C32 C33 O1 -3.9(2) . . . . ?
C37 C32 C33 C34 -5.7(2) . . . . ?
C31 C32 C33 C34 -179.30(13) . . . . ?
O1 C33 C34 C35 -174.51(14) . . . . ?
C32 C33 C34 C35 1.2(2) . . . . ?
C33 C34 C35 C36 2.9(2) . . . . ?
C34 C35 C36 C37 -2.2(2) . . . . ?
C35 C36 C37 C32 -2.6(2) . . . . ?
C33 C32 C37 C36 6.5(2) . . . . ?
C31 C32 C37 C36 -179.52(14) . . . . ?
C39 N3 C38 N2 -178.44(15) . . . . ?
C39 N3 C38 S1 2.5(2) . . . . ?
N1 N2 C38 N3 -4.0(2) . . . . ?
N1 N2 C38 S1 175.14(10) . . . . ?

_refine_diff_density_max         0.515
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.049



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Ti3d
_database_code_depnum_ccdc_archive 'CCDC 2377766'
loop_
_audit_author_name
_audit_author_address
'Marc Schmidtmann'
;Carl von Ossietzky Universitaet Oldenburg
Germany
;
_audit_update_record             
;
2024-08-15 deposited with the CCDC.	2024-09-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/3
_shelx_SHELXL_version_number     2019/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_structural     '[Ti2(C5H5)2(C9H10N3OS)2] [CF3SO3]2 *3C4H8O'
_chemical_formula_sum            'C42 H54 F6 N6 O11 S4 Ti2'
_chemical_formula_weight         1156.95

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'
F F 0.0171 0.0103 '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'
O O 0.0106 0.0060 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

_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.
;

loop_
_space_group_symop_operation_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                   13.7863(7)
_cell_length_b                   22.5048(13)
_cell_length_c                   17.5439(10)
_cell_angle_alpha                90
_cell_angle_beta                 105.069(2)
_cell_angle_gamma                90
_cell_volume                     5256.0(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9663
_cell_measurement_theta_min      2.36
_cell_measurement_theta_max      30.05

_exptl_crystal_description       block
_exptl_crystal_colour            'yellow green orange'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.462
_exptl_crystal_F_000             2392
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.544
_shelx_estimated_absorpt_T_min   0.938
_shelx_estimated_absorpt_T_max   0.979
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9135
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'I\mS microfocus'
_diffrn_measurement_device_type  'Bruker Photon III CPAD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            95632
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_av_R_equivalents  0.0504
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.777
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             7702
_reflns_number_gt                6819
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT V8.40B'
_computing_data_reduction        'Bruker SAINT V8.40B'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0600P)²+13.5000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         7702
_refine_ls_number_parameters     331
_refine_ls_number_restraints     30
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0556
_refine_ls_wR_factor_ref         0.1434
_refine_ls_wR_factor_gt          0.1387
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_restrained_S_all      1.116
_refine_ls_shift/su_max          0.000
_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_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 0.49451(3) 0.10819(2) 0.33992(2) 0.01837(9) Uani 1 1 d . . . . .
S1 S 0.60958(4) 0.18019(3) 0.42497(4) 0.03889(18) Uani 1 1 d . . . . .
O1 O 0.40305(10) 0.11062(6) 0.22741(8) 0.0186(3) Uani 1 1 d . . . . .
N1 N 0.39391(13) 0.17956(8) 0.35468(10) 0.0217(3) Uani 1 1 d . . . . .
N2 N 0.42570(15) 0.22028(9) 0.41430(12) 0.0281(4) Uani 1 1 d . . . . .
H2 H 0.387(3) 0.2427(15) 0.421(2) 0.039(9) Uiso 1 1 d . . . . .
N3 N 0.54710(16) 0.25945(11) 0.51444(15) 0.0372(5) Uani 1 1 d . . . . .
H3 H 0.508(3) 0.2774(17) 0.523(2) 0.048(10) Uiso 1 1 d . . . . .
C1 C 0.42872(18) 0.01008(10) 0.34019(14) 0.0284(4) Uani 1 1 d . . . . .
H1 H 0.392192 -0.008794 0.293009 0.034 Uiso 1 1 calc R U . . .
C2 C 0.38796(17) 0.04667(11) 0.38937(14) 0.0278(4) Uani 1 1 d . . . . .
H2A H 0.319014 0.056493 0.381319 0.033 Uiso 1 1 calc R U . . .
C3 C 0.46728(18) 0.06607(11) 0.45246(13) 0.0294(5) Uani 1 1 d . . . . .
H3A H 0.461423 0.091625 0.494139 0.035 Uiso 1 1 calc R U . . .
C4 C 0.55767(18) 0.04065(12) 0.44272(14) 0.0312(5) Uani 1 1 d . . . . .
H4 H 0.622901 0.045857 0.476969 0.037 Uiso 1 1 calc R U . . .
C5 C 0.53333(18) 0.00650(10) 0.37349(15) 0.0295(5) Uani 1 1 d . . . . .
H5 H 0.579467 -0.015338 0.352558 0.035 Uiso 1 1 calc R U . . .
C6 C 0.30097(15) 0.11011(9) 0.21021(12) 0.0197(4) Uani 1 1 d . . . . .
C7 C 0.24503(16) 0.07574(10) 0.14806(13) 0.0256(4) Uani 1 1 d . . . . .
H7 H 0.278415 0.053880 0.116090 0.031 Uiso 1 1 calc R U . . .
C8 C 0.14106(17) 0.07310(11) 0.13238(14) 0.0295(5) Uani 1 1 d . . . . .
H8 H 0.104221 0.048953 0.090342 0.035 Uiso 1 1 calc R U . . .
C9 C 0.09015(16) 0.10548(11) 0.17759(14) 0.0274(4) Uani 1 1 d . . . . .
H9 H 0.019092 0.103114 0.167093 0.033 Uiso 1 1 calc R U . . .
C10 C 0.14411(15) 0.14083(10) 0.23751(13) 0.0239(4) Uani 1 1 d . . . . .
H10 H 0.109468 0.163716 0.267578 0.029 Uiso 1 1 calc R U . . .
C11 C 0.25006(15) 0.14394(9) 0.25548(12) 0.0203(4) Uani 1 1 d . . . . .
C12 C 0.29928(16) 0.18288(10) 0.31874(13) 0.0230(4) Uani 1 1 d . . . . .
H12 H 0.260206 0.212691 0.335064 0.028 Uiso 1 1 calc R U . . .
C13 C 0.52307(17) 0.22268(11) 0.45387(15) 0.0308(5) Uani 1 1 d . . . . .
C14 C 0.6496(2) 0.26932(18) 0.5604(2) 0.0615(11) Uani 1 1 d . . . . .
H14A H 0.649842 0.296966 0.603606 0.092 Uiso 1 1 calc R U . . .
H14B H 0.688884 0.286212 0.526418 0.092 Uiso 1 1 calc R U . . .
H14C H 0.679480 0.231448 0.582246 0.092 Uiso 1 1 calc R U . . .
S2 S 0.30303(4) 0.34164(3) 0.49881(3) 0.02467(12) Uani 1 1 d . . . . .
F22 F 0.42724(16) 0.41247(13) 0.45399(18) 0.0877(9) Uani 1 1 d . . . . .
F23 F 0.27276(18) 0.43917(10) 0.41622(18) 0.0840(9) Uani 1 1 d . . . . .
F24 F 0.3574(2) 0.45082(10) 0.5380(2) 0.0945(10) Uani 1 1 d . . . . .
O2 O 0.21241(14) 0.35319(11) 0.52113(12) 0.0433(5) Uani 1 1 d . . . . .
O3 O 0.38738(13) 0.32191(8) 0.56173(10) 0.0323(4) Uani 1 1 d . . . . .
O4 O 0.29058(15) 0.30907(9) 0.42628(11) 0.0384(4) Uani 1 1 d . . . . .
C15 C 0.3419(2) 0.41491(15) 0.4756(3) 0.0562(9) Uani 1 1 d . . . . .
O5 O 0.500000 0.11045(12) 0.750000 0.0522(8) Uani 1 2 d S T P . .
C16 C 0.4805(3) 0.14730(13) 0.68114(18) 0.0501(8) Uani 1 1 d . . . . .
H16A H 0.409340 0.143763 0.650805 0.060 Uiso 1 1 calc R U . . .
H16B H 0.523737 0.135506 0.646641 0.060 Uiso 1 1 calc R U . . .
C17 C 0.5034(5) 0.20964(15) 0.7099(2) 0.0782(15) Uani 1 1 d . . . . .
H17A H 0.571692 0.221287 0.707226 0.094 Uiso 1 1 calc R U . . .
H17B H 0.454263 0.237723 0.677587 0.094 Uiso 1 1 calc R U . . .
O6A O 0.2922(7) 0.3130(4) 0.2331(5) 0.1113(14) Uiso 0.5 1 d D . P A 1
C18A C 0.2679(13) 0.3763(9) 0.2247(8) 0.1113(14) Uiso 0.5 1 d D . P A 1
H18A H 0.315491 0.399319 0.266114 0.134 Uiso 0.5 1 calc R U P A 1
H18B H 0.199006 0.383263 0.229879 0.134 Uiso 0.5 1 calc R U P A 1
C19A C 0.2755(12) 0.3945(6) 0.1464(9) 0.1113(14) Uiso 0.5 1 d D . P A 1
H19A H 0.295439 0.436651 0.144604 0.134 Uiso 0.5 1 calc R U P A 1
H19B H 0.213378 0.386464 0.104449 0.134 Uiso 0.5 1 calc R U P A 1
C20A C 0.3628(11) 0.3502(7) 0.1443(9) 0.1113(14) Uiso 0.5 1 d D . P A 1
H20A H 0.348273 0.330080 0.092380 0.134 Uiso 0.5 1 calc R U P A 1
H20B H 0.426731 0.372275 0.151930 0.134 Uiso 0.5 1 calc R U P A 1
C21A C 0.3715(11) 0.3067(6) 0.2065(9) 0.1113(14) Uiso 0.5 1 d D . P A 1
H21A H 0.374180 0.266017 0.185565 0.134 Uiso 0.5 1 calc R U P A 1
H21B H 0.433322 0.313636 0.249212 0.134 Uiso 0.5 1 calc R U P A 1
O6B O 0.3476(13) 0.4356(8) 0.2284(10) 0.1113(14) Uiso 0.25 1 d D . P B 2
C18B C 0.289(2) 0.3845(18) 0.2338(14) 0.1113(14) Uiso 0.25 1 d D . P B 2
H18C H 0.236104 0.394430 0.260214 0.134 Uiso 0.25 1 calc R U P B 2
H18D H 0.332338 0.352925 0.264611 0.134 Uiso 0.25 1 calc R U P B 2
C19B C 0.2454(18) 0.3646(12) 0.1540(14) 0.1113(14) Uiso 0.25 1 d D . P B 2
H19C H 0.174363 0.377188 0.134886 0.134 Uiso 0.25 1 calc R U P B 2
H19D H 0.249786 0.320923 0.149268 0.134 Uiso 0.25 1 calc R U P B 2
C20B C 0.315(2) 0.3978(13) 0.1086(13) 0.1113(14) Uiso 0.25 1 d D . P B 2
H20C H 0.352273 0.368569 0.085220 0.134 Uiso 0.25 1 calc R U P B 2
H20D H 0.273325 0.422495 0.065607 0.134 Uiso 0.25 1 calc R U P B 2
C21B C 0.3842(18) 0.4351(12) 0.1654(13) 0.1113(14) Uiso 0.25 1 d D . P B 2
H21C H 0.452795 0.418095 0.178513 0.134 Uiso 0.25 1 calc R U P B 2
H21D H 0.386340 0.475730 0.144371 0.134 Uiso 0.25 1 calc R U P B 2
O6C O 0.4048(14) 0.3463(9) 0.1419(11) 0.1113(14) Uiso 0.25 1 d D . P C 3
C18C C 0.4124(19) 0.3239(11) 0.2168(15) 0.1113(14) Uiso 0.25 1 d D . P C 3
H18E H 0.479445 0.332497 0.252345 0.134 Uiso 0.25 1 calc R U P C 3
H18F H 0.401410 0.280433 0.214916 0.134 Uiso 0.25 1 calc R U P C 3
C19C C 0.334(2) 0.3542(11) 0.2433(14) 0.1113(14) Uiso 0.25 1 d D . P C 3
H19E H 0.357947 0.366288 0.299368 0.134 Uiso 0.25 1 calc R U P C 3
H19F H 0.273364 0.329401 0.235896 0.134 Uiso 0.25 1 calc R U P C 3
C20C C 0.316(2) 0.4095(11) 0.1864(16) 0.1113(14) Uiso 0.25 1 d D . P C 3
H20E H 0.243183 0.418134 0.168349 0.134 Uiso 0.25 1 calc R U P C 3
H20F H 0.350306 0.444852 0.214528 0.134 Uiso 0.25 1 calc R U P C 3
C21C C 0.355(2) 0.3962(11) 0.1191(14) 0.1113(14) Uiso 0.25 1 d D . P C 3
H21E H 0.300181 0.390318 0.070597 0.134 Uiso 0.25 1 calc R U P C 3
H21F H 0.400209 0.428121 0.109994 0.134 Uiso 0.25 1 calc R U P C 3


_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 O1 2.0482(15) . ?
Ti1 O1 2.0639(14) 2_655 ?
Ti1 N1 2.1810(18) . ?
Ti1 C3 2.307(2) . ?
Ti1 C2 2.343(2) . ?
Ti1 C4 2.346(2) . ?
Ti1 C1 2.387(2) . ?
Ti1 C5 2.389(2) . ?
Ti1 S1 2.4774(7) . ?
Ti1 Ti1 3.1977(7) 2_655 ?
S1 C13 1.705(2) . ?
O1 C6 1.360(2) . ?
N1 C12 1.295(3) . ?
N1 N2 1.374(3) . ?
N2 C13 1.342(3) . ?
N2 H2 0.77(3) . ?
N3 C13 1.319(3) . ?
N3 C14 1.451(3) . ?
N3 H3 0.72(4) . ?
C1 C5 1.410(3) . ?
C1 C2 1.411(3) . ?
C1 H1 0.9500 . ?
C2 C3 1.408(3) . ?
C2 H2A 0.9500 . ?
C3 C4 1.421(3) . ?
C3 H3A 0.9500 . ?
C4 C5 1.402(4) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 C7 1.395(3) . ?
C6 C11 1.412(3) . ?
C7 C8 1.389(3) . ?
C7 H7 0.9500 . ?
C8 C9 1.394(3) . ?
C8 H8 0.9500 . ?
C9 C10 1.373(3) . ?
C9 H9 0.9500 . ?
C10 C11 1.414(3) . ?
C10 H10 0.9500 . ?
C11 C12 1.438(3) . ?
C12 H12 0.9500 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
S2 O2 1.4269(18) . ?
S2 O4 1.4397(19) . ?
S2 O3 1.4494(18) . ?
S2 C15 1.813(3) . ?
F22 C15 1.328(4) . ?
F23 C15 1.333(4) . ?
F24 C15 1.333(5) . ?
O5 C16 1.432(3) . ?
O5 C16 1.432(3) 2_656 ?
C16 C17 1.497(5) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 C17 1.434(7) 2_656 ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
O6A C21A 1.303(14) . ?
O6A C18A 1.46(2) . ?
C18A C19A 1.464(16) . ?
C18A H18A 0.9900 . ?
C18A H18B 0.9900 . ?
C19A C20A 1.570(16) . ?
C19A H19A 0.9900 . ?
C19A H19B 0.9900 . ?
C20A C21A 1.449(16) . ?
C20A H20A 0.9900 . ?
C20A H20B 0.9900 . ?
C21A H21A 0.9900 . ?
C21A H21B 0.9900 . ?
O6B C21B 1.330(19) . ?
O6B C18B 1.42(3) . ?
C18B C19B 1.445(19) . ?
C18B H18C 0.9900 . ?
C18B H18D 0.9900 . ?
C19B C20B 1.58(2) . ?
C19B H19C 0.9900 . ?
C19B H19D 0.9900 . ?
C20B C21B 1.45(2) . ?
C20B H20C 0.9900 . ?
C20B H20D 0.9900 . ?
C21B H21C 0.9900 . ?
C21B H21D 0.9900 . ?
O6C C21C 1.323(19) . ?
O6C C18C 1.38(2) . ?
C18C C19C 1.45(2) . ?
C18C H18E 0.9900 . ?
C18C H18F 0.9900 . ?
C19C C20C 1.57(2) . ?
C19C H19E 0.9900 . ?
C19C H19F 0.9900 . ?
C20C C21C 1.45(2) . ?
C20C H20E 0.9900 . ?
C20C H20F 0.9900 . ?
C21C H21E 0.9900 . ?
C21C H21F 0.9900 . ?

