# Electronic Supplementary Material (ESI) for Polymer Chemistry.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_mo_dm11665_0m
_database_code_depnum_ccdc_archive 'CCDC 1887509'
_audit_update_record             
;
2018-12-27 deposited with the CCDC.	2019-05-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H16 Cl3 F6 N O S Ti'
_chemical_formula_weight         586.65

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'
O O 0.0106 0.0060 '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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/c

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

_cell_length_a                   7.0364(16)
_cell_length_b                   21.638(5)
_cell_length_c                   15.514(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 96.356(4)
_cell_angle_gamma                90.00
_cell_volume                     2347.6(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    133(2)
_cell_measurement_reflns_used    3848
_cell_measurement_theta_min      2.30
_cell_measurement_theta_max      27.14

_exptl_crystal_description       prism
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.660
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1176
_exptl_absorpt_coefficient_mu    0.857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8144
_exptl_absorpt_correction_T_max  0.9831
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      133(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17123
_diffrn_reflns_av_R_equivalents  0.0680
_diffrn_reflns_av_sigmaI/netI    0.0653
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.62
_diffrn_reflns_theta_max         27.00
_reflns_number_total             5092
_reflns_number_gt                3962
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0680P)²+8.5363P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5092
_refine_ls_number_parameters     326
_refine_ls_number_restraints     30
_refine_ls_R_factor_all          0.0859
_refine_ls_R_factor_gt           0.0641
_refine_ls_wR_factor_ref         0.1663
_refine_ls_wR_factor_gt          0.1556
_refine_ls_goodness_of_fit_ref   1.059
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.31473(11) 0.63362(4) 0.83193(5) 0.0163(2) Uani 1 1 d . . .
N1 N 0.5573(5) 0.64870(17) 0.9258(2) 0.0159(7) Uani 1 1 d . . .
O1 O 0.2189(4) 0.70099(14) 0.8817(2) 0.0205(7) Uani 1 1 d . . .
S1 S 0.50672(15) 0.53669(5) 0.80430(8) 0.0222(3) Uani 1 1 d . . .
F1 F -0.477(2) 0.9137(7) 0.9496(12) 0.085(4) Uani 0.50 1 d PU A 1
F2 F -0.285(2) 0.9630(6) 0.8820(8) 0.091(4) Uani 0.50 1 d PU A 1
F3 F -0.267(4) 0.9691(12) 1.0167(11) 0.058(4) Uani 0.50 1 d PU A 1
F1' F -0.473(2) 0.9057(7) 0.9987(9) 0.068(4) Uani 0.50 1 d PU A 2
F2' F -0.4057(17) 0.9329(5) 0.8754(7) 0.066(3) Uani 0.50 1 d PU A 2
F3' F -0.268(4) 0.9753(11) 0.9880(13) 0.059(5) Uani 0.50 1 d PU A 2
F4 F 1.3129(4) 0.60026(15) 1.2127(2) 0.0363(8) Uani 1 1 d . . .
F5 F 1.2780(4) 0.68094(14) 1.2902(2) 0.0349(7) Uani 1 1 d . . .
F6 F 1.1490(4) 0.59473(14) 1.32084(18) 0.0321(7) Uani 1 1 d . . .
C1 C 0.2449(6) 0.7325(2) 0.9551(3) 0.0167(8) Uani 1 1 d . . .
C2 C 0.3957(6) 0.7197(2) 1.0144(3) 0.0200(9) Uani 1 1 d . . .
H2 H 0.4003 0.7390 1.0696 0.024 Uiso 1 1 calc R . .
C3 C 0.5503(6) 0.6783(2) 0.9991(3) 0.0164(9) Uani 1 1 d . . .
C4 C 0.7359(6) 0.6178(2) 0.9066(3) 0.0206(9) Uani 1 1 d . . .
H4A H 0.8352 0.6231 0.9565 0.025 Uiso 1 1 calc R . .
H4B H 0.7827 0.6375 0.8554 0.025 Uiso 1 1 calc R . .
C5 C 0.7028(7) 0.5494(2) 0.8891(3) 0.0251(10) Uani 1 1 d . . .
H5A H 0.6736 0.5287 0.9430 0.030 Uiso 1 1 calc R . .
H5B H 0.8209 0.5307 0.8714 0.030 Uiso 1 1 calc R . .
C6 C 0.6195(7) 0.5472(2) 0.7070(3) 0.0286(11) Uani 1 1 d . . .
H6A H 0.6998 0.5843 0.7126 0.043 Uiso 1 1 calc R . .
H6B H 0.5214 0.5520 0.6575 0.043 Uiso 1 1 calc R . .
H6C H 0.6990 0.5111 0.6978 0.043 Uiso 1 1 calc R . .
C7 C 0.0979(6) 0.7808(2) 0.9607(3) 0.0194(9) Uani 1 1 d . . .
C8 C 0.1301(7) 0.8317(2) 1.0161(3) 0.0230(10) Uani 1 1 d . . .
H8 H 0.2443 0.8345 1.0547 0.028 Uiso 1 1 calc R . .
C9 C -0.0070(7) 0.8782(2) 1.0140(3) 0.0272(11) Uani 1 1 d . . .
H9 H 0.0134 0.9128 1.0517 0.033 Uiso 1 1 calc R . .
C10 C -0.1712(7) 0.8745(2) 0.9578(3) 0.0263(10) Uani 1 1 d . A .
C11 C -0.2078(7) 0.8232(2) 0.9037(3) 0.0253(10) Uani 1 1 d . . .
H11 H -0.3248 0.8198 0.8671 0.030 Uiso 1 1 calc R . .
C12 C -0.0704(6) 0.7775(2) 0.9045(3) 0.0206(9) Uani 1 1 d . . .
H12 H -0.0911 0.7433 0.8662 0.025 Uiso 1 1 calc R . .
C13 C -0.3151(10) 0.9254(3) 0.9529(4) 0.0459(16) Uani 1 1 d . . .
C14 C 0.7052(6) 0.6698(2) 1.0721(3) 0.0172(9) Uani 1 1 d . . .
C15 C 0.8219(6) 0.7185(2) 1.1045(3) 0.0182(9) Uani 1 1 d . . .
H15 H 0.7961 0.7595 1.0845 0.022 Uiso 1 1 calc R . .
C16 C 0.9763(6) 0.7067(2) 1.1663(3) 0.0191(9) Uani 1 1 d . . .
H16 H 1.0581 0.7394 1.1879 0.023 Uiso 1 1 calc R . .
C17 C 1.0102(6) 0.6471(2) 1.1960(3) 0.0189(9) Uani 1 1 d . . .
C18 C 0.8868(7) 0.5991(2) 1.1687(3) 0.0233(10) Uani 1 1 d . . .
H18 H 0.9060 0.5588 1.1924 0.028 Uiso 1 1 calc R . .
C19 C 0.7351(7) 0.6113(2) 1.1062(3) 0.0245(10) Uani 1 1 d . . .
H19 H 0.6503 0.5788 1.0864 0.029 Uiso 1 1 calc R . .
C20 C 1.1856(7) 0.6313(2) 1.2548(3) 0.0239(10) Uani 1 1 d . . .
Cl1 Cl 0.47561(17) 0.68760(5) 0.73424(7) 0.0251(3) Uani 1 1 d . . .
Cl2 Cl 0.08060(18) 0.60175(7) 0.73033(8) 0.0373(3) Uani 1 1 d . . .
Cl3 Cl 0.21833(15) 0.56699(5) 0.93780(8) 0.0247(3) Uani 1 1 d . . .