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
O1 Ti1 O1 77.83(6) . 2_655 ?
O1 Ti1 N1 81.00(6) . . ?
O1 Ti1 N1 126.82(6) 2_655 . ?
O1 Ti1 C3 129.74(7) . . ?
O1 Ti1 C3 142.04(7) 2_655 . ?
N1 Ti1 C3 87.19(8) . . ?
O1 Ti1 C2 94.84(7) . . ?
O1 Ti1 C2 144.65(7) 2_655 . ?
N1 Ti1 C2 84.95(8) . . ?
C3 Ti1 C2 35.24(8) . . ?
O1 Ti1 C4 140.40(8) . . ?
O1 Ti1 C4 106.54(7) 2_655 . ?
N1 Ti1 C4 120.41(8) . . ?
C3 Ti1 C4 35.56(8) . . ?
C2 Ti1 C4 58.38(8) . . ?
O1 Ti1 C1 83.54(7) . . ?
O1 Ti1 C1 110.02(7) 2_655 . ?
N1 Ti1 C1 115.29(7) . . ?
C3 Ti1 C1 58.12(9) . . ?
C2 Ti1 C1 34.68(8) . . ?
C4 Ti1 C1 57.63(9) . . ?
O1 Ti1 C5 107.78(8) . . ?
O1 Ti1 C5 91.36(7) 2_655 . ?
N1 Ti1 C5 141.70(7) . . ?
C3 Ti1 C5 58.08(8) . . ?
C2 Ti1 C5 57.62(8) . . ?
C4 Ti1 C5 34.44(9) . . ?
C1 Ti1 C5 34.35(8) . . ?
O1 Ti1 S1 134.46(5) . . ?
O1 Ti1 S1 84.33(4) 2_655 . ?
N1 Ti1 S1 76.95(5) . . ?
C3 Ti1 S1 88.53(7) . . ?
C2 Ti1 S1 121.89(6) . . ?
C4 Ti1 S1 84.79(7) . . ?
C1 Ti1 S1 141.97(6) . . ?
C5 Ti1 S1 114.25(7) . . ?
O1 Ti1 Ti1 39.13(4) . 2_655 ?
O1 Ti1 Ti1 38.78(4) 2_655 2_655 ?
N1 Ti1 Ti1 108.17(5) . 2_655 ?
C3 Ti1 Ti1 154.73(7) . 2_655 ?
C2 Ti1 Ti1 124.08(6) . 2_655 ?
C4 Ti1 Ti1 130.93(6) . 2_655 ?
C1 Ti1 Ti1 96.74(6) . 2_655 ?
C5 Ti1 Ti1 100.27(6) . 2_655 ?
S1 Ti1 Ti1 114.02(2) . 2_655 ?
C13 S1 Ti1 99.09(8) . . ?
C6 O1 Ti1 123.75(12) . . ?
C6 O1 Ti1 134.04(13) . 2_655 ?
Ti1 O1 Ti1 102.09(6) . 2_655 ?
C12 N1 N2 114.44(18) . . ?
C12 N1 Ti1 125.16(15) . . ?
N2 N1 Ti1 119.66(14) . . ?
C13 N2 N1 119.91(19) . . ?
C13 N2 H2 123(3) . . ?
N1 N2 H2 117(3) . . ?
C13 N3 C14 123.2(2) . . ?
C13 N3 H3 118(3) . . ?
C14 N3 H3 118(3) . . ?
C5 C1 C2 107.9(2) . . ?
C5 C1 Ti1 72.88(13) . . ?
C2 C1 Ti1 70.94(13) . . ?
C5 C1 H1 126.1 . . ?
C2 C1 H1 126.1 . . ?
Ti1 C1 H1 121.8 . . ?
C3 C2 C1 108.1(2) . . ?
C3 C2 Ti1 70.99(13) . . ?
C1 C2 Ti1 74.38(12) . . ?
C3 C2 H2A 126.0 . . ?
C1 C2 H2A 126.0 . . ?
Ti1 C2 H2A 120.4 . . ?
C2 C3 C4 107.9(2) . . ?
C2 C3 Ti1 73.78(12) . . ?
C4 C3 Ti1 73.72(13) . . ?
C2 C3 H3A 126.1 . . ?
C4 C3 H3A 126.1 . . ?
Ti1 C3 H3A 118.4 . . ?
C5 C4 C3 107.7(2) . . ?
C5 C4 Ti1 74.44(13) . . ?
C3 C4 Ti1 70.72(13) . . ?
C5 C4 H4 126.1 . . ?
C3 C4 H4 126.1 . . ?
Ti1 C4 H4 120.5 . . ?
C4 C5 C1 108.4(2) . . ?
C4 C5 Ti1 71.12(14) . . ?
C1 C5 Ti1 72.77(13) . . ?
C4 C5 H5 125.8 . . ?
C1 C5 H5 125.8 . . ?
Ti1 C5 H5 122.0 . . ?
O1 C6 C7 120.52(18) . . ?
O1 C6 C11 120.51(18) . . ?
C7 C6 C11 118.97(18) . . ?
C8 C7 C6 120.7(2) . . ?
C8 C7 H7 119.6 . . ?
C6 C7 H7 119.6 . . ?
C7 C8 C9 120.8(2) . . ?
C7 C8 H8 119.6 . . ?
C9 C8 H8 119.6 . . ?
C10 C9 C8 119.1(2) . . ?
C10 C9 H9 120.5 . . ?
C8 C9 H9 120.5 . . ?
C9 C10 C11 121.5(2) . . ?
C9 C10 H10 119.3 . . ?
C11 C10 H10 119.3 . . ?
C6 C11 C10 118.94(19) . . ?
C6 C11 C12 123.98(18) . . ?
C10 C11 C12 117.07(18) . . ?
N1 C12 C11 123.64(19) . . ?
N1 C12 H12 118.2 . . ?
C11 C12 H12 118.2 . . ?
N3 C13 N2 116.7(2) . . ?
N3 C13 S1 122.85(19) . . ?
N2 C13 S1 120.41(17) . . ?
N3 C14 H14A 109.5 . . ?
N3 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N3 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
O2 S2 O4 115.07(13) . . ?
O2 S2 O3 115.67(11) . . ?
O4 S2 O3 113.87(11) . . ?
O2 S2 C15 103.13(15) . . ?
O4 S2 C15 103.83(17) . . ?
O3 S2 C15 102.95(14) . . ?
F22 C15 F23 107.5(3) . . ?
F22 C15 F24 107.2(3) . . ?
F23 C15 F24 108.9(3) . . ?
F22 C15 S2 111.2(2) . . ?
F23 C15 S2 110.8(2) . . ?
F24 C15 S2 111.1(3) . . ?
C16 O5 C16 109.2(3) . 2_656 ?
O5 C16 C17 106.4(2) . . ?
O5 C16 H16A 110.5 . . ?
C17 C16 H16A 110.5 . . ?
O5 C16 H16B 110.5 . . ?
C17 C16 H16B 110.5 . . ?
H16A C16 H16B 108.6 . . ?
C17 C17 C16 105.6(2) 2_656 . ?
C17 C17 H17A 110.6 2_656 . ?
C16 C17 H17A 110.6 . . ?
C17 C17 H17B 110.6 2_656 . ?
C16 C17 H17B 110.6 . . ?
H17A C17 H17B 108.8 . . ?
C21A O6A C18A 105.1(10) . . ?
O6A C18A C19A 107.3(12) . . ?
O6A C18A H18A 110.2 . . ?
C19A C18A H18A 110.2 . . ?
O6A C18A H18B 110.2 . . ?
C19A C18A H18B 110.2 . . ?
H18A C18A H18B 108.5 . . ?
C18A C19A C20A 94.9(12) . . ?
C18A C19A H19A 112.7 . . ?
C20A C19A H19A 112.7 . . ?
C18A C19A H19B 112.7 . . ?
C20A C19A H19B 112.7 . . ?
H19A C19A H19B 110.2 . . ?
C21A C20A C19A 109.0(11) . . ?
C21A C20A H20A 109.9 . . ?
C19A C20A H20A 109.9 . . ?
C21A C20A H20B 109.9 . . ?
C19A C20A H20B 109.9 . . ?
H20A C20A H20B 108.3 . . ?
O6A C21A C20A 106.4(11) . . ?
O6A C21A H21A 110.4 . . ?
C20A C21A H21A 110.4 . . ?
O6A C21A H21B 110.4 . . ?
C20A C21A H21B 110.4 . . ?
H21A C21A H21B 108.6 . . ?
C21B O6B C18B 113.0(16) . . ?
O6B C18B C19B 106.7(18) . . ?
O6B C18B H18C 110.4 . . ?
C19B C18B H18C 110.4 . . ?
O6B C18B H18D 110.4 . . ?
C19B C18B H18D 110.4 . . ?
H18C C18B H18D 108.6 . . ?
C18B C19B C20B 100.7(15) . . ?
C18B C19B H19C 111.6 . . ?
C20B C19B H19C 111.6 . . ?
C18B C19B H19D 111.6 . . ?
C20B C19B H19D 111.6 . . ?
H19C C19B H19D 109.4 . . ?
C21B C20B C19B 107.7(15) . . ?
C21B C20B H20C 110.2 . . ?
C19B C20B H20C 110.2 . . ?
C21B C20B H20D 110.2 . . ?
C19B C20B H20D 110.2 . . ?
H20C C20B H20D 108.5 . . ?
O6B C21B C20B 104.5(17) . . ?
O6B C21B H21C 110.9 . . ?
C20B C21B H21C 110.9 . . ?
O6B C21B H21D 110.9 . . ?
C20B C21B H21D 110.9 . . ?
H21C C21B H21D 108.9 . . ?
C21C O6C C18C 120.1(16) . . ?
O6C C18C C19C 104.7(16) . . ?
O6C C18C H18E 110.8 . . ?
C19C C18C H18E 110.8 . . ?
O6C C18C H18F 110.8 . . ?
C19C C18C H18F 110.8 . . ?
H18E C18C H18F 108.9 . . ?
C18C C19C C20C 100.3(16) . . ?
C18C C19C H19E 111.7 . . ?
C20C C19C H19E 111.7 . . ?
C18C C19C H19F 111.7 . . ?
C20C C19C H19F 111.7 . . ?
H19E C19C H19F 109.5 . . ?
C21C C20C C19C 108.7(16) . . ?
C21C C20C H20E 109.9 . . ?
C19C C20C H20E 109.9 . . ?
C21C C20C H20F 109.9 . . ?
C19C C20C H20F 109.9 . . ?
H20E C20C H20F 108.3 . . ?
O6C C21C C20C 101.7(17) . . ?
O6C C21C H21E 111.4 . . ?
C20C C21C H21E 111.4 . . ?
O6C C21C H21F 111.4 . . ?
C20C C21C H21F 111.4 . . ?
H21E C21C H21F 109.3 . . ?

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
C12 N1 N2 C13 -177.5(2) . . . . ?
Ti1 N1 N2 C13 11.9(3) . . . . ?
C5 C1 C2 C3 0.5(3) . . . . ?
Ti1 C1 C2 C3 -63.44(16) . . . . ?
C5 C1 C2 Ti1 63.98(15) . . . . ?
C1 C2 C3 C4 -0.7(3) . . . . ?
Ti1 C2 C3 C4 -66.39(16) . . . . ?
C1 C2 C3 Ti1 65.66(16) . . . . ?
C2 C3 C4 C5 0.6(3) . . . . ?
Ti1 C3 C4 C5 -65.78(16) . . . . ?
C2 C3 C4 Ti1 66.43(16) . . . . ?
C3 C4 C5 C1 -0.3(3) . . . . ?
Ti1 C4 C5 C1 -63.64(16) . . . . ?
C3 C4 C5 Ti1 63.33(16) . . . . ?
C2 C1 C5 C4 -0.1(3) . . . . ?
Ti1 C1 C5 C4 62.58(16) . . . . ?
C2 C1 C5 Ti1 -62.72(15) . . . . ?
Ti1 O1 C6 C7 -138.12(17) . . . . ?
Ti1 O1 C6 C7 37.1(3) 2_655 . . . ?
Ti1 O1 C6 C11 41.3(2) . . . . ?
Ti1 O1 C6 C11 -143.45(16) 2_655 . . . ?
O1 C6 C7 C8 177.3(2) . . . . ?
C11 C6 C7 C8 -2.2(3) . . . . ?
C6 C7 C8 C9 1.0(4) . . . . ?
C7 C8 C9 C10 0.9(4) . . . . ?
C8 C9 C10 C11 -1.6(3) . . . . ?
O1 C6 C11 C10 -177.97(18) . . . . ?
C7 C6 C11 C10 1.4(3) . . . . ?
O1 C6 C11 C12 3.3(3) . . . . ?
C7 C6 C11 C12 -177.3(2) . . . . ?
C9 C10 C11 C6 0.4(3) . . . . ?
C9 C10 C11 C12 179.3(2) . . . . ?
N2 N1 C12 C11 -179.0(2) . . . . ?
Ti1 N1 C12 C11 -9.0(3) . . . . ?
C6 C11 C12 N1 -19.2(3) . . . . ?
C10 C11 C12 N1 162.0(2) . . . . ?
C14 N3 C13 N2 -176.7(3) . . . . ?
C14 N3 C13 S1 2.7(5) . . . . ?
N1 N2 C13 N3 -174.7(2) . . . . ?
N1 N2 C13 S1 5.9(3) . . . . ?
Ti1 S1 C13 N3 163.9(2) . . . . ?
Ti1 S1 C13 N2 -16.8(2) . . . . ?
O2 S2 C15 F22 179.4(3) . . . . ?
O4 S2 C15 F22 -60.2(3) . . . . ?
O3 S2 C15 F22 58.7(3) . . . . ?
O2 S2 C15 F23 -61.1(3) . . . . ?
O4 S2 C15 F23 59.3(3) . . . . ?
O3 S2 C15 F23 178.2(3) . . . . ?
O2 S2 C15 F24 60.1(3) . . . . ?
O4 S2 C15 F24 -179.6(2) . . . . ?
O3 S2 C15 F24 -60.6(3) . . . . ?
C16 O5 C16 C17 8.1(3) 2_656 . . . ?
O5 C16 C17 C17 -21.9(7) . . . 2_656 ?
C21A O6A C18A C19A 44.7(16) . . . . ?
O6A C18A C19A C20A -32.9(15) . . . . ?
C18A C19A C20A C21A 14.2(17) . . . . ?
C18A O6A C21A C20A -32.4(15) . . . . ?
C19A C20A C21A O6A 11.3(17) . . . . ?
C21B O6B C18B C19B -29(4) . . . . ?
O6B C18B C19B C20B 18(3) . . . . ?
C18B C19B C20B C21B -4(3) . . . . ?
C18B O6B C21B C20B 26(3) . . . . ?
C19B C20B C21B O6B -13(3) . . . . ?
C21C O6C C18C C19C 17(4) . . . . ?
O6C C18C C19C C20C -20(3) . . . . ?
C18C C19C C20C C21C 19(3) . . . . ?
C18C O6C C21C C20C -4(4) . . . . ?
C19C C20C C21C O6C -10(3) . . . . ?

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 H2 O4 0.77(3) 2.01(3) 2.777(3) 171(3) . yes
N3 H3 O3 0.72(4) 2.20(4) 2.909(3) 171(4) . yes

_refine_diff_density_max         1.629
_refine_diff_density_min         -0.638
_refine_diff_density_rms         0.083



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Ti1a
_database_code_depnum_ccdc_archive 'CCDC 2377765'
loop_
_audit_author_name
_audit_author_address
'Marc Schmidtmann'
;Carl von Ossietzky Universitaet Oldenburg
Germany
;
_audit_update_record             
;
2024-08-15 deposited with the CCDC.	2024-09-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_structural     Ti(C15H18)(C15H19)(C9H9N3HS)
_chemical_formula_sum            'C39 H47 N3 S Ti'
_chemical_formula_weight         637.75

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'
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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   11.6805(6)
_cell_length_b                   12.0032(6)
_cell_length_c                   12.9169(7)
_cell_angle_alpha                92.218(3)
_cell_angle_beta                 107.971(3)
_cell_angle_gamma                109.627(2)
_cell_volume                     1601.95(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9814
_cell_measurement_theta_min      2.27
_cell_measurement_theta_max      40.25

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_F_000             680
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.350
_exptl_crystal_size_min          0.250
_exptl_absorpt_coefficient_mu    0.366
_shelx_estimated_absorpt_T_min   0.868
_shelx_estimated_absorpt_T_max   0.914
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_correction_T_min  0.8918
_exptl_absorpt_correction_T_max  0.9319
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_absorpt_special_details   
;
 numerical absorption correction followed by scaling based on
 symmetry-related measurements (multi-scan)
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            100842
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         1.679
_diffrn_reflns_theta_max         40.248
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             20177
_reflns_number_gt                17407
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT V8.40B'
_computing_data_reduction        'Bruker SAINT V8.40B'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0400P)²+0.3000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         20177
_refine_ls_number_parameters     402
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0283
_refine_ls_wR_factor_ref         0.0812
_refine_ls_wR_factor_gt          0.0773
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_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_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 0.24484(2) 0.29837(2) 0.23427(2) 0.00881(2) Uani 1 1 d . . . . .
S1 S 0.33690(2) 0.25765(2) 0.08518(2) 0.01074(2) Uani 1 1 d . . . . .
N1 N 0.20847(5) 0.11085(4) 0.18171(4) 0.01137(7) Uani 1 1 d . . . . .
N2 N 0.13682(5) -0.00264(4) 0.19418(4) 0.01234(7) Uani 1 1 d . . . . .
N3 N 0.24997(5) 0.01497(4) 0.04243(4) 0.01388(8) Uani 1 1 d . . . . .
H3 H 0.2129(11) -0.0525(10) 0.0601(10) 0.024(3) Uiso 1 1 d . . . . .
C1 C 0.13525(5) 0.40594(5) 0.14413(5) 0.01183(8) Uani 1 1 d . . . . .
C2 C 0.10487(5) 0.39000(5) 0.24431(5) 0.01375(8) Uani 1 1 d . . . . .
H2 H 0.129415 0.451771 0.303971 0.017 Uiso 1 1 calc R U . . .
C3 C 0.03238(6) 0.26696(6) 0.23895(5) 0.01603(9) Uani 1 1 d . . . . .
H3A H 0.002562 0.231979 0.294987 0.019 Uiso 1 1 calc R U . . .
C4 C 0.01258(5) 0.20612(5) 0.13587(5) 0.01590(9) Uani 1 1 d . . . . .
H4 H -0.035115 0.123058 0.109914 0.019 Uiso 1 1 calc R U . . .
C5 C 0.07479(5) 0.28807(5) 0.07741(5) 0.01368(8) Uani 1 1 d . . . . .
H5 H 0.076814 0.269252 0.006033 0.016 Uiso 1 1 calc R U . . .
C6 C 0.24472(5) 0.49801(5) 0.13769(4) 0.01135(8) Uani 1 1 d . . . . .
C7 C 0.27687(6) 0.50833(5) 0.03273(5) 0.01302(8) Uani 1 1 d . . . . .
H7 H 0.247551 0.426936 -0.010632 0.016 Uiso 1 1 calc R U . . .
C8 C 0.42371(6) 0.57245(5) 0.06139(5) 0.01541(9) Uani 1 1 d . . . . .
H8A H 0.469518 0.524255 0.104503 0.018 Uiso 1 1 calc R U . . .
H8B H 0.444467 0.580120 -0.007356 0.018 Uiso 1 1 calc R U . . .
C9 C 0.46995(6) 0.69717(5) 0.12845(5) 0.01452(9) Uani 1 1 d . . . . .
H9 H 0.565283 0.737812 0.146001 0.017 Uiso 1 1 calc R U . . .
C10 C 0.43963(6) 0.68476(5) 0.23583(5) 0.01435(9) Uani 1 1 d . . . . .
H10A H 0.467966 0.765072 0.279020 0.017 Uiso 1 1 calc R U . . .
H10B H 0.486914 0.638729 0.280838 0.017 Uiso 1 1 calc R U . . .
C11 C 0.29339(6) 0.61983(5) 0.20816(5) 0.01269(8) Uani 1 1 d . . . . .
H11 H 0.272901 0.610229 0.277719 0.015 Uiso 1 1 calc R U . . .
C12 C 0.20738(6) 0.58462(5) -0.03538(5) 0.01625(9) Uani 1 1 d . . . . .
H12A H 0.227344 0.593003 -0.104450 0.020 Uiso 1 1 calc R U . . .
H12B H 0.112637 0.544486 -0.055046 0.020 Uiso 1 1 calc R U . . .
C13 C 0.39893(6) 0.77157(5) 0.06040(5) 0.01537(9) Uani 1 1 d . . . . .
H13A H 0.428297 0.852411 0.102950 0.018 Uiso 1 1 calc R U . . .
H13B H 0.419185 0.780696 -0.008496 0.018 Uiso 1 1 calc R U . . .
C14 C 0.22181(6) 0.69499(5) 0.13974(5) 0.01577(9) Uani 1 1 d . . . . .
H14A H 0.127390 0.654758 0.122114 0.019 Uiso 1 1 calc R U . . .
H14B H 0.249381 0.774972 0.183260 0.019 Uiso 1 1 calc R U . . .
C15 C 0.25268(6) 0.70891(5) 0.03266(5) 0.01521(9) Uani 1 1 d . . . . .
H15 H 0.206881 0.757895 -0.010919 0.018 Uiso 1 1 calc R U . . .
C16 C 0.44556(5) 0.28673(5) 0.36167(4) 0.01125(8) Uani 1 1 d . . . . .
C17 C 0.34785(6) 0.24493(5) 0.41040(5) 0.01375(8) Uani 1 1 d . . . . .
H17 H 0.315281 0.166319 0.426652 0.016 Uiso 1 1 calc R U . . .
C18 C 0.30749(6) 0.33948(6) 0.43050(5) 0.01543(9) Uani 1 1 d . . . . .
H18 H 0.244152 0.335948 0.463306 0.019 Uiso 1 1 calc R U . . .
C19 C 0.37801(6) 0.44043(5) 0.39319(5) 0.01382(8) Uani 1 1 d . . . . .
H19 H 0.369970 0.516567 0.395964 0.017 Uiso 1 1 calc R U . . .
C20 C 0.46258(5) 0.40804(5) 0.35103(5) 0.01193(8) Uani 1 1 d . . . . .
H20 H 0.521232 0.459073 0.320566 0.014 Uiso 1 1 calc R U . . .
C21 C 0.51857(6) 0.21581(5) 0.33070(5) 0.01319(8) Uani 1 1 d . . . . .
H21 H 0.461059 0.163520 0.258490 0.016 Uiso 1 1 calc R U . . .
C22 C 0.64448(6) 0.29515(6) 0.31422(5) 0.01723(10) Uani 1 1 d . . . . .
H22 H 0.625112 0.350942 0.261820 0.021 Uiso 1 1 calc R U . . .
C23 C 0.69838(8) 0.21353(8) 0.26556(6) 0.02545(15) Uani 1 1 d . . . . .
H23A H 0.633841 0.166389 0.194336 0.031 Uiso 1 1 calc R U . . .
H23B H 0.777649 0.262944 0.251908 0.031 Uiso 1 1 calc R U . . .
C24 C 0.72982(8) 0.12851(8) 0.34615(6) 0.02633(15) Uani 1 1 d . . . . .
H24 H 0.764903 0.075550 0.314302 0.032 Uiso 1 1 calc R U . . .
C25 C 0.60582(9) 0.05145(7) 0.36543(6) 0.02628(15) Uani 1 1 d . . . . .
H25A H 0.625045 -0.004203 0.416795 0.032 Uiso 1 1 calc R U . . .
H25B H 0.540939 0.003224 0.294763 0.032 Uiso 1 1 calc R U . . .
C26 C 0.55097(7) 0.13239(6) 0.41415(5) 0.01779(10) Uani 1 1 d . . . . .
H26 H 0.470470 0.081697 0.426865 0.021 Uiso 1 1 calc R U . . .
C27 C 0.74587(6) 0.36825(7) 0.42451(7) 0.02274(12) Uani 1 1 d . . . . .
H27A H 0.712386 0.421872 0.456029 0.027 Uiso 1 1 calc R U . . .
H27B H 0.825839 0.418427 0.412327 0.027 Uiso 1 1 calc R U . . .
C28 C 0.83046(8) 0.20169(9) 0.45633(6) 0.02987(17) Uani 1 1 d . . . . .
H28A H 0.910940 0.251280 0.444583 0.036 Uiso 1 1 calc R U . . .
H28B H 0.851348 0.147014 0.508207 0.036 Uiso 1 1 calc R U . . .
C29 C 0.65154(8) 0.20600(7) 0.52376(5) 0.02145(12) Uani 1 1 d . . . . .
H29A H 0.670498 0.151643 0.576669 0.026 Uiso 1 1 calc R U . . .
H29B H 0.616873 0.258446 0.555361 0.026 Uiso 1 1 calc R U . . .
C30 C 0.77623(7) 0.28273(8) 0.50525(6) 0.02428(13) Uani 1 1 d . . . . .
H30 H 0.841667 0.330346 0.577103 0.029 Uiso 1 1 calc R U . . .
C31 C 0.25957(5) 0.11373(4) 0.10207(4) 0.01030(7) Uani 1 1 d . . . . .
C32 C 0.30225(7) 0.01758(5) -0.04608(6) 0.01831(10) Uani 1 1 d . . . . .
H32A H 0.280947 0.075394 -0.092580 0.027 Uiso 1 1 calc R U . . .
H32B H 0.264729 -0.062223 -0.090629 0.027 Uiso 1 1 calc R U . . .
H32C H 0.396411 0.041316 -0.014854 0.027 Uiso 1 1 calc R U . . .
C33 C 0.07728(6) -0.00402(5) 0.26358(5) 0.01329(8) Uani 1 1 d . . . . .
H33 H 0.091491 0.069983 0.304153 0.016 Uiso 1 1 calc R U . . .
C34 C -0.01101(5) -0.11412(5) 0.28270(5) 0.01285(8) Uani 1 1 d . . . . .
C35 C -0.02141(6) -0.22856(5) 0.24307(5) 0.01716(10) Uani 1 1 d . . . . .
H35 H 0.032077 -0.237196 0.203292 0.021 Uiso 1 1 calc R U . . .
C36 C -0.10980(8) -0.32955(6) 0.26179(6) 0.02358(13) Uani 1 1 d . . . . .
H36 H -0.115630 -0.407012 0.235596 0.028 Uiso 1 1 calc R U . . .
C37 C -0.19001(7) -0.31797(7) 0.31879(7) 0.02569(14) Uani 1 1 d . . . . .
H37 H -0.251179 -0.387350 0.330390 0.031 Uiso 1 1 calc R U . . .
C38 C -0.18029(7) -0.20477(7) 0.35857(7) 0.02481(13) Uani 1 1 d . . . . .
H38 H -0.235014 -0.196573 0.397206 0.030 Uiso 1 1 calc R U . . .
C39 C -0.09023(7) -0.10338(6) 0.34172(6) 0.01872(10) Uani 1 1 d . . . . .
H39 H -0.082400 -0.026111 0.370535 0.022 Uiso 1 1 calc R U . . .


_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 N1 2.1839(5) . ?
Ti1 C1 2.2289(5) . ?
Ti1 C2 2.2862(6) . ?
Ti1 C5 2.3234(6) . ?
Ti1 C19 2.3490(6) . ?
Ti1 C20 2.3888(5) . ?
Ti1 C18 2.3916(6) . ?
Ti1 C3 2.4021(6) . ?
Ti1 C4 2.4386(6) . ?
Ti1 C17 2.4449(6) . ?
Ti1 C16 2.4660(5) . ?
Ti1 S1 2.58107(19) . ?
S1 C31 1.7175(5) . ?
N1 C31 1.3354(7) . ?
N1 N2 1.3843(6) . ?
N2 C33 1.2906(7) . ?
N3 C31 1.3409(7) . ?
N3 C32 1.4497(8) . ?
N3 H3 0.858(12) . ?
C1 C6 1.4094(8) . ?
C1 C2 1.4470(8) . ?
C1 C5 1.4498(8) . ?
C2 C3 1.4208(8) . ?
C2 H2 0.9500 . ?
C3 C4 1.4074(9) . ?
C3 H3A 0.9500 . ?
C4 C5 1.4078(8) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 C7 1.5135(8) . ?
C6 C11 1.5196(8) . ?
C7 C8 1.5396(9) . ?
C7 C12 1.5467(8) . ?
C7 H7 1.0000 . ?
C8 C9 1.5332(8) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.5346(9) . ?
C9 C13 1.5385(8) . ?
C9 H9 1.0000 . ?
C10 C11 1.5364(8) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C14 1.5513(8) . ?
C11 H11 1.0000 . ?
C12 C15 1.5360(8) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 C15 1.5331(9) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 C15 1.5350(9) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15 1.0000 . ?
C16 C20 1.4200(7) . ?
C16 C17 1.4261(8) . ?
C16 C21 1.5112(8) . ?
C17 C18 1.4106(8) . ?
C17 H17 0.9500 . ?
C18 C19 1.4138(9) . ?
C18 H18 0.9500 . ?
C19 C20 1.4132(8) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C21 C22 1.5438(9) . ?
C21 C26 1.5473(8) . ?
C21 H21 1.0000 . ?
C22 C23 1.5369(9) . ?
C22 C27 1.5382(10) . ?
C22 H22 1.0000 . ?
C23 C24 1.5356(10) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.5349(13) . ?
C24 C28 1.5349(12) . ?
C24 H24 1.0000 . ?
C25 C26 1.5394(9) . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C26 C29 1.5313(10) . ?
C26 H26 1.0000 . ?
C27 C30 1.5383(11) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C28 C30 1.5363(11) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 C30 1.5354(12) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30 1.0000 . ?
C32 H32A 0.9800 . ?
C32 H32B 0.9800 . ?
C32 H32C 0.9800 . ?
C33 C34 1.4621(8) . ?
C33 H33 0.9500 . ?
C34 C35 1.3997(9) . ?
C34 C39 1.4006(8) . ?
C35 C36 1.3892(9) . ?
C35 H35 0.9500 . ?
C36 C37 1.3944(12) . ?
C36 H36 0.9500 . ?
C37 C38 1.3891(12) . ?
C37 H37 0.9500 . ?
C38 C39 1.3917(9) . ?
C38 H38 0.9500 . ?
C39 H39 0.9500 . ?

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 Ti1 C1 125.75(2) . . ?
N1 Ti1 C2 130.36(2) . . ?
C1 Ti1 C2 37.36(2) . . ?
N1 Ti1 C5 88.68(2) . . ?
C1 Ti1 C5 37.07(2) . . ?
C2 Ti1 C5 59.97(2) . . ?
N1 Ti1 C19 135.433(19) . . ?
C1 Ti1 C19 98.54(2) . . ?
C2 Ti1 C19 81.03(2) . . ?
C5 Ti1 C19 135.36(2) . . ?
N1 Ti1 C20 113.261(19) . . ?
C1 Ti1 C20 116.26(2) . . ?
C2 Ti1 C20 113.11(2) . . ?
C5 Ti1 C20 147.14(2) . . ?
C19 Ti1 C20 34.69(2) . . ?
N1 Ti1 C18 110.15(2) . . ?
C1 Ti1 C18 114.34(2) . . ?
C2 Ti1 C18 81.44(2) . . ?
C5 Ti1 C18 139.56(2) . . ?
C19 Ti1 C18 34.69(2) . . ?
C20 Ti1 C18 57.13(2) . . ?
N1 Ti1 C3 96.40(2) . . ?
C1 Ti1 C3 60.38(2) . . ?
C2 Ti1 C3 35.17(2) . . ?
C5 Ti1 C3 58.03(2) . . ?
C19 Ti1 C3 102.20(2) . . ?
C20 Ti1 C3 136.63(2) . . ?
C18 Ti1 C3 83.83(2) . . ?
N1 Ti1 C4 74.49(2) . . ?
C1 Ti1 C4 59.48(2) . . ?
C2 Ti1 C4 57.77(2) . . ?
C5 Ti1 C4 34.28(2) . . ?
C19 Ti1 C4 135.49(2) . . ?
C20 Ti1 C4 170.17(2) . . ?
C18 Ti1 C4 115.28(2) . . ?
C3 Ti1 C4 33.79(2) . . ?
N1 Ti1 C17 79.883(19) . . ?
C1 Ti1 C17 148.11(2) . . ?
C2 Ti1 C17 112.83(2) . . ?
C5 Ti1 C17 156.05(2) . . ?
C19 Ti1 C17 56.85(2) . . ?
C20 Ti1 C17 56.314(19) . . ?
C18 Ti1 C17 33.89(2) . . ?
C3 Ti1 C17 102.14(2) . . ?
C4 Ti1 C17 121.78(2) . . ?
N1 Ti1 C16 81.452(18) . . ?
C1 Ti1 C16 150.220(19) . . ?
C2 Ti1 C16 135.91(2) . . ?
C5 Ti1 C16 163.67(2) . . ?
C19 Ti1 C16 57.122(19) . . ?
C20 Ti1 C16 33.968(18) . . ?
C18 Ti1 C16 56.667(19) . . ?
C3 Ti1 C16 135.78(2) . . ?
C4 Ti1 C16 149.698(19) . . ?
C17 Ti1 C16 33.760(19) . . ?
N1 Ti1 S1 63.823(13) . . ?
C1 Ti1 S1 97.409(16) . . ?
C2 Ti1 S1 134.567(16) . . ?
C5 Ti1 S1 80.501(16) . . ?
C19 Ti1 S1 120.370(16) . . ?
C20 Ti1 S1 87.523(15) . . ?
C18 Ti1 S1 139.802(15) . . ?
C3 Ti1 S1 135.120(17) . . ?
C4 Ti1 S1 101.644(17) . . ?
C17 Ti1 S1 112.248(15) . . ?
C16 Ti1 S1 83.472(14) . . ?
C31 S1 Ti1 79.540(18) . . ?
C31 N1 N2 114.93(4) . . ?
C31 N1 Ti1 104.39(3) . . ?
N2 N1 Ti1 139.81(4) . . ?
C33 N2 N1 114.45(5) . . ?
C31 N3 C32 123.52(5) . . ?
C31 N3 H3 117.0(8) . . ?
C32 N3 H3 119.4(8) . . ?
C6 C1 C2 123.79(5) . . ?
C6 C1 C5 124.96(5) . . ?
C2 C1 C5 105.37(5) . . ?
C6 C1 Ti1 95.26(3) . . ?
C2 C1 Ti1 73.47(3) . . ?
C5 C1 Ti1 75.01(3) . . ?
C3 C2 C1 108.93(5) . . ?
C3 C2 Ti1 76.87(3) . . ?
C1 C2 Ti1 69.17(3) . . ?
C3 C2 H2 125.5 . . ?
C1 C2 H2 125.5 . . ?
Ti1 C2 H2 120.1 . . ?
C4 C3 C2 107.86(5) . . ?
C4 C3 Ti1 74.53(3) . . ?
C2 C3 Ti1 67.96(3) . . ?
C4 C3 H3A 126.1 . . ?
C2 C3 H3A 126.1 . . ?
Ti1 C3 H3A 123.0 . . ?
C3 C4 C5 109.08(5) . . ?
C3 C4 Ti1 71.68(3) . . ?
C5 C4 Ti1 68.37(3) . . ?
C3 C4 H4 125.5 . . ?
C5 C4 H4 125.5 . . ?
Ti1 C4 H4 126.1 . . ?
C4 C5 C1 108.73(5) . . ?
C4 C5 Ti1 77.34(3) . . ?
C1 C5 Ti1 67.92(3) . . ?
C4 C5 H5 125.6 . . ?
C1 C5 H5 125.6 . . ?
Ti1 C5 H5 120.7 . . ?
C1 C6 C7 122.31(5) . . ?
C1 C6 C11 119.34(5) . . ?
C7 C6 C11 111.50(4) . . ?
C6 C7 C8 109.61(5) . . ?
C6 C7 C12 108.28(5) . . ?
C8 C7 C12 108.60(5) . . ?
C6 C7 H7 110.1 . . ?
C8 C7 H7 110.1 . . ?
C12 C7 H7 110.1 . . ?
C9 C8 C7 110.59(5) . . ?
C9 C8 H8A 109.5 . . ?
C7 C8 H8A 109.5 . . ?
C9 C8 H8B 109.5 . . ?
C7 C8 H8B 109.5 . . ?
H8A C8 H8B 108.1 . . ?
C8 C9 C10 109.37(5) . . ?
C8 C9 C13 109.10(5) . . ?
C10 C9 C13 109.48(5) . . ?
C8 C9 H9 109.6 . . ?
C10 C9 H9 109.6 . . ?
C13 C9 H9 109.6 . . ?
C9 C10 C11 109.29(5) . . ?
C9 C10 H10A 109.8 . . ?
C11 C10 H10A 109.8 . . ?
C9 C10 H10B 109.8 . . ?
C11 C10 H10B 109.8 . . ?
H10A C10 H10B 108.3 . . ?
C6 C11 C10 111.57(5) . . ?
C6 C11 C14 106.92(5) . . ?
C10 C11 C14 108.78(5) . . ?
C6 C11 H11 109.8 . . ?
C10 C11 H11 109.8 . . ?
C14 C11 H11 109.8 . . ?
C15 C12 C7 109.44(5) . . ?
C15 C12 H12A 109.8 . . ?
C7 C12 H12A 109.8 . . ?
C15 C12 H12B 109.8 . . ?
C7 C12 H12B 109.8 . . ?
H12A C12 H12B 108.2 . . ?
C15 C13 C9 109.70(5) . . ?
C15 C13 H13A 109.7 . . ?
C9 C13 H13A 109.7 . . ?
C15 C13 H13B 109.7 . . ?
C9 C13 H13B 109.7 . . ?
H13A C13 H13B 108.2 . . ?
C15 C14 C11 109.75(5) . . ?
C15 C14 H14A 109.7 . . ?
C11 C14 H14A 109.7 . . ?
C15 C14 H14B 109.7 . . ?
C11 C14 H14B 109.7 . . ?
H14A C14 H14B 108.2 . . ?
C13 C15 C14 109.52(5) . . ?
C13 C15 C12 109.43(5) . . ?
C14 C15 C12 109.42(5) . . ?
C13 C15 H15 109.5 . . ?
C14 C15 H15 109.5 . . ?
C12 C15 H15 109.5 . . ?
C20 C16 C17 106.57(5) . . ?
C20 C16 C21 127.17(5) . . ?
C17 C16 C21 126.24(5) . . ?
C20 C16 Ti1 70.03(3) . . ?
C17 C16 Ti1 72.31(3) . . ?
C21 C16 Ti1 123.91(4) . . ?
C18 C17 C16 108.79(5) . . ?
C18 C17 Ti1 70.98(3) . . ?
C16 C17 Ti1 73.93(3) . . ?
C18 C17 H17 125.6 . . ?
C16 C17 H17 125.6 . . ?
Ti1 C17 H17 121.2 . . ?
C17 C18 C19 107.89(5) . . ?
C17 C18 Ti1 75.12(3) . . ?
C19 C18 Ti1 71.01(3) . . ?
C17 C18 H18 126.1 . . ?
C19 C18 H18 126.1 . . ?
Ti1 C18 H18 119.6 . . ?
C20 C19 C18 107.90(5) . . ?
C20 C19 Ti1 74.19(3) . . ?
C18 C19 Ti1 74.30(3) . . ?
C20 C19 H19 126.0 . . ?
C18 C19 H19 126.1 . . ?
Ti1 C19 H19 117.5 . . ?
C19 C20 C16 108.85(5) . . ?
C19 C20 Ti1 71.11(3) . . ?
C16 C20 Ti1 76.00(3) . . ?
C19 C20 H20 125.6 . . ?
C16 C20 H20 125.6 . . ?
Ti1 C20 H20 119.1 . . ?
C16 C21 C22 113.27(5) . . ?
C16 C21 C26 113.23(5) . . ?
C22 C21 C26 108.68(5) . . ?
C16 C21 H21 107.1 . . ?
C22 C21 H21 107.1 . . ?
C26 C21 H21 107.1 . . ?
C23 C22 C27 109.19(5) . . ?
C23 C22 C21 108.45(6) . . ?
C27 C22 C21 110.92(5) . . ?
C23 C22 H22 109.4 . . ?
C27 C22 H22 109.4 . . ?
C21 C22 H22 109.4 . . ?
C24 C23 C22 109.74(5) . . ?
C24 C23 H23A 109.7 . . ?
C22 C23 H23A 109.7 . . ?
C24 C23 H23B 109.7 . . ?
C22 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
C25 C24 C28 109.34(6) . . ?
C25 C24 C23 109.14(6) . . ?
C28 C24 C23 109.67(8) . . ?
C25 C24 H24 109.6 . . ?
C28 C24 H24 109.6 . . ?
C23 C24 H24 109.6 . . ?
C24 C25 C26 109.88(6) . . ?
C24 C25 H25A 109.7 . . ?
C26 C25 H25A 109.7 . . ?
C24 C25 H25B 109.7 . . ?
C26 C25 H25B 109.7 . . ?
H25A C25 H25B 108.2 . . ?
C29 C26 C25 109.34(6) . . ?
C29 C26 C21 110.52(5) . . ?
C25 C26 C21 108.41(5) . . ?
C29 C26 H26 109.5 . . ?
C25 C26 H26 109.5 . . ?
C21 C26 H26 109.5 . . ?
C22 C27 C30 109.59(6) . . ?
C22 C27 H27A 109.8 . . ?
C30 C27 H27A 109.8 . . ?
C22 C27 H27B 109.8 . . ?
C30 C27 H27B 109.8 . . ?
H27A C27 H27B 108.2 . . ?
C24 C28 C30 109.47(6) . . ?
C24 C28 H28A 109.8 . . ?
C30 C28 H28A 109.8 . . ?
C24 C28 H28B 109.8 . . ?
C30 C28 H28B 109.8 . . ?
H28A C28 H28B 108.2 . . ?
C26 C29 C30 109.86(5) . . ?
C26 C29 H29A 109.7 . . ?
C30 C29 H29A 109.7 . . ?
C26 C29 H29B 109.7 . . ?
C30 C29 H29B 109.7 . . ?
H29A C29 H29B 108.2 . . ?
C29 C30 C28 109.87(7) . . ?
C29 C30 C27 109.16(5) . . ?
C28 C30 C27 109.21(6) . . ?
C29 C30 H30 109.5 . . ?
C28 C30 H30 109.5 . . ?
C27 C30 H30 109.5 . . ?
N1 C31 N3 123.32(5) . . ?
N1 C31 S1 112.09(4) . . ?
N3 C31 S1 124.60(4) . . ?
N3 C32 H32A 109.5 . . ?
N3 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
N3 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
N2 C33 C34 123.09(5) . . ?
N2 C33 H33 118.5 . . ?
C34 C33 H33 118.5 . . ?
C35 C34 C39 119.02(5) . . ?
C35 C34 C33 123.11(5) . . ?
C39 C34 C33 117.86(5) . . ?
C36 C35 C34 120.12(6) . . ?
C36 C35 H35 119.9 . . ?
C34 C35 H35 119.9 . . ?
C35 C36 C37 120.43(7) . . ?
C35 C36 H36 119.8 . . ?
C37 C36 H36 119.8 . . ?
C38 C37 C36 119.86(6) . . ?
C38 C37 H37 120.1 . . ?
C36 C37 H37 120.1 . . ?
C37 C38 C39 119.86(7) . . ?
C37 C38 H38 120.1 . . ?
C39 C38 H38 120.1 . . ?
C38 C39 C34 120.67(6) . . ?
C38 C39 H39 119.7 . . ?
C34 C39 H39 119.7 . . ?

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
C31 N1 N2 C33 -173.42(5) . . . . ?
Ti1 N1 N2 C33 -6.32(8) . . . . ?
C6 C1 C2 C3 -152.42(5) . . . . ?
C5 C1 C2 C3 1.60(6) . . . . ?
Ti1 C1 C2 C3 -67.21(4) . . . . ?
C6 C1 C2 Ti1 -85.21(5) . . . . ?
C5 C1 C2 Ti1 68.82(4) . . . . ?
C1 C2 C3 C4 -2.12(7) . . . . ?
Ti1 C2 C3 C4 -64.35(4) . . . . ?
C1 C2 C3 Ti1 62.23(4) . . . . ?
C2 C3 C4 C5 1.79(7) . . . . ?
Ti1 C3 C4 C5 -58.31(4) . . . . ?
C2 C3 C4 Ti1 60.11(4) . . . . ?
C3 C4 C5 C1 -0.79(7) . . . . ?
Ti1 C4 C5 C1 -61.13(4) . . . . ?
C3 C4 C5 Ti1 60.34(4) . . . . ?
C6 C1 C5 C4 153.13(5) . . . . ?
C2 C1 C5 C4 -0.51(6) . . . . ?
Ti1 C1 C5 C4 67.22(4) . . . . ?
C6 C1 C5 Ti1 85.91(5) . . . . ?
C2 C1 C5 Ti1 -67.73(4) . . . . ?
C2 C1 C6 C7 176.97(5) . . . . ?
C5 C1 C6 C7 27.98(8) . . . . ?
Ti1 C1 C6 C7 103.35(5) . . . . ?
C2 C1 C6 C11 -34.51(8) . . . . ?
C5 C1 C6 C11 176.51(5) . . . . ?
Ti1 C1 C6 C11 -108.12(5) . . . . ?
C1 C6 C7 C8 -153.11(5) . . . . ?
C11 C6 C7 C8 56.18(6) . . . . ?
C1 C6 C7 C12 88.58(6) . . . . ?
C11 C6 C7 C12 -62.14(6) . . . . ?
C6 C7 C8 C9 -58.43(6) . . . . ?
C12 C7 C8 C9 59.68(6) . . . . ?
C7 C8 C9 C10 60.13(6) . . . . ?
C7 C8 C9 C13 -59.60(6) . . . . ?
C8 C9 C10 C11 -58.56(6) . . . . ?
C13 C9 C10 C11 60.93(6) . . . . ?
C1 C6 C11 C10 151.79(5) . . . . ?
C7 C6 C11 C10 -56.53(6) . . . . ?
C1 C6 C11 C14 -89.39(6) . . . . ?
C7 C6 C11 C14 62.30(6) . . . . ?
C9 C10 C11 C6 57.10(6) . . . . ?
C9 C10 C11 C14 -60.61(6) . . . . ?
C6 C7 C12 C15 59.15(6) . . . . ?
C8 C7 C12 C15 -59.80(6) . . . . ?
C8 C9 C13 C15 59.52(6) . . . . ?
C10 C9 C13 C15 -60.14(6) . . . . ?
C6 C11 C14 C15 -60.50(6) . . . . ?
C10 C11 C14 C15 60.12(6) . . . . ?
C9 C13 C15 C14 59.39(6) . . . . ?
C9 C13 C15 C12 -60.55(6) . . . . ?
C11 C14 C15 C13 -59.54(6) . . . . ?
C11 C14 C15 C12 60.41(6) . . . . ?
C7 C12 C15 C13 60.77(6) . . . . ?
C7 C12 C15 C14 -59.22(6) . . . . ?
C20 C16 C17 C18 -0.82(6) . . . . ?
C21 C16 C17 C18 177.65(5) . . . . ?
Ti1 C16 C17 C18 -62.86(4) . . . . ?
C20 C16 C17 Ti1 62.04(4) . . . . ?
C21 C16 C17 Ti1 -119.48(5) . . . . ?
C16 C17 C18 C19 0.83(7) . . . . ?
Ti1 C17 C18 C19 -63.92(4) . . . . ?
C16 C17 C18 Ti1 64.76(4) . . . . ?
C17 C18 C19 C20 -0.52(7) . . . . ?
Ti1 C18 C19 C20 -67.16(4) . . . . ?
C17 C18 C19 Ti1 66.65(4) . . . . ?
C18 C19 C20 C16 0.01(6) . . . . ?
Ti1 C19 C20 C16 -67.23(4) . . . . ?
C18 C19 C20 Ti1 67.24(4) . . . . ?
C17 C16 C20 C19 0.50(6) . . . . ?
C21 C16 C20 C19 -177.96(5) . . . . ?
Ti1 C16 C20 C19 64.05(4) . . . . ?
C17 C16 C20 Ti1 -63.55(4) . . . . ?
C21 C16 C20 Ti1 118.00(5) . . . . ?
C20 C16 C21 C22 16.18(8) . . . . ?
C17 C16 C21 C22 -161.99(5) . . . . ?
Ti1 C16 C21 C22 105.80(5) . . . . ?
C20 C16 C21 C26 140.51(6) . . . . ?
C17 C16 C21 C26 -37.65(8) . . . . ?
Ti1 C16 C21 C26 -129.87(5) . . . . ?
C16 C21 C22 C23 -171.13(5) . . . . ?
C26 C21 C22 C23 62.10(6) . . . . ?
C16 C21 C22 C27 68.98(6) . . . . ?
C26 C21 C22 C27 -57.79(6) . . . . ?
C27 C22 C23 C24 59.63(9) . . . . ?
C21 C22 C23 C24 -61.34(8) . . . . ?
C22 C23 C24 C25 60.06(9) . . . . ?
C22 C23 C24 C28 -59.69(9) . . . . ?
C28 C24 C25 C26 60.09(7) . . . . ?
C23 C24 C25 C26 -59.87(8) . . . . ?
C24 C25 C26 C29 -59.72(7) . . . . ?
C24 C25 C26 C21 60.83(7) . . . . ?
C16 C21 C26 C29 -68.77(7) . . . . ?
C22 C21 C26 C29 58.02(7) . . . . ?
C16 C21 C26 C25 171.40(6) . . . . ?
C22 C21 C26 C25 -61.80(7) . . . . ?
C23 C22 C27 C30 -60.11(7) . . . . ?
C21 C22 C27 C30 59.35(7) . . . . ?
C25 C24 C28 C30 -59.77(9) . . . . ?
C23 C24 C28 C30 59.86(9) . . . . ?
C25 C26 C29 C30 59.16(7) . . . . ?
C21 C26 C29 C30 -60.10(7) . . . . ?
C26 C29 C30 C28 -59.41(7) . . . . ?
C26 C29 C30 C27 60.32(7) . . . . ?
C24 C28 C30 C29 59.55(9) . . . . ?
C24 C28 C30 C27 -60.16(9) . . . . ?
C22 C27 C30 C29 -59.68(7) . . . . ?
C22 C27 C30 C28 60.46(8) . . . . ?
N2 N1 C31 N3 -3.94(8) . . . . ?
Ti1 N1 C31 N3 -175.39(5) . . . . ?
N2 N1 C31 S1 175.60(4) . . . . ?
Ti1 N1 C31 S1 4.15(4) . . . . ?
C32 N3 C31 N1 178.28(6) . . . . ?
C32 N3 C31 S1 -1.21(9) . . . . ?
Ti1 S1 C31 N1 -3.46(4) . . . . ?
Ti1 S1 C31 N3 176.08(5) . . . . ?
N1 N2 C33 C34 175.35(5) . . . . ?
N2 C33 C34 C35 11.82(9) . . . . ?
N2 C33 C34 C39 -166.90(6) . . . . ?
C39 C34 C35 C36 0.38(10) . . . . ?
C33 C34 C35 C36 -178.32(6) . . . . ?
C34 C35 C36 C37 0.86(11) . . . . ?
C35 C36 C37 C38 -0.95(12) . . . . ?
C36 C37 C38 C39 -0.22(12) . . . . ?
C37 C38 C39 C34 1.49(12) . . . . ?
C35 C34 C39 C38 -1.56(10) . . . . ?
C33 C34 C39 C38 177.21(6) . . . . ?

_refine_diff_density_max         0.604
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.059



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Ti1c
_database_code_depnum_ccdc_archive 'CCDC 2377767'
loop_
_audit_author_name
_audit_author_address
'Marc Schmidtmann'
;Carl von Ossietzky Universitaet Oldenburg
Germany
;
_audit_update_record             
;
2024-08-15 deposited with the CCDC.	2024-09-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/3
_shelx_SHELXL_version_number     2019/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_structural     'Ti(C15H18)(C15H19)(C8H9N4S) *C6H6'
_chemical_formula_sum            'C44 H52 N4 S Ti'
_chemical_formula_weight         716.85

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'
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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_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.
;

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'
'-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                   23.3583(14)
_cell_length_b                   10.5011(5)
_cell_length_c                   30.2781(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     7426.8(7)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9880
_cell_measurement_theta_min      2.20
_cell_measurement_theta_max      27.07

_exptl_crystal_description       rod
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_F_000             3056
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    0.324
_shelx_estimated_absorpt_T_min   0.923
_shelx_estimated_absorpt_T_max   0.994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9099
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'I\mS microfocus'
_diffrn_measurement_device_type  'Bruker Photon III CPAD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            134443
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_av_R_equivalents  0.0786
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_theta_min         1.345
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             8197
_reflns_number_gt                7084
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT V8.40B'
_computing_data_reduction        'Bruker SAINT V8.40B'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0300P)²+8.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         8197
_refine_ls_number_parameters     456
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0449
_refine_ls_wR_factor_ref         0.0954
_refine_ls_wR_factor_gt          0.0909
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.085
_refine_ls_shift/su_max          0.002
_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_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 0.65408(2) 0.67033(3) 0.68514(2) 0.01114(8) Uani 1 1 d . . . . .
S1 S 0.59735(2) 0.45931(4) 0.68354(2) 0.01467(10) Uani 1 1 d . . . . .
N1 N 0.67338(6) 0.53727(14) 0.63005(5) 0.0137(3) Uani 1 1 d . . . . .
N2 N 0.70653(6) 0.52449(14) 0.59285(5) 0.0139(3) Uani 1 1 d . . . . .
N3 N 0.63772(7) 0.33247(15) 0.61271(5) 0.0162(3) Uani 1 1 d . . . . .
H3 H 0.6601(10) 0.326(2) 0.5905(8) 0.021(6) Uiso 1 1 d . . . . .
N4 N 0.80766(7) 0.71504(15) 0.53490(5) 0.0178(3) Uani 1 1 d . . . . .
C1 C 0.69020(7) 0.64444(17) 0.75234(6) 0.0126(3) Uani 1 1 d . . . . .
C2 C 0.71175(7) 0.76390(17) 0.73652(6) 0.0141(4) Uani 1 1 d . . . . .
H2 H 0.702139 0.845297 0.748034 0.017 Uiso 1 1 calc R U . . .
C3 C 0.74999(8) 0.74058(18) 0.70066(6) 0.0171(4) Uani 1 1 d . . . . .
H3A H 0.769220 0.803356 0.683613 0.020 Uiso 1 1 calc R U . . .
C4 C 0.75406(8) 0.60884(19) 0.69513(6) 0.0172(4) Uani 1 1 d . . . . .
H4 H 0.777563 0.566757 0.674093 0.021 Uiso 1 1 calc R U . . .
C5 C 0.71792(7) 0.54876(18) 0.72559(6) 0.0150(4) Uani 1 1 d . . . . .
H5 H 0.712504 0.459424 0.728221 0.018 Uiso 1 1 calc R U . . .
C6 C 0.63729(7) 0.62422(17) 0.77366(6) 0.0133(3) Uani 1 1 d . . . . .
C7 C 0.62315(8) 0.49131(17) 0.79042(6) 0.0156(4) Uani 1 1 d . . . . .
H7 H 0.639398 0.425902 0.769945 0.019 Uiso 1 1 calc R U . . .
C8 C 0.55845(8) 0.47152(19) 0.79533(6) 0.0197(4) Uani 1 1 d . . . . .
H8A H 0.539841 0.477815 0.766030 0.024 Uiso 1 1 calc R U . . .
H8B H 0.550818 0.385539 0.807377 0.024 Uiso 1 1 calc R U . . .
C9 C 0.53357(8) 0.57254(19) 0.82638(6) 0.0216(4) Uani 1 1 d . . . . .
H9 H 0.491333 0.559621 0.829382 0.026 Uiso 1 1 calc R U . . .
C10 C 0.54543(8) 0.70492(19) 0.80715(6) 0.0194(4) Uani 1 1 d . . . . .
H10A H 0.529163 0.770813 0.826878 0.023 Uiso 1 1 calc R U . . .
H10B H 0.526720 0.712796 0.777939 0.023 Uiso 1 1 calc R U . . .
C11 C 0.61021(8) 0.72618(17) 0.80219(6) 0.0154(4) Uani 1 1 d . . . . .
H11 H 0.617824 0.812323 0.789395 0.018 Uiso 1 1 calc R U . . .
C12 C 0.65146(9) 0.47939(19) 0.83656(6) 0.0213(4) Uani 1 1 d . . . . .
H12A H 0.643915 0.393771 0.848950 0.026 Uiso 1 1 calc R U . . .
H12B H 0.693415 0.490365 0.833879 0.026 Uiso 1 1 calc R U . . .
C13 C 0.56209(9) 0.5612(2) 0.87187(7) 0.0261(5) Uani 1 1 d . . . . .
H13A H 0.545812 0.625589 0.892170 0.031 Uiso 1 1 calc R U . . .
H13B H 0.554531 0.475753 0.884411 0.031 Uiso 1 1 calc R U . . .
C14 C 0.63829(9) 0.71482(19) 0.84849(6) 0.0201(4) Uani 1 1 d . . . . .
H14A H 0.680061 0.729241 0.846094 0.024 Uiso 1 1 calc R U . . .
H14B H 0.622198 0.780265 0.868486 0.024 Uiso 1 1 calc R U . . .
C15 C 0.62687(9) 0.5817(2) 0.86739(6) 0.0238(4) Uani 1 1 d . . . . .
H15 H 0.645219 0.574326 0.897120 0.029 Uiso 1 1 calc R U . . .
C16 C 0.60492(7) 0.77536(17) 0.62241(6) 0.0138(3) Uani 1 1 d . . . . .
C17 C 0.64524(8) 0.85982(17) 0.64163(6) 0.0161(4) Uani 1 1 d . . . . .
H17 H 0.678514 0.892564 0.627609 0.019 Uiso 1 1 calc R U . . .
C18 C 0.62728(8) 0.88698(17) 0.68544(6) 0.0177(4) Uani 1 1 d . . . . .
H18 H 0.645467 0.943964 0.705373 0.021 Uiso 1 1 calc R U . . .
C19 C 0.57794(8) 0.81484(18) 0.69414(6) 0.0172(4) Uani 1 1 d . . . . .
H19 H 0.557337 0.812822 0.721181 0.021 Uiso 1 1 calc R U . . .
C20 C 0.56441(8) 0.74580(18) 0.65548(6) 0.0159(4) Uani 1 1 d . . . . .
H20 H 0.533133 0.688731 0.652257 0.019 Uiso 1 1 calc R U . . .
C21 C 0.60607(8) 0.73354(17) 0.57483(6) 0.0147(4) Uani 1 1 d . . . . .
H21 H 0.643813 0.690851 0.569971 0.018 Uiso 1 1 calc R U . . .
C22 C 0.55964(8) 0.63656(18) 0.56180(6) 0.0170(4) Uani 1 1 d . . . . .
H22 H 0.559974 0.564001 0.583185 0.020 Uiso 1 1 calc R U . . .
C23 C 0.57429(9) 0.5870(2) 0.51538(6) 0.0237(4) Uani 1 1 d . . . . .
H23A H 0.546253 0.521168 0.506482 0.028 Uiso 1 1 calc R U . . .
H23B H 0.612834 0.547823 0.515572 0.028 Uiso 1 1 calc R U . . .
C24 C 0.57293(9) 0.6981(2) 0.48216(6) 0.0233(4) Uani 1 1 d . . . . .
H24 H 0.582093 0.665600 0.451930 0.028 Uiso 1 1 calc R U . . .
C25 C 0.61705(9) 0.7985(2) 0.49561(6) 0.0233(4) Uani 1 1 d . . . . .
H25A H 0.616118 0.870319 0.474441 0.028 Uiso 1 1 calc R U . . .
H25B H 0.655905 0.760879 0.495024 0.028 Uiso 1 1 calc R U . . .
C26 C 0.60351(8) 0.84732(18) 0.54241(6) 0.0174(4) Uani 1 1 d . . . . .
H26 H 0.632508 0.912621 0.551207 0.021 Uiso 1 1 calc R U . . .
C27 C 0.49964(8) 0.69739(19) 0.56104(6) 0.0181(4) Uani 1 1 d . . . . .
H27A H 0.470908 0.633035 0.552118 0.022 Uiso 1 1 calc R U . . .
H27B H 0.489598 0.728243 0.590953 0.022 Uiso 1 1 calc R U . . .
C28 C 0.51306(9) 0.7590(2) 0.48205(6) 0.0232(4) Uani 1 1 d . . . . .
H28A H 0.512018 0.830204 0.460622 0.028 Uiso 1 1 calc R U . . .
H28B H 0.484198 0.695168 0.472975 0.028 Uiso 1 1 calc R U . . .
C29 C 0.54364(8) 0.90728(18) 0.54273(6) 0.0197(4) Uani 1 1 d . . . . .
H29A H 0.534563 0.938338 0.572796 0.024 Uiso 1 1 calc R U . . .
H29B H 0.542728 0.980930 0.522331 0.024 Uiso 1 1 calc R U . . .
C30 C 0.49891(8) 0.80874(19) 0.52842(6) 0.0196(4) Uani 1 1 d . . . . .
H30 H 0.460083 0.848867 0.528273 0.024 Uiso 1 1 calc R U . . .
C31 C 0.63880(7) 0.43671(17) 0.63758(6) 0.0135(3) Uani 1 1 d . . . . .
C32 C 0.60048(9) 0.22483(19) 0.62215(7) 0.0236(4) Uani 1 1 d . . . . .
H32A H 0.607110 0.157528 0.600316 0.035 Uiso 1 1 calc R U . . .
H32B H 0.560423 0.252307 0.620708 0.035 Uiso 1 1 calc R U . . .
H32C H 0.608802 0.192130 0.651773 0.035 Uiso 1 1 calc R U . . .
C33 C 0.74060(7) 0.61695(18) 0.58360(6) 0.0149(4) Uani 1 1 d . . . . .
H33 H 0.746510 0.683559 0.604332 0.018 Uiso 1 1 calc R U . . .
C34 C 0.77024(7) 0.61916(17) 0.54097(6) 0.0148(4) Uani 1 1 d . . . . .
C35 C 0.75784(8) 0.5310(2) 0.50774(6) 0.0210(4) Uani 1 1 d . . . . .
H35 H 0.732026 0.462805 0.513045 0.025 Uiso 1 1 calc R U . . .
C36 C 0.78380(9) 0.5449(2) 0.46704(7) 0.0268(5) Uani 1 1 d . . . . .
H36 H 0.775252 0.487498 0.443705 0.032 Uiso 1 1 calc R U . . .
C37 C 0.82244(9) 0.6433(2) 0.46056(7) 0.0270(5) Uani 1 1 d . . . . .
H37 H 0.840992 0.654411 0.432901 0.032 Uiso 1 1 calc R U . . .
C38 C 0.83324(9) 0.7247(2) 0.49526(7) 0.0228(4) Uani 1 1 d . . . . .
H38 H 0.860220 0.791229 0.490957 0.027 Uiso 1 1 calc R U . . .
C39 C 0.42657(10) 0.5433(2) 0.65289(9) 0.0359(6) Uani 1 1 d . . . . .
H39 H 0.457824 0.509252 0.636657 0.043 Uiso 1 1 calc R U . . .
C40 C 0.37486(12) 0.5591(2) 0.63258(10) 0.0422(6) Uani 1 1 d . . . . .
H40 H 0.370494 0.536808 0.602353 0.051 Uiso 1 1 calc R U . . .
C41 C 0.32953(11) 0.6067(3) 0.65556(12) 0.0512(8) Uani 1 1 d . . . . .
H41 H 0.293498 0.616311 0.641397 0.061 Uiso 1 1 calc R U . . .
C42 C 0.33559(13) 0.6408(3) 0.69908(12) 0.0549(9) Uani 1 1 d . . . . .
H42 H 0.303882 0.674437 0.714896 0.066 Uiso 1 1 calc R U . . .
C43 C 0.38816(15) 0.6262(2) 0.71998(9) 0.0511(8) Uani 1 1 d . . . . .
H43 H 0.392793 0.650218 0.750018 0.061 Uiso 1 1 calc R U . . .
C44 C 0.43404(11) 0.5758(2) 0.69620(9) 0.0401(6) Uani 1 1 d . . . . .
H44 H 0.470180 0.564107 0.710011 0.048 Uiso 1 1 calc R U . . .


_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 C1 2.2193(17) . ?
Ti1 N1 2.2222(15) . ?
Ti1 C2 2.2804(18) . ?
Ti1 C5 2.3136(18) . ?
Ti1 C19 2.3536(18) . ?
Ti1 C18 2.3596(18) . ?
Ti1 C17 2.3954(18) . ?
Ti1 C3 2.4051(19) . ?
Ti1 C20 2.4127(18) . ?
Ti1 C4 2.4418(18) . ?
Ti1 C16 2.4784(18) . ?
Ti1 S1 2.5823(5) . ?
Ti1 C6 2.7516(18) . ?
S1 C31 1.7118(18) . ?
N1 C31 1.349(2) . ?
N1 N2 1.374(2) . ?
N2 C33 1.286(2) . ?
N3 C31 1.329(2) . ?
N3 C32 1.455(2) . ?
N3 H3 0.85(2) . ?
N4 C38 1.345(2) . ?
N4 C34 1.346(2) . ?
C1 C6 1.410(2) . ?
C1 C2 1.434(2) . ?
C1 C5 1.444(2) . ?
C2 C3 1.427(2) . ?
C2 H2 0.9500 . ?
C3 C4 1.397(3) . ?
C3 H3A 0.9500 . ?
C4 C5 1.400(3) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 C11 1.514(2) . ?
C6 C7 1.521(2) . ?
C7 C8 1.533(3) . ?
C7 C12 1.551(3) . ?
C7 H7 1.0000 . ?
C8 C9 1.532(3) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.532(3) . ?
C9 C13 1.535(3) . ?
C9 H9 1.0000 . ?
C10 C11 1.537(3) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C14 1.552(3) . ?
C11 H11 1.0000 . ?
C12 C15 1.535(3) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 C15 1.534(3) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 C15 1.533(3) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15 1.0000 . ?
C16 C20 1.412(2) . ?
C16 C17 1.419(3) . ?
C16 C21 1.506(2) . ?
C17 C18 1.420(3) . ?
C17 H17 0.9500 . ?
C18 C19 1.404(3) . ?
C18 H18 0.9500 . ?
C19 C20 1.413(3) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C21 C22 1.539(3) . ?
C21 C26 1.547(2) . ?
C21 H21 1.0000 . ?
C22 C23 1.537(3) . ?
C22 C27 1.540(3) . ?
C22 H22 1.0000 . ?
C23 C24 1.540(3) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.530(3) . ?
C24 C28 1.538(3) . ?
C24 H24 1.0000 . ?
C25 C26 1.540(3) . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C26 C29 1.534(3) . ?
C26 H26 1.0000 . ?
C27 C30 1.531(3) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C28 C30 1.534(3) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 C30 1.533(3) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30 1.0000 . ?
C32 H32A 0.9800 . ?
C32 H32B 0.9800 . ?
C32 H32C 0.9800 . ?
C33 C34 1.465(2) . ?
C33 H33 0.9500 . ?
C34 C35 1.398(3) . ?
C35 C36 1.381(3) . ?
C35 H35 0.9500 . ?
C36 C37 1.386(3) . ?
C36 H36 0.9500 . ?
C37 C38 1.378(3) . ?
C37 H37 0.9500 . ?
C38 H38 0.9500 . ?
C39 C40 1.365(4) . ?
C39 C44 1.366(4) . ?
C39 H39 0.9500 . ?
C40 C41 1.362(4) . ?
C40 H40 0.9500 . ?
C41 C42 1.373(5) . ?
C41 H41 0.9500 . ?
C42 C43 1.390(5) . ?
C42 H42 0.9500 . ?
C43 C44 1.396(4) . ?
C43 H43 0.9500 . ?
C44 H44 0.9500 . ?

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
C1 Ti1 N1 122.27(6) . . ?
C1 Ti1 C2 37.14(6) . . ?
N1 Ti1 C2 131.54(6) . . ?
C1 Ti1 C5 37.07(6) . . ?
N1 Ti1 C5 85.39(6) . . ?
C2 Ti1 C5 59.73(6) . . ?
C1 Ti1 C19 105.09(6) . . ?
N1 Ti1 C19 130.21(6) . . ?
C2 Ti1 C19 95.14(7) . . ?
C5 Ti1 C19 141.40(6) . . ?
C1 Ti1 C18 102.44(7) . . ?
N1 Ti1 C18 131.53(6) . . ?
C2 Ti1 C18 74.85(7) . . ?
C5 Ti1 C18 134.50(7) . . ?
C19 Ti1 C18 34.67(7) . . ?
C1 Ti1 C17 129.70(6) . . ?
N1 Ti1 C17 97.29(6) . . ?
C2 Ti1 C17 93.91(6) . . ?
C5 Ti1 C17 143.61(7) . . ?
C19 Ti1 C17 57.52(6) . . ?
C18 Ti1 C17 34.75(6) . . ?
C1 Ti1 C3 60.29(6) . . ?
N1 Ti1 C3 98.65(6) . . ?
C2 Ti1 C3 35.34(6) . . ?
C5 Ti1 C3 57.69(7) . . ?
C19 Ti1 C3 118.92(7) . . ?
C18 Ti1 C3 87.17(7) . . ?
C17 Ti1 C3 86.15(7) . . ?
C1 Ti1 C20 135.36(6) . . ?
N1 Ti1 C20 95.93(6) . . ?
C2 Ti1 C20 128.70(7) . . ?
C5 Ti1 C20 159.68(7) . . ?
C19 Ti1 C20 34.45(6) . . ?
C18 Ti1 C20 56.94(7) . . ?
C17 Ti1 C20 56.47(6) . . ?
C3 Ti1 C20 141.32(7) . . ?
C1 Ti1 C4 59.36(6) . . ?
N1 Ti1 C4 74.49(6) . . ?
C2 Ti1 C4 57.62(6) . . ?
C5 Ti1 C4 34.12(6) . . ?
C19 Ti1 C4 151.50(7) . . ?
C18 Ti1 C4 120.54(7) . . ?
C17 Ti1 C4 111.73(7) . . ?
C3 Ti1 C4 33.49(6) . . ?
C20 Ti1 C4 164.41(6) . . ?
C1 Ti1 C16 158.95(6) . . ?
N1 Ti1 C16 78.37(6) . . ?
C2 Ti1 C16 127.21(6) . . ?
C5 Ti1 C16 161.76(6) . . ?
C19 Ti1 C16 56.75(6) . . ?
C18 Ti1 C16 56.70(6) . . ?
C17 Ti1 C16 33.79(6) . . ?
C3 Ti1 C16 116.41(6) . . ?
C20 Ti1 C16 33.53(6) . . ?
C4 Ti1 C16 130.97(6) . . ?
C1 Ti1 S1 96.15(5) . . ?
N1 Ti1 S1 63.28(4) . . ?
C2 Ti1 S1 133.29(5) . . ?
C5 Ti1 S1 82.37(5) . . ?
C19 Ti1 S1 99.66(5) . . ?
C18 Ti1 S1 133.74(5) . . ?
C17 Ti1 S1 131.17(5) . . ?
C3 Ti1 S1 138.15(5) . . ?
C20 Ti1 S1 80.18(5) . . ?
C4 Ti1 S1 105.44(5) . . ?
C16 Ti1 S1 97.45(4) . . ?
C1 Ti1 C6 30.65(6) . . ?
N1 Ti1 C6 130.50(6) . . ?
C2 Ti1 C6 59.71(6) . . ?
C5 Ti1 C6 58.62(6) . . ?
C19 Ti1 C6 83.87(6) . . ?
C18 Ti1 C6 97.36(6) . . ?
C17 Ti1 C6 132.04(6) . . ?
C3 Ti1 C6 89.80(6) . . ?
C20 Ti1 C6 107.26(6) . . ?
C4 Ti1 C6 88.23(6) . . ?
C16 Ti1 C6 139.36(6) . . ?
S1 Ti1 C6 78.12(4) . . ?
C31 S1 Ti1 81.03(6) . . ?
C31 N1 N2 113.55(14) . . ?
C31 N1 Ti1 104.12(11) . . ?
N2 N1 Ti1 142.32(12) . . ?
C33 N2 N1 116.97(15) . . ?
C33 N2 Ti1 93.53(11) . . ?
N1 N2 Ti1 23.44(8) . . ?
C31 N3 C32 122.70(16) . . ?
C31 N3 H3 120.2(16) . . ?
C32 N3 H3 117.0(15) . . ?
C38 N4 C34 117.83(16) . . ?
C6 C1 C2 126.31(16) . . ?
C6 C1 C5 123.02(16) . . ?
C2 C1 C5 105.31(15) . . ?
C6 C1 Ti1 96.02(11) . . ?
C2 C1 Ti1 73.75(10) . . ?
C5 C1 Ti1 75.02(10) . . ?
C3 C2 C1 108.89(16) . . ?
C3 C2 Ti1 77.11(10) . . ?
C1 C2 Ti1 69.12(10) . . ?
C3 C2 H2 125.6 . . ?
C1 C2 H2 125.6 . . ?
Ti1 C2 H2 119.9 . . ?
C4 C3 C2 107.68(16) . . ?
C4 C3 Ti1 74.70(11) . . ?
C2 C3 Ti1 67.55(10) . . ?
C4 C3 H3A 126.2 . . ?
C2 C3 H3A 126.2 . . ?
Ti1 C3 H3A 123.2 . . ?
C3 C4 C5 109.05(16) . . ?
C3 C4 Ti1 71.81(11) . . ?
C5 C4 Ti1 67.92(10) . . ?
C3 C4 H4 125.5 . . ?
C5 C4 H4 125.5 . . ?
Ti1 C4 H4 126.4 . . ?
C4 C5 C1 109.04(16) . . ?
C4 C5 Ti1 77.96(11) . . ?
C1 C5 Ti1 67.91(9) . . ?
C4 C5 H5 125.5 . . ?
C1 C5 H5 125.5 . . ?
Ti1 C5 H5 120.2 . . ?
C1 C6 C11 121.38(16) . . ?
C1 C6 C7 118.75(16) . . ?
C11 C6 C7 111.58(15) . . ?
C1 C6 Ti1 53.33(9) . . ?
C11 C6 Ti1 119.39(11) . . ?
C7 C6 Ti1 121.14(11) . . ?
C6 C7 C8 111.77(15) . . ?
C6 C7 C12 106.38(15) . . ?
C8 C7 C12 108.79(15) . . ?
C6 C7 H7 109.9 . . ?
C8 C7 H7 109.9 . . ?
C12 C7 H7 109.9 . . ?
C9 C8 C7 109.85(16) . . ?
C9 C8 H8A 109.7 . . ?
C7 C8 H8A 109.7 . . ?
C9 C8 H8B 109.7 . . ?
C7 C8 H8B 109.7 . . ?
H8A C8 H8B 108.2 . . ?
C8 C9 C10 109.05(15) . . ?
C8 C9 C13 109.40(17) . . ?
C10 C9 C13 109.45(17) . . ?
C8 C9 H9 109.6 . . ?
C10 C9 H9 109.6 . . ?
C13 C9 H9 109.6 . . ?
C9 C10 C11 110.30(16) . . ?
C9 C10 H10A 109.6 . . ?
C11 C10 H10A 109.6 . . ?
C9 C10 H10B 109.6 . . ?
C11 C10 H10B 109.6 . . ?
H10A C10 H10B 108.1 . . ?
C6 C11 C10 111.36(15) . . ?
C6 C11 C14 106.52(15) . . ?
C10 C11 C14 108.46(15) . . ?
C6 C11 Ti1 39.93(8) . . ?
C10 C11 Ti1 109.87(11) . . ?
C14 C11 Ti1 136.79(11) . . ?
C6 C11 H11 110.1 . . ?
C10 C11 H11 110.1 . . ?
C14 C11 H11 110.1 . . ?
Ti1 C11 H11 74.1 . . ?
C15 C12 C7 109.37(15) . . ?
C15 C12 H12A 109.8 . . ?
C7 C12 H12A 109.8 . . ?
C15 C12 H12B 109.8 . . ?
C7 C12 H12B 109.8 . . ?
H12A C12 H12B 108.2 . . ?
C15 C13 C9 109.75(16) . . ?
C15 C13 H13A 109.7 . . ?
C9 C13 H13A 109.7 . . ?
C15 C13 H13B 109.7 . . ?
C9 C13 H13B 109.7 . . ?
H13A C13 H13B 108.2 . . ?
C15 C14 C11 109.48(16) . . ?
C15 C14 H14A 109.8 . . ?
C11 C14 H14A 109.8 . . ?
C15 C14 H14B 109.8 . . ?
C11 C14 H14B 109.8 . . ?
H14A C14 H14B 108.2 . . ?
C14 C15 C13 109.45(17) . . ?
C14 C15 C12 110.24(16) . . ?
C13 C15 C12 108.91(17) . . ?
C14 C15 H15 109.4 . . ?
C13 C15 H15 109.4 . . ?
C12 C15 H15 109.4 . . ?
C20 C16 C17 106.94(16) . . ?
C20 C16 C21 128.76(17) . . ?
C17 C16 C21 124.25(16) . . ?
C20 C16 Ti1 70.68(10) . . ?
C17 C16 Ti1 69.90(10) . . ?
C21 C16 Ti1 126.52(12) . . ?
C16 C17 C18 108.22(16) . . ?
C16 C17 Ti1 76.32(10) . . ?
C18 C17 Ti1 71.25(10) . . ?
C16 C17 H17 125.9 . . ?
C18 C17 H17 125.9 . . ?
Ti1 C17 H17 118.4 . . ?
C19 C18 C17 108.01(16) . . ?
C19 C18 Ti1 72.44(10) . . ?
C17 C18 Ti1 74.00(10) . . ?
C19 C18 H18 126.0 . . ?
C17 C18 H18 126.0 . . ?
Ti1 C18 H18 119.4 . . ?
C18 C19 C20 107.77(16) . . ?
C18 C19 Ti1 72.90(10) . . ?
C20 C19 Ti1 75.06(10) . . ?
C18 C19 H19 126.1 . . ?
C20 C19 H19 126.1 . . ?
Ti1 C19 H19 117.9 . . ?
C16 C20 C19 108.96(16) . . ?
C16 C20 Ti1 75.79(10) . . ?
C19 C20 Ti1 70.49(10) . . ?
C16 C20 H20 125.5 . . ?
C19 C20 H20 125.5 . . ?
Ti1 C20 H20 119.9 . . ?
C16 C21 C22 115.18(15) . . ?
C16 C21 C26 112.39(15) . . ?
C22 C21 C26 108.73(14) . . ?
C16 C21 Ti1 33.75(8) . . ?
C22 C21 Ti1 109.67(11) . . ?
C26 C21 Ti1 138.24(11) . . ?
C16 C21 H21 106.7 . . ?
C22 C21 H21 106.7 . . ?
C26 C21 H21 106.7 . . ?
Ti1 C21 H21 77.2 . . ?
C23 C22 C21 107.53(16) . . ?
C23 C22 C27 109.23(15) . . ?
C21 C22 C27 111.74(15) . . ?
C23 C22 H22 109.4 . . ?
C21 C22 H22 109.4 . . ?
C27 C22 H22 109.4 . . ?
C22 C23 C24 109.65(16) . . ?
C22 C23 H23A 109.7 . . ?
C24 C23 H23A 109.7 . . ?
C22 C23 H23B 109.7 . . ?
C24 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
C25 C24 C28 109.05(17) . . ?
C25 C24 C23 109.51(16) . . ?
C28 C24 C23 109.59(17) . . ?
C25 C24 H24 109.6 . . ?
C28 C24 H24 109.6 . . ?
C23 C24 H24 109.6 . . ?
C24 C25 C26 109.64(16) . . ?
C24 C25 H25A 109.7 . . ?
C26 C25 H25A 109.7 . . ?
C24 C25 H25B 109.7 . . ?
C26 C25 H25B 109.7 . . ?
H25A C25 H25B 108.2 . . ?
C29 C26 C25 109.26(16) . . ?
C29 C26 C21 110.37(15) . . ?
C25 C26 C21 108.59(16) . . ?
C29 C26 H26 109.5 . . ?
C25 C26 H26 109.5 . . ?
C21 C26 H26 109.5 . . ?
C30 C27 C22 109.66(15) . . ?
C30 C27 H27A 109.7 . . ?
C22 C27 H27A 109.7 . . ?
C30 C27 H27B 109.7 . . ?
C22 C27 H27B 109.7 . . ?
H27A C27 H27B 108.2 . . ?
C30 C28 C24 109.62(15) . . ?
C30 C28 H28A 109.7 . . ?
C24 C28 H28A 109.7 . . ?
C30 C28 H28B 109.7 . . ?
C24 C28 H28B 109.7 . . ?
H28A C28 H28B 108.2 . . ?
C30 C29 C26 110.03(16) . . ?
C30 C29 H29A 109.7 . . ?
C26 C29 H29A 109.7 . . ?
C30 C29 H29B 109.7 . . ?
C26 C29 H29B 109.7 . . ?
H29A C29 H29B 108.2 . . ?
C27 C30 C29 109.00(15) . . ?
C27 C30 C28 109.17(16) . . ?
C29 C30 C28 109.96(16) . . ?
C27 C30 H30 109.6 . . ?
C29 C30 H30 109.6 . . ?
C28 C30 H30 109.6 . . ?
N3 C31 N1 124.09(16) . . ?
N3 C31 S1 124.34(14) . . ?
N1 C31 S1 111.56(13) . . ?
N3 C31 Ti1 172.69(13) . . ?
N1 C31 Ti1 48.73(9) . . ?
S1 C31 Ti1 62.83(6) . . ?
N3 C32 H32A 109.5 . . ?
N3 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
N3 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
N2 C33 C34 119.75(16) . . ?
N2 C33 Ti1 66.29(10) . . ?
C34 C33 Ti1 169.16(12) . . ?
N2 C33 H33 120.1 . . ?
C34 C33 H33 120.1 . . ?
Ti1 C33 H33 54.7 . . ?
N4 C34 C35 122.13(17) . . ?
N4 C34 C33 116.04(16) . . ?
C35 C34 C33 121.73(17) . . ?
C36 C35 C34 118.78(18) . . ?
C36 C35 H35 120.6 . . ?
C34 C35 H35 120.6 . . ?
C35 C36 C37 119.40(19) . . ?
C35 C36 H36 120.3 . . ?
C37 C36 H36 120.3 . . ?
C38 C37 C36 118.26(19) . . ?
C38 C37 H37 120.9 . . ?
C36 C37 H37 120.9 . . ?
N4 C38 C37 123.56(19) . . ?
N4 C38 H38 118.2 . . ?
C37 C38 H38 118.2 . . ?
C40 C39 C44 121.0(2) . . ?
C40 C39 H39 119.5 . . ?
C44 C39 H39 119.5 . . ?
C41 C40 C39 120.1(3) . . ?
C41 C40 H40 119.9 . . ?
C39 C40 H40 119.9 . . ?
C40 C41 C42 120.4(3) . . ?
C40 C41 H41 119.8 . . ?
C42 C41 H41 119.8 . . ?
C41 C42 C43 120.0(2) . . ?
C41 C42 H42 120.0 . . ?
C43 C42 H42 120.0 . . ?
C42 C43 C44 119.0(3) . . ?
C42 C43 H43 120.5 . . ?
C44 C43 H43 120.5 . . ?
C39 C44 C43 119.5(3) . . ?
C39 C44 H44 120.3 . . ?
C43 C44 H44 120.3 . . ?

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
C31 N1 N2 C33 179.98(15) . . . . ?
Ti1 N1 N2 C33 0.7(3) . . . . ?
C31 N1 N2 Ti1 179.2(3) . . . . ?
C6 C1 C2 C3 -152.97(17) . . . . ?
C5 C1 C2 C3 1.48(19) . . . . ?
Ti1 C1 C2 C3 -67.48(13) . . . . ?
C6 C1 C2 Ti1 -85.49(17) . . . . ?
C5 C1 C2 Ti1 68.96(11) . . . . ?
C1 C2 C3 C4 -2.1(2) . . . . ?
Ti1 C2 C3 C4 -64.45(13) . . . . ?
C1 C2 C3 Ti1 62.30(12) . . . . ?
C2 C3 C4 C5 2.0(2) . . . . ?
Ti1 C3 C4 C5 -57.86(13) . . . . ?
C2 C3 C4 Ti1 59.82(12) . . . . ?
C3 C4 C5 C1 -1.1(2) . . . . ?
Ti1 C4 C5 C1 -61.29(12) . . . . ?
C3 C4 C5 Ti1 60.24(13) . . . . ?
C6 C1 C5 C4 155.24(17) . . . . ?
C2 C1 C5 C4 -0.28(19) . . . . ?
Ti1 C1 C5 C4 67.78(13) . . . . ?
C6 C1 C5 Ti1 87.46(16) . . . . ?
C2 C1 C5 Ti1 -68.06(11) . . . . ?
C2 C1 C6 C11 -31.0(3) . . . . ?
C5 C1 C6 C11 178.76(16) . . . . ?
Ti1 C1 C6 C11 -105.22(15) . . . . ?
C2 C1 C6 C7 -176.68(16) . . . . ?
C5 C1 C6 C7 33.1(2) . . . . ?
Ti1 C1 C6 C7 109.09(15) . . . . ?
C2 C1 C6 Ti1 74.23(16) . . . . ?
C5 C1 C6 Ti1 -76.03(15) . . . . ?
C1 C6 C7 C8 -157.17(16) . . . . ?
C11 C6 C7 C8 54.0(2) . . . . ?
Ti1 C6 C7 C8 -94.84(16) . . . . ?
C1 C6 C7 C12 84.22(19) . . . . ?
C11 C6 C7 C12 -64.62(18) . . . . ?
Ti1 C6 C7 C12 146.55(12) . . . . ?
C6 C7 C8 C9 -57.1(2) . . . . ?
C12 C7 C8 C9 60.0(2) . . . . ?
C7 C8 C9 C10 59.7(2) . . . . ?
C7 C8 C9 C13 -60.0(2) . . . . ?
C8 C9 C10 C11 -59.8(2) . . . . ?
C13 C9 C10 C11 59.9(2) . . . . ?
C1 C6 C11 C10 158.47(16) . . . . ?
C7 C6 C11 C10 -53.6(2) . . . . ?
Ti1 C6 C11 C10 95.81(16) . . . . ?
C1 C6 C11 C14 -83.5(2) . . . . ?
C7 C6 C11 C14 64.45(18) . . . . ?
Ti1 C6 C11 C14 -146.11(12) . . . . ?
C1 C6 C11 Ti1 62.66(15) . . . . ?
C7 C6 C11 Ti1 -149.44(19) . . . . ?
C9 C10 C11 C6 57.0(2) . . . . ?
C9 C10 C11 C14 -59.89(19) . . . . ?
C9 C10 C11 Ti1 99.77(14) . . . . ?
C6 C7 C12 C15 60.1(2) . . . . ?
C8 C7 C12 C15 -60.5(2) . . . . ?
C8 C9 C13 C15 60.1(2) . . . . ?
C10 C9 C13 C15 -59.4(2) . . . . ?
C6 C11 C14 C15 -59.88(19) . . . . ?
C10 C11 C14 C15 60.1(2) . . . . ?
Ti1 C11 C14 C15 -91.39(19) . . . . ?
C11 C14 C15 C13 -60.5(2) . . . . ?
C11 C14 C15 C12 59.2(2) . . . . ?
C9 C13 C15 C14 60.1(2) . . . . ?
C9 C13 C15 C12 -60.5(2) . . . . ?
C7 C12 C15 C14 -59.4(2) . . . . ?
C7 C12 C15 C13 60.7(2) . . . . ?
C20 C16 C17 C18 -3.3(2) . . . . ?
C21 C16 C17 C18 174.21(16) . . . . ?
Ti1 C16 C17 C18 -64.63(12) . . . . ?
C20 C16 C17 Ti1 61.33(12) . . . . ?
C21 C16 C17 Ti1 -121.16(17) . . . . ?
C16 C17 C18 C19 3.0(2) . . . . ?
Ti1 C17 C18 C19 -64.96(13) . . . . ?
C16 C17 C18 Ti1 67.99(13) . . . . ?
C17 C18 C19 C20 -1.6(2) . . . . ?
Ti1 C18 C19 C20 -67.56(13) . . . . ?
C17 C18 C19 Ti1 65.99(13) . . . . ?
C17 C16 C20 C19 2.4(2) . . . . ?
C21 C16 C20 C19 -175.01(17) . . . . ?
Ti1 C16 C20 C19 63.17(12) . . . . ?
C17 C16 C20 Ti1 -60.82(12) . . . . ?
C21 C16 C20 Ti1 121.82(18) . . . . ?
C18 C19 C20 C16 -0.5(2) . . . . ?
Ti1 C19 C20 C16 -66.60(13) . . . . ?
C18 C19 C20 Ti1 66.10(13) . . . . ?
C20 C16 C21 C22 -5.8(3) . . . . ?
C17 C16 C21 C22 177.28(16) . . . . ?
Ti1 C16 C21 C22 88.05(18) . . . . ?
C20 C16 C21 C26 119.5(2) . . . . ?
C17 C16 C21 C26 -57.4(2) . . . . ?
Ti1 C16 C21 C26 -146.68(13) . . . . ?
C20 C16 C21 Ti1 -93.8(2) . . . . ?
C17 C16 C21 Ti1 89.2(2) . . . . ?
C16 C21 C22 C23 -169.63(15) . . . . ?
C26 C21 C22 C23 63.21(19) . . . . ?
Ti1 C21 C22 C23 -133.50(12) . . . . ?
C16 C21 C22 C27 70.5(2) . . . . ?
C26 C21 C22 C27 -56.65(19) . . . . ?
Ti1 C21 C22 C27 106.64(13) . . . . ?
C21 C22 C23 C24 -62.1(2) . . . . ?
C27 C22 C23 C24 59.4(2) . . . . ?
C22 C23 C24 C25 60.4(2) . . . . ?
C22 C23 C24 C28 -59.2(2) . . . . ?
C28 C24 C25 C26 60.9(2) . . . . ?
C23 C24 C25 C26 -59.0(2) . . . . ?
C24 C25 C26 C29 -60.3(2) . . . . ?
C24 C25 C26 C21 60.1(2) . . . . ?
C16 C21 C26 C29 -71.53(19) . . . . ?
C22 C21 C26 C29 57.20(19) . . . . ?
Ti1 C21 C26 C29 -98.81(18) . . . . ?
C16 C21 C26 C25 168.72(15) . . . . ?
C22 C21 C26 C25 -62.55(19) . . . . ?
Ti1 C21 C26 C25 141.45(14) . . . . ?
C23 C22 C27 C30 -60.3(2) . . . . ?
C21 C22 C27 C30 58.5(2) . . . . ?
C25 C24 C28 C30 -60.2(2) . . . . ?
C23 C24 C28 C30 59.7(2) . . . . ?
C25 C26 C29 C30 58.9(2) . . . . ?
C21 C26 C29 C30 -60.42(19) . . . . ?
C22 C27 C30 C29 -59.4(2) . . . . ?
C22 C27 C30 C28 60.8(2) . . . . ?
C26 C29 C30 C27 61.0(2) . . . . ?
C26 C29 C30 C28 -58.7(2) . . . . ?
C24 C28 C30 C27 -60.4(2) . . . . ?
C24 C28 C30 C29 59.1(2) . . . . ?
C32 N3 C31 N1 179.04(17) . . . . ?
C32 N3 C31 S1 0.0(3) . . . . ?
N2 N1 C31 N3 2.3(2) . . . . ?
Ti1 N1 C31 N3 -178.18(15) . . . . ?
N2 N1 C31 S1 -178.59(11) . . . . ?
Ti1 N1 C31 S1 0.94(14) . . . . ?
N2 N1 C31 Ti1 -179.53(17) . . . . ?
Ti1 S1 C31 N3 178.32(16) . . . . ?
Ti1 S1 C31 N1 -0.79(11) . . . . ?
N1 N2 C33 C34 -170.21(15) . . . . ?
Ti1 N2 C33 C34 -169.92(14) . . . . ?
N1 N2 C33 Ti1 -0.29(11) . . . . ?
C38 N4 C34 C35 0.3(3) . . . . ?
C38 N4 C34 C33 -176.19(17) . . . . ?
N2 C33 C34 N4 -176.22(16) . . . . ?
Ti1 C33 C34 N4 62.3(7) . . . . ?
N2 C33 C34 C35 7.3(3) . . . . ?
Ti1 C33 C34 C35 -114.2(6) . . . . ?
N4 C34 C35 C36 -1.7(3) . . . . ?
C33 C34 C35 C36 174.58(18) . . . . ?
C34 C35 C36 C37 1.7(3) . . . . ?
C35 C36 C37 C38 -0.4(3) . . . . ?
C34 N4 C38 C37 1.1(3) . . . . ?
C36 C37 C38 N4 -1.1(3) . . . . ?
C44 C39 C40 C41 -0.6(4) . . . . ?
C39 C40 C41 C42 0.9(4) . . . . ?
C40 C41 C42 C43 -0.4(4) . . . . ?
C41 C42 C43 C44 -0.5(4) . . . . ?
C40 C39 C44 C43 -0.2(4) . . . . ?
C42 C43 C44 C39 0.8(4) . . . . ?

_refine_diff_density_max         0.331
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.053



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_Ti2b
_database_code_depnum_ccdc_archive 'CCDC 2377768'
loop_
_audit_author_name
_audit_author_address
'Marc Schmidtmann'
;Carl von Ossietzky Universitaet Oldenburg
Germany
;
_audit_update_record             
;
2024-08-15 deposited with the CCDC.	2024-09-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/3
_shelx_SHELXL_version_number     2019/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_structural     Ti(C20H18)(C20H19)(C7H8N3S2)
_chemical_formula_sum            'C47 H45 N3 S2 Ti'
_chemical_formula_weight         763.88

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'
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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   14.4377(5)
_cell_length_b                   12.5870(5)
_cell_length_c                   21.9625(8)
_cell_angle_alpha                90
_cell_angle_beta                 97.4150(15)
_cell_angle_gamma                90
_cell_volume                     3957.8(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9314
_cell_measurement_theta_min      2.47
_cell_measurement_theta_max      30.07

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_F_000             1608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.090
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    0.359
_shelx_estimated_absorpt_T_min   0.958
_shelx_estimated_absorpt_T_max   0.982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9392
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'SADABS-2016/2 (Sheldrick)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'I\mS microfocus'
_diffrn_measurement_device_type  'Bruker Photon III CPAD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            235418
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         1.598
_diffrn_reflns_theta_max         30.033
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             11566
_reflns_number_gt                10485
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX3'
_computing_cell_refinement       'Bruker SAINT V8.40B'
_computing_data_reduction        'Bruker SAINT V8.40B'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0450P)²+1.9000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         11566
_refine_ls_number_parameters     487
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0350
_refine_ls_wR_factor_ref         0.0939
_refine_ls_wR_factor_gt          0.0909
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.068
_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_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 0.15194(2) 0.26179(2) 0.08503(2) 0.01498(5) Uani 1 1 d . . . . .
S1 S 0.19008(2) 0.06177(2) 0.09453(2) 0.02072(6) Uani 1 1 d . . . . .
S2 S -0.13955(2) 0.20759(3) 0.27272(2) 0.02740(7) Uani 1 1 d . . . . .
N1 N 0.07389(7) 0.17131(8) 0.14571(4) 0.01910(18) Uani 1 1 d . . . . .
N2 N 0.00648(7) 0.18449(8) 0.18417(4) 0.01994(19) Uani 1 1 d . . . . .
N3 N 0.08334(9) -0.00603(9) 0.17987(5) 0.0263(2) Uani 1 1 d . . . . .
H3 H 0.0402(12) 0.0084(14) 0.2018(8) 0.026(4) Uiso 1 1 d . . . . .
C1 C 0.12380(8) 0.26795(9) -0.01702(5) 0.01692(19) Uani 1 1 d . . . . .
C2 C 0.10348(8) 0.37184(9) 0.00610(5) 0.0174(2) Uani 1 1 d . . . . .
H2 H 0.138190 0.434674 0.001157 0.021 Uiso 1 1 calc R U . . .
C3 C 0.02349(8) 0.36513(9) 0.03734(5) 0.0191(2) Uani 1 1 d . . . . .
H3A H -0.003409 0.421693 0.057705 0.023 Uiso 1 1 calc R U . . .
C4 C -0.00874(8) 0.25952(10) 0.03270(5) 0.0197(2) Uani 1 1 d . . . . .
H4 H -0.062486 0.233261 0.048564 0.024 Uiso 1 1 calc R U . . .
C5 C 0.05120(8) 0.19924(9) 0.00088(5) 0.0185(2) Uani 1 1 d . . . . .
H5 H 0.045233 0.125366 -0.007579 0.022 Uiso 1 1 calc R U . . .
C6 C 0.21477(8) 0.23346(9) -0.02712(5) 0.0179(2) Uani 1 1 d . . . . .
C7 C 0.22979(8) 0.12061(9) -0.04418(5) 0.0187(2) Uani 1 1 d . . . . .
C8 C 0.16259(8) 0.06696(9) -0.08483(5) 0.0206(2) Uani 1 1 d . . . . .
H8 H 0.107905 0.103707 -0.101983 0.025 Uiso 1 1 calc R U . . .
C9 C 0.17431(9) -0.03902(10) -0.10060(6) 0.0230(2) Uani 1 1 d . . . . .
H9 H 0.126710 -0.073508 -0.127380 0.028 Uiso 1 1 calc R U . . .
C10 C 0.25430(9) -0.09530(10) -0.07791(6) 0.0230(2) Uani 1 1 d . . . . .
C11 C 0.32317(9) -0.04089(10) -0.04000(6) 0.0244(2) Uani 1 1 d . . . . .
H11 H 0.379907 -0.076248 -0.025572 0.029 Uiso 1 1 calc R U . . .
C12 C 0.31096(8) 0.06396(10) -0.02274(6) 0.0230(2) Uani 1 1 d . . . . .
H12 H 0.358715 0.097891 0.004192 0.028 Uiso 1 1 calc R U . . .
C13 C 0.26438(10) -0.21232(10) -0.09103(7) 0.0289(3) Uani 1 1 d . . . . .
H13A H 0.227879 -0.253696 -0.064752 0.043 Uiso 1 1 calc R U . . .
H13B H 0.330316 -0.232633 -0.082606 0.043 Uiso 1 1 calc R U . . .
H13C H 0.241476 -0.226512 -0.134226 0.043 Uiso 1 1 calc R U . . .
C14 C 0.28262(8) 0.31389(9) -0.04481(5) 0.0187(2) Uani 1 1 d . . . . .
C15 C 0.37965(8) 0.30645(10) -0.02858(6) 0.0243(2) Uani 1 1 d . . . . .
H15 H 0.404320 0.250821 -0.002082 0.029 Uiso 1 1 calc R U . . .
C16 C 0.44061(9) 0.37859(11) -0.05037(7) 0.0270(3) Uani 1 1 d . . . . .
H16 H 0.505916 0.370702 -0.038629 0.032 Uiso 1 1 calc R U . . .
C17 C 0.40822(9) 0.46200(10) -0.08894(6) 0.0258(2) Uani 1 1 d . . . . .
C18 C 0.31197(9) 0.47176(10) -0.10432(6) 0.0247(2) Uani 1 1 d . . . . .
H18 H 0.287701 0.528865 -0.129819 0.030 Uiso 1 1 calc R U . . .
C19 C 0.25062(8) 0.39943(10) -0.08305(6) 0.0216(2) Uani 1 1 d . . . . .
H19 H 0.185370 0.408095 -0.094683 0.026 Uiso 1 1 calc R U . . .
C20 C 0.47458(11) 0.53783(12) -0.11408(8) 0.0368(3) Uani 1 1 d . . . . .
H20A H 0.483429 0.600601 -0.087563 0.055 Uiso 1 1 calc R U . . .
H20B H 0.448615 0.559563 -0.155642 0.055 Uiso 1 1 calc R U . . .
H20C H 0.534842 0.502650 -0.115370 0.055 Uiso 1 1 calc R U . . .
C21 C 0.20458(8) 0.43009(9) 0.13496(5) 0.0172(2) Uani 1 1 d . . . . .
C22 C 0.27220(8) 0.39291(9) 0.09833(5) 0.0192(2) Uani 1 1 d . . . . .
H22 H 0.289971 0.427874 0.063291 0.023 Uiso 1 1 calc R U . . .
C23 C 0.30860(8) 0.29535(9) 0.12266(6) 0.0215(2) Uani 1 1 d . . . . .
H23 H 0.356121 0.254354 0.107740 0.026 Uiso 1 1 calc R U . . .
C24 C 0.26143(8) 0.26996(9) 0.17321(6) 0.0217(2) Uani 1 1 d . . . . .
H24 H 0.271041 0.208055 0.197972 0.026 Uiso 1 1 calc R U . . .
C25 C 0.19714(8) 0.35288(9) 0.18068(5) 0.0194(2) Uani 1 1 d . . . . .
H25 H 0.156184 0.355860 0.211188 0.023 Uiso 1 1 calc R U . . .
C26 C 0.15971(8) 0.53890(9) 0.12698(5) 0.01709(19) Uani 1 1 d . . . . .
H26 H 0.120420 0.539634 0.086004 0.021 Uiso 1 1 calc R U . . .
C27 C 0.09676(8) 0.56907(9) 0.17461(5) 0.0193(2) Uani 1 1 d . . . . .
C28 C 0.12402(9) 0.55681(10) 0.23764(6) 0.0230(2) Uani 1 1 d . . . . .
H28 H 0.181962 0.523668 0.251697 0.028 Uiso 1 1 calc R U . . .
C29 C 0.06745(10) 0.59249(10) 0.27993(6) 0.0268(3) Uani 1 1 d . . . . .
H29 H 0.086806 0.581994 0.322503 0.032 Uiso 1 1 calc R U . . .
C30 C -0.01699(10) 0.64328(11) 0.26123(7) 0.0296(3) Uani 1 1 d . . . . .
C31 C -0.04316(9) 0.65778(11) 0.19866(7) 0.0290(3) Uani 1 1 d . . . . .
H31 H -0.099814 0.693770 0.184805 0.035 Uiso 1 1 calc R U . . .
C32 C 0.01242(8) 0.62034(10) 0.15593(6) 0.0233(2) Uani 1 1 d . . . . .
H32 H -0.007559 0.629954 0.113356 0.028 Uiso 1 1 calc R U . . .
C33 C -0.07788(12) 0.67937(15) 0.30793(8) 0.0428(4) Uani 1 1 d . . . . .
H33A H -0.108093 0.617590 0.324064 0.064 Uiso 1 1 calc R U . . .
H33B H -0.125707 0.728187 0.288509 0.064 Uiso 1 1 calc R U . . .
H33C H -0.039483 0.715842 0.341652 0.064 Uiso 1 1 calc R U . . .
C34 C 0.23524(8) 0.62346(9) 0.12540(5) 0.0179(2) Uani 1 1 d . . . . .
C35 C 0.31521(9) 0.62465(11) 0.16807(6) 0.0269(3) Uani 1 1 d . . . . .
H35 H 0.324176 0.571044 0.198718 0.032 Uiso 1 1 calc R U . . .
C36 C 0.38203(9) 0.70341(11) 0.16632(6) 0.0286(3) Uani 1 1 d . . . . .
H36 H 0.436231 0.702639 0.195873 0.034 Uiso 1 1 calc R U . . .
C37 C 0.37156(9) 0.78340(10) 0.12237(6) 0.0235(2) Uani 1 1 d . . . . .
C38 C 0.29032(10) 0.78346(11) 0.08104(7) 0.0292(3) Uani 1 1 d . . . . .
H38 H 0.280126 0.838597 0.051392 0.035 Uiso 1 1 calc R U . . .
C39 C 0.22349(9) 0.70400(10) 0.08230(6) 0.0257(2) Uani 1 1 d . . . . .
H39 H 0.168932 0.705156 0.053060 0.031 Uiso 1 1 calc R U . . .
C40 C 0.44665(10) 0.86634(11) 0.11951(7) 0.0324(3) Uani 1 1 d . . . . .
H40A H 0.473347 0.886047 0.161279 0.049 Uiso 1 1 calc R U . . .
H40B H 0.419389 0.929327 0.097904 0.049 Uiso 1 1 calc R U . . .
H40C H 0.495874 0.837395 0.097490 0.049 Uiso 1 1 calc R U . . .
C41 C 0.10885(8) 0.07333(9) 0.14474(5) 0.0198(2) Uani 1 1 d . . . . .
C42 C 0.11708(11) -0.11452(10) 0.17692(7) 0.0323(3) Uani 1 1 d . . . . .
H42A H 0.088571 -0.147790 0.138696 0.048 Uiso 1 1 calc R U . . .
H42B H 0.100246 -0.154885 0.212040 0.048 Uiso 1 1 calc R U . . .
H42C H 0.185154 -0.114010 0.178046 0.048 Uiso 1 1 calc R U . . .
C43 C -0.02853(8) 0.27833(10) 0.18608(5) 0.0201(2) Uani 1 1 d . . . . .
H43 H -0.008044 0.332925 0.161112 0.024 Uiso 1 1 calc R U . . .
C44 C -0.09858(8) 0.30196(10) 0.22565(5) 0.0213(2) Uani 1 1 d . . . . .
C45 C -0.13771(9) 0.39965(10) 0.23364(6) 0.0253(2) Uani 1 1 d . . . . .
H45 H -0.124265 0.461541 0.211624 0.030 Uiso 1 1 calc R U . . .
C46 C -0.20050(10) 0.39800(12) 0.27844(7) 0.0310(3) Uani 1 1 d . . . . .
H46 H -0.233610 0.458581 0.289751 0.037 Uiso 1 1 calc R U . . .
C47 C -0.20779(10) 0.29989(13) 0.30325(6) 0.0321(3) Uani 1 1 d . . . . .
H47 H -0.246337 0.284234 0.334026 0.039 Uiso 1 1 calc R U . . .


_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 N1 2.1750(10) . ?
Ti1 C1 2.2268(11) . ?
Ti1 C2 2.2583(11) . ?
Ti1 C5 2.3360(11) . ?
Ti1 C24 2.3388(12) . ?
Ti1 C23 2.3441(11) . ?
Ti1 C22 2.3860(11) . ?
Ti1 C3 2.3930(11) . ?
Ti1 C25 2.4081(11) . ?
Ti1 C4 2.4526(11) . ?
Ti1 C21 2.4601(11) . ?
Ti1 S1 2.5798(4) . ?
S1 C41 1.7165(12) . ?
S2 C47 1.7148(15) . ?
S2 C44 1.7285(12) . ?
N1 C41 1.3338(15) . ?
N1 N2 1.3785(13) . ?
N2 C43 1.2876(16) . ?
N3 C41 1.3423(15) . ?
N3 C42 1.4541(17) . ?
N3 H3 0.854(17) . ?
C1 C6 1.4275(15) . ?
C1 C2 1.4464(15) . ?
C1 C5 1.4518(15) . ?
C2 C3 1.4199(16) . ?
C2 H2 0.9500 . ?
C3 C4 1.4078(16) . ?
C3 H3A 0.9500 . ?
C4 C5 1.4032(16) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 C7 1.4921(16) . ?
C6 C14 1.4945(15) . ?
C7 C12 1.4004(17) . ?
C7 C8 1.4038(16) . ?
C8 C9 1.3939(16) . ?
C8 H8 0.9500 . ?
C9 C10 1.3911(18) . ?
C9 H9 0.9500 . ?
C10 C11 1.3918(18) . ?
C10 C13 1.5115(17) . ?
C11 C12 1.3906(17) . ?
C11 H11 0.9500 . ?
C12 H12 0.9500 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 C15 1.4033(16) . ?
C14 C19 1.4064(16) . ?
C15 C16 1.3917(17) . ?
C15 H15 0.9500 . ?
C16 C17 1.3915(19) . ?
C16 H16 0.9500 . ?
C17 C18 1.3924(18) . ?
C17 C20 1.5068(17) . ?
C18 C19 1.3922(16) . ?
C18 H18 0.9500 . ?
C19 H19 0.9500 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 C25 1.4113(16) . ?
C21 C22 1.4221(16) . ?
C21 C26 1.5155(15) . ?
C22 C23 1.4133(16) . ?
C22 H22 0.9500 . ?
C23 C24 1.4120(18) . ?
C23 H23 0.9500 . ?
C24 C25 1.4202(17) . ?
C24 H24 0.9500 . ?
C25 H25 0.9500 . ?
C26 C27 1.5199(16) . ?
C26 C34 1.5275(15) . ?
C26 H26 1.0000 . ?
C27 C32 1.3924(16) . ?
C27 C28 1.3980(17) . ?
C28 C29 1.3883(17) . ?
C28 H28 0.9500 . ?
C29 C30 1.391(2) . ?
C29 H29 0.9500 . ?
C30 C31 1.389(2) . ?
C30 C33 1.5046(19) . ?
C31 C32 1.3932(18) . ?
C31 H31 0.9500 . ?
C32 H32 0.9500 . ?
C33 H33A 0.9800 . ?
C33 H33B 0.9800 . ?
C33 H33C 0.9800 . ?
C34 C39 1.3824(16) . ?
C34 C35 1.3900(16) . ?
C35 C36 1.3874(17) . ?
C35 H35 0.9500 . ?
C36 C37 1.3895(18) . ?
C36 H36 0.9500 . ?
C37 C38 1.3874(19) . ?
C37 C40 1.5121(17) . ?
C38 C39 1.3924(18) . ?
C38 H38 0.9500 . ?
C39 H39 0.9500 . ?
C40 H40A 0.9800 . ?
C40 H40B 0.9800 . ?
C40 H40C 0.9800 . ?
C42 H42A 0.9800 . ?
C42 H42B 0.9800 . ?
C42 H42C 0.9800 . ?
C43 C44 1.4468(16) . ?
C43 H43 0.9500 . ?
C44 C45 1.3738(18) . ?
C45 C46 1.4215(18) . ?
C45 H45 0.9500 . ?
C46 C47 1.359(2) . ?
C46 H46 0.9500 . ?
C47 H47 0.9500 . ?

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 Ti1 C1 126.39(4) . . ?
N1 Ti1 C2 131.13(4) . . ?
C1 Ti1 C2 37.62(4) . . ?
N1 Ti1 C5 89.39(4) . . ?
C1 Ti1 C5 37.01(4) . . ?
C2 Ti1 C5 59.99(4) . . ?
N1 Ti1 C24 82.17(4) . . ?
C1 Ti1 C24 147.98(4) . . ?
C2 Ti1 C24 135.89(4) . . ?
C5 Ti1 C24 162.79(4) . . ?
N1 Ti1 C23 115.53(4) . . ?
C1 Ti1 C23 113.01(4) . . ?
C2 Ti1 C23 110.45(4) . . ?
C5 Ti1 C23 144.45(4) . . ?
C24 Ti1 C23 35.10(4) . . ?
N1 Ti1 C22 135.53(4) . . ?
C1 Ti1 C22 97.73(4) . . ?
C2 Ti1 C22 79.52(4) . . ?
C5 Ti1 C22 134.34(4) . . ?
C24 Ti1 C22 57.65(4) . . ?
C23 Ti1 C22 34.75(4) . . ?
N1 Ti1 C3 96.85(4) . . ?
C1 Ti1 C3 60.67(4) . . ?
C2 Ti1 C3 35.40(4) . . ?
C5 Ti1 C3 57.91(4) . . ?
C24 Ti1 C3 137.84(4) . . ?
C23 Ti1 C3 135.59(4) . . ?
C22 Ti1 C3 100.85(4) . . ?
N1 Ti1 C25 79.53(4) . . ?
C1 Ti1 C25 148.76(4) . . ?
C2 Ti1 C25 113.56(4) . . ?
C5 Ti1 C25 157.15(4) . . ?
C24 Ti1 C25 34.78(4) . . ?
C23 Ti1 C25 57.73(4) . . ?
C22 Ti1 C25 56.83(4) . . ?
C3 Ti1 C25 103.32(4) . . ?
N1 Ti1 C4 75.38(4) . . ?
C1 Ti1 C4 59.34(4) . . ?
C2 Ti1 C4 57.78(4) . . ?
C5 Ti1 C4 33.97(4) . . ?
C24 Ti1 C4 152.36(4) . . ?
C23 Ti1 C4 168.12(4) . . ?
C22 Ti1 C4 134.01(4) . . ?
C3 Ti1 C4 33.75(4) . . ?
C25 Ti1 C4 123.22(4) . . ?
N1 Ti1 C21 109.41(4) . . ?
C1 Ti1 C21 115.11(4) . . ?
C2 Ti1 C21 82.03(4) . . ?
C5 Ti1 C21 140.16(4) . . ?
C24 Ti1 C21 57.05(4) . . ?
C23 Ti1 C21 57.26(4) . . ?
C22 Ti1 C21 34.08(4) . . ?
C3 Ti1 C21 84.51(4) . . ?
C25 Ti1 C21 33.68(4) . . ?
C4 Ti1 C21 115.98(4) . . ?
N1 Ti1 S1 63.99(3) . . ?
C1 Ti1 S1 97.16(3) . . ?
C2 Ti1 S1 134.62(3) . . ?
C5 Ti1 S1 80.77(3) . . ?
C24 Ti1 S1 82.04(3) . . ?
C23 Ti1 S1 87.78(3) . . ?
C22 Ti1 S1 121.39(3) . . ?
C3 Ti1 S1 135.32(3) . . ?
C25 Ti1 S1 111.29(3) . . ?
C4 Ti1 S1 101.87(3) . . ?
C21 Ti1 S1 138.92(3) . . ?
C41 S1 Ti1 79.21(4) . . ?
C47 S2 C44 91.52(7) . . ?
C41 N1 N2 114.81(10) . . ?
C41 N1 Ti1 104.32(7) . . ?
N2 N1 Ti1 140.81(8) . . ?
C43 N2 N1 116.21(10) . . ?
C41 N3 C42 123.70(12) . . ?
C41 N3 H3 116.1(12) . . ?
C42 N3 H3 119.8(12) . . ?
C6 C1 C2 124.18(10) . . ?
C6 C1 C5 124.88(10) . . ?
C2 C1 C5 104.91(9) . . ?
C6 C1 Ti1 95.39(7) . . ?
C2 C1 Ti1 72.37(6) . . ?
C5 C1 Ti1 75.58(6) . . ?
C3 C2 C1 109.29(10) . . ?
C3 C2 Ti1 77.48(6) . . ?
C1 C2 Ti1 70.01(6) . . ?
C3 C2 H2 125.4 . . ?
C1 C2 H2 125.4 . . ?
Ti1 C2 H2 118.9 . . ?
C4 C3 C2 107.64(10) . . ?
C4 C3 Ti1 75.45(7) . . ?
C2 C3 Ti1 67.12(6) . . ?
C4 C3 H3A 126.2 . . ?
C2 C3 H3A 126.2 . . ?
Ti1 C3 H3A 122.8 . . ?
C5 C4 C3 109.10(10) . . ?
C5 C4 Ti1 68.46(6) . . ?
C3 C4 Ti1 70.80(6) . . ?
C5 C4 H4 125.4 . . ?
C3 C4 H4 125.4 . . ?
Ti1 C4 H4 126.9 . . ?
C4 C5 C1 109.03(10) . . ?
C4 C5 Ti1 77.58(7) . . ?
C1 C5 Ti1 67.41(6) . . ?
C4 C5 H5 125.5 . . ?
C1 C5 H5 125.5 . . ?
Ti1 C5 H5 121.1 . . ?
C1 C6 C7 119.67(10) . . ?
C1 C6 C14 118.78(10) . . ?
C7 C6 C14 117.27(10) . . ?
C12 C7 C8 116.65(11) . . ?
C12 C7 C6 122.87(10) . . ?
C8 C7 C6 120.45(10) . . ?
C9 C8 C7 121.48(11) . . ?
C9 C8 H8 119.3 . . ?
C7 C8 H8 119.3 . . ?
C10 C9 C8 121.34(11) . . ?
C10 C9 H9 119.3 . . ?
C8 C9 H9 119.3 . . ?
C9 C10 C11 117.36(11) . . ?
C9 C10 C13 121.60(12) . . ?
C11 C10 C13 120.97(12) . . ?
C12 C11 C10 121.61(12) . . ?
C12 C11 H11 119.2 . . ?
C10 C11 H11 119.2 . . ?
C11 C12 C7 121.44(11) . . ?
C11 C12 H12 119.3 . . ?
C7 C12 H12 119.3 . . ?
C10 C13 H13A 109.5 . . ?
C10 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C10 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C15 C14 C19 116.29(10) . . ?
C15 C14 C6 123.72(11) . . ?
C19 C14 C6 119.86(10) . . ?
C16 C15 C14 121.61(12) . . ?
C16 C15 H15 119.2 . . ?
C14 C15 H15 119.2 . . ?
C17 C16 C15 121.58(12) . . ?
C17 C16 H16 119.2 . . ?
C15 C16 H16 119.2 . . ?
C16 C17 C18 117.44(11) . . ?
C16 C17 C20 121.42(12) . . ?
C18 C17 C20 121.14(13) . . ?
C19 C18 C17 121.27(12) . . ?
C19 C18 H18 119.4 . . ?
C17 C18 H18 119.4 . . ?
C18 C19 C14 121.78(11) . . ?
C18 C19 H19 119.1 . . ?
C14 C19 H19 119.1 . . ?
C17 C20 H20A 109.5 . . ?
C17 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C17 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C25 C21 C22 107.26(10) . . ?
C25 C21 C26 129.34(10) . . ?
C22 C21 C26 123.11(10) . . ?
C25 C21 Ti1 71.14(6) . . ?
C22 C21 Ti1 70.10(6) . . ?
C26 C21 Ti1 128.59(7) . . ?
C23 C22 C21 108.71(10) . . ?
C23 C22 Ti1 71.00(6) . . ?
C21 C22 Ti1 75.81(6) . . ?
C23 C22 H22 125.6 . . ?
C21 C22 H22 125.6 . . ?
Ti1 C22 H22 119.3 . . ?
C24 C23 C22 107.49(10) . . ?
C24 C23 Ti1 72.25(7) . . ?
C22 C23 Ti1 74.24(6) . . ?
C24 C23 H23 126.3 . . ?
C22 C23 H23 126.3 . . ?
Ti1 C23 H23 119.2 . . ?
C23 C24 C25 108.24(10) . . ?
C23 C24 Ti1 72.66(7) . . ?
C25 C24 Ti1 75.28(7) . . ?
C23 C24 H24 125.9 . . ?
C25 C24 H24 125.9 . . ?
Ti1 C24 H24 118.1 . . ?
C21 C25 C24 108.25(10) . . ?
C21 C25 Ti1 75.18(6) . . ?
C24 C25 Ti1 69.94(7) . . ?
C21 C25 H25 125.9 . . ?
C24 C25 H25 125.9 . . ?
Ti1 C25 H25 120.7 . . ?
C21 C26 C27 115.52(9) . . ?
C21 C26 C34 109.68(9) . . ?
C27 C26 C34 109.49(9) . . ?
C21 C26 H26 107.3 . . ?
C27 C26 H26 107.3 . . ?
C34 C26 H26 107.3 . . ?
C32 C27 C28 117.82(11) . . ?
C32 C27 C26 119.41(11) . . ?
C28 C27 C26 122.48(10) . . ?
C29 C28 C27 120.80(12) . . ?
C29 C28 H28 119.6 . . ?
C27 C28 H28 119.6 . . ?
C28 C29 C30 121.34(12) . . ?
C28 C29 H29 119.3 . . ?
C30 C29 H29 119.3 . . ?
C31 C30 C29 117.94(12) . . ?
C31 C30 C33 121.76(14) . . ?
C29 C30 C33 120.30(14) . . ?
C30 C31 C32 121.00(13) . . ?
C30 C31 H31 119.5 . . ?
C32 C31 H31 119.5 . . ?
C27 C32 C31 121.08(12) . . ?
C27 C32 H32 119.5 . . ?
C31 C32 H32 119.5 . . ?
C30 C33 H33A 109.5 . . ?
C30 C33 H33B 109.5 . . ?
H33A C33 H33B 109.5 . . ?
C30 C33 H33C 109.5 . . ?
H33A C33 H33C 109.5 . . ?
H33B C33 H33C 109.5 . . ?
C39 C34 C35 118.14(11) . . ?
C39 C34 C26 120.11(10) . . ?
C35 C34 C26 121.70(10) . . ?
C36 C35 C34 120.60(12) . . ?
C36 C35 H35 119.7 . . ?
C34 C35 H35 119.7 . . ?
C35 C36 C37 121.56(12) . . ?
C35 C36 H36 119.2 . . ?
C37 C36 H36 119.2 . . ?
C38 C37 C36 117.51(11) . . ?
C38 C37 C40 121.50(12) . . ?
C36 C37 C40 120.98(12) . . ?
C37 C38 C39 121.07(12) . . ?
C37 C38 H38 119.5 . . ?
C39 C38 H38 119.5 . . ?
C34 C39 C38 121.08(12) . . ?
C34 C39 H39 119.5 . . ?
C38 C39 H39 119.5 . . ?
C37 C40 H40A 109.5 . . ?
C37 C40 H40B 109.5 . . ?
H40A C40 H40B 109.5 . . ?
C37 C40 H40C 109.5 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
N1 C41 N3 123.12(11) . . ?
N1 C41 S1 112.33(8) . . ?
N3 C41 S1 124.55(10) . . ?
N3 C42 H42A 109.5 . . ?
N3 C42 H42B 109.5 . . ?
H42A C42 H42B 109.5 . . ?
N3 C42 H42C 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
N2 C43 C44 121.07(11) . . ?
N2 C43 H43 119.5 . . ?
C44 C43 H43 119.5 . . ?
C45 C44 C43 126.26(11) . . ?
C45 C44 S2 111.14(9) . . ?
C43 C44 S2 122.53(10) . . ?
C44 C45 C46 112.63(12) . . ?
C44 C45 H45 123.7 . . ?
C46 C45 H45 123.7 . . ?
C47 C46 C45 112.34(13) . . ?
C47 C46 H46 123.8 . . ?
C45 C46 H46 123.8 . . ?
C46 C47 S2 112.37(10) . . ?
C46 C47 H47 123.8 . . ?
S2 C47 H47 123.8 . . ?

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
C41 N1 N2 C43 179.96(10) . . . . ?
Ti1 N1 N2 C43 3.52(17) . . . . ?
C6 C1 C2 C3 -152.64(11) . . . . ?
C5 C1 C2 C3 1.03(12) . . . . ?
Ti1 C1 C2 C3 -68.18(8) . . . . ?
C6 C1 C2 Ti1 -84.45(10) . . . . ?
C5 C1 C2 Ti1 69.21(7) . . . . ?
C1 C2 C3 C4 -1.80(13) . . . . ?
Ti1 C2 C3 C4 -65.14(8) . . . . ?
C1 C2 C3 Ti1 63.34(7) . . . . ?
C2 C3 C4 C5 1.88(13) . . . . ?
Ti1 C3 C4 C5 -57.85(8) . . . . ?
C2 C3 C4 Ti1 59.73(8) . . . . ?
C3 C4 C5 C1 -1.25(13) . . . . ?
Ti1 C4 C5 C1 -60.52(7) . . . . ?
C3 C4 C5 Ti1 59.28(8) . . . . ?
C6 C1 C5 C4 153.55(11) . . . . ?
C2 C1 C5 C4 0.13(12) . . . . ?
Ti1 C1 C5 C4 67.05(8) . . . . ?
C6 C1 C5 Ti1 86.50(11) . . . . ?
C2 C1 C5 Ti1 -66.92(7) . . . . ?
C2 C1 C6 C7 172.95(10) . . . . ?
C5 C1 C6 C7 24.46(17) . . . . ?
Ti1 C1 C6 C7 100.63(10) . . . . ?
C2 C1 C6 C14 -30.89(16) . . . . ?
C5 C1 C6 C14 -179.38(10) . . . . ?
Ti1 C1 C6 C14 -103.21(10) . . . . ?
C1 C6 C7 C12 -142.71(12) . . . . ?
C14 C6 C7 C12 60.77(15) . . . . ?
C1 C6 C7 C8 39.28(16) . . . . ?
C14 C6 C7 C8 -117.24(12) . . . . ?
C12 C7 C8 C9 3.02(17) . . . . ?
C6 C7 C8 C9 -178.85(11) . . . . ?
C7 C8 C9 C10 -1.68(18) . . . . ?
C8 C9 C10 C11 -1.49(18) . . . . ?
C8 C9 C10 C13 175.42(12) . . . . ?
C9 C10 C11 C12 3.24(19) . . . . ?
C13 C10 C11 C12 -173.69(12) . . . . ?
C10 C11 C12 C7 -1.9(2) . . . . ?
C8 C7 C12 C11 -1.28(18) . . . . ?
C6 C7 C12 C11 -179.36(11) . . . . ?
C1 C6 C14 C15 148.53(12) . . . . ?
C7 C6 C14 C15 -54.74(16) . . . . ?
C1 C6 C14 C19 -35.65(16) . . . . ?
C7 C6 C14 C19 121.08(12) . . . . ?
C19 C14 C15 C16 -1.37(18) . . . . ?
C6 C14 C15 C16 174.58(12) . . . . ?
C14 C15 C16 C17 0.5(2) . . . . ?
C15 C16 C17 C18 0.9(2) . . . . ?
C15 C16 C17 C20 -177.99(13) . . . . ?
C16 C17 C18 C19 -1.41(19) . . . . ?
C20 C17 C18 C19 177.53(13) . . . . ?
C17 C18 C19 C14 0.49(19) . . . . ?
C15 C14 C19 C18 0.91(18) . . . . ?
C6 C14 C19 C18 -175.22(11) . . . . ?
C25 C21 C22 C23 -2.08(13) . . . . ?
C26 C21 C22 C23 172.34(10) . . . . ?
Ti1 C21 C22 C23 -63.89(8) . . . . ?
C25 C21 C22 Ti1 61.80(8) . . . . ?
C26 C21 C22 Ti1 -123.78(10) . . . . ?
C21 C22 C23 C24 1.93(13) . . . . ?
Ti1 C22 C23 C24 -65.10(8) . . . . ?
C21 C22 C23 Ti1 67.03(8) . . . . ?
C22 C23 C24 C25 -1.03(13) . . . . ?
Ti1 C23 C24 C25 -67.47(8) . . . . ?
C22 C23 C24 Ti1 66.43(8) . . . . ?
C22 C21 C25 C24 1.43(13) . . . . ?
C26 C21 C25 C24 -172.53(11) . . . . ?
Ti1 C21 C25 C24 62.56(8) . . . . ?
C22 C21 C25 Ti1 -61.13(8) . . . . ?
C26 C21 C25 Ti1 124.91(11) . . . . ?
C23 C24 C25 C21 -0.25(13) . . . . ?
Ti1 C24 C25 C21 -65.98(8) . . . . ?
C23 C24 C25 Ti1 65.72(8) . . . . ?
C25 C21 C26 C27 -0.72(16) . . . . ?
C22 C21 C26 C27 -173.83(10) . . . . ?
Ti1 C21 C26 C27 96.14(11) . . . . ?
C25 C21 C26 C34 123.57(12) . . . . ?
C22 C21 C26 C34 -49.54(14) . . . . ?
Ti1 C21 C26 C34 -139.58(8) . . . . ?
C21 C26 C27 C32 -138.18(11) . . . . ?
C34 C26 C27 C32 97.44(12) . . . . ?
C21 C26 C27 C28 48.23(15) . . . . ?
C34 C26 C27 C28 -76.15(13) . . . . ?
C32 C27 C28 C29 1.52(17) . . . . ?
C26 C27 C28 C29 175.21(11) . . . . ?
C27 C28 C29 C30 -1.29(19) . . . . ?
C28 C29 C30 C31 -0.24(19) . . . . ?
C28 C29 C30 C33 178.85(13) . . . . ?
C29 C30 C31 C32 1.50(19) . . . . ?
C33 C30 C31 C32 -177.59(13) . . . . ?
C28 C27 C32 C31 -0.27(18) . . . . ?
C26 C27 C32 C31 -174.16(11) . . . . ?
C30 C31 C32 C27 -1.25(19) . . . . ?
C21 C26 C34 C39 135.99(12) . . . . ?
C27 C26 C34 C39 -96.28(13) . . . . ?
C21 C26 C34 C35 -46.59(15) . . . . ?
C27 C26 C34 C35 81.13(14) . . . . ?
C39 C34 C35 C36 -1.4(2) . . . . ?
C26 C34 C35 C36 -178.86(12) . . . . ?
C34 C35 C36 C37 0.1(2) . . . . ?
C35 C36 C37 C38 1.7(2) . . . . ?
C35 C36 C37 C40 -177.66(13) . . . . ?
C36 C37 C38 C39 -2.3(2) . . . . ?
C40 C37 C38 C39 177.08(13) . . . . ?
C35 C34 C39 C38 0.8(2) . . . . ?
C26 C34 C39 C38 178.32(12) . . . . ?
C37 C38 C39 C34 1.0(2) . . . . ?
N2 N1 C41 N3 -2.23(17) . . . . ?
Ti1 N1 C41 N3 175.44(10) . . . . ?
N2 N1 C41 S1 178.43(8) . . . . ?
Ti1 N1 C41 S1 -3.89(9) . . . . ?
C42 N3 C41 N1 176.58(12) . . . . ?
C42 N3 C41 S1 -4.17(19) . . . . ?
Ti1 S1 C41 N1 3.23(8) . . . . ?
Ti1 S1 C41 N3 -176.09(11) . . . . ?
N1 N2 C43 C44 -178.88(10) . . . . ?
N2 C43 C44 C45 176.84(12) . . . . ?
N2 C43 C44 S2 0.20(16) . . . . ?
C47 S2 C44 C45 -0.56(10) . . . . ?
C47 S2 C44 C43 176.52(11) . . . . ?
C43 C44 C45 C46 -176.48(12) . . . . ?
S2 C44 C45 C46 0.48(14) . . . . ?
C44 C45 C46 C47 -0.10(18) . . . . ?
C45 C46 C47 S2 -0.34(17) . . . . ?
C44 S2 C47 C46 0.52(12) . . . . ?

_refine_diff_density_max         0.435
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.052