_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 1.814(3) . ?
Ti1 N1 2.143(4) . ?
Ti1 Cl2 2.2580(14) . ?
Ti1 Cl1 2.3070(14) . ?
Ti1 Cl3 2.3417(14) . ?
Ti1 S1 2.5567(14) . ?
N1 C3 1.311(6) . ?
N1 C4 1.482(5) . ?
O1 C1 1.323(5) . ?
S1 C6 1.796(5) . ?
S1 C5 1.818(5) . ?
F1 C13 1.161(16) . ?
F2 C13 1.403(12) . ?
F3 C13 1.38(3) . ?
F1' C13 1.449(15) . ?
F2' C13 1.307(10) . ?
F3' C13 1.24(3) . ?
F4 C20 1.345(5) . ?
F5 C20 1.342(6) . ?
F6 C20 1.341(6) . ?
C1 C2 1.354(6) . ?
C1 C7 1.481(6) . ?
C2 C3 1.449(6) . ?
C2 H2 0.9500 . ?
C3 C14 1.494(6) . ?
C4 C5 1.520(6) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
C7 C12 1.393(6) . ?
C7 C8 1.399(7) . ?
C8 C9 1.392(7) . ?
C8 H8 0.9500 . ?
C9 C10 1.371(7) . ?
C9 H9 0.9500 . ?
C10 C11 1.399(7) . ?
C10 C13 1.492(7) . ?
C11 C12 1.381(6) . ?
C11 H11 0.9500 . ?
C12 H12 0.9500 . ?
C14 C19 1.380(6) . ?
C14 C15 1.395(6) . ?
C15 C16 1.391(6) . ?
C15 H15 0.9500 . ?
C16 C17 1.380(6) . ?
C16 H16 0.9500 . ?
C17 C18 1.391(6) . ?
C17 C20 1.491(6) . ?
C18 C19 1.386(6) . ?
C18 H18 0.9500 . ?
C19 H19 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
O1 Ti1 N1 83.91(14) . . ?
O1 Ti1 Cl2 105.40(11) . . ?
N1 Ti1 Cl2 170.31(11) . . ?
O1 Ti1 Cl1 96.03(11) . . ?
N1 Ti1 Cl1 87.58(11) . . ?
Cl2 Ti1 Cl1 93.97(6) . . ?
O1 Ti1 Cl3 92.65(11) . . ?
N1 Ti1 Cl3 83.55(10) . . ?
Cl2 Ti1 Cl3 93.21(6) . . ?
Cl1 Ti1 Cl3 166.86(5) . . ?
O1 Ti1 S1 163.50(11) . . ?
N1 Ti1 S1 80.97(10) . . ?
Cl2 Ti1 S1 89.46(6) . . ?
Cl1 Ti1 S1 89.91(5) . . ?
Cl3 Ti1 S1 79.16(5) . . ?
C3 N1 C4 120.6(4) . . ?
C3 N1 Ti1 124.1(3) . . ?
C4 N1 Ti1 115.1(3) . . ?
C1 O1 Ti1 139.3(3) . . ?
C6 S1 C5 102.6(2) . . ?
C6 S1 Ti1 109.13(18) . . ?
C5 S1 Ti1 97.34(15) . . ?
O1 C1 C2 120.2(4) . . ?
O1 C1 C7 112.6(4) . . ?
C2 C1 C7 127.2(4) . . ?
C1 C2 C3 124.1(4) . . ?
C1 C2 H2 117.9 . . ?
C3 C2 H2 117.9 . . ?
N1 C3 C2 123.0(4) . . ?
N1 C3 C14 120.2(4) . . ?
C2 C3 C14 116.7(4) . . ?
N1 C4 C5 111.1(4) . . ?
N1 C4 H4A 109.4 . . ?
C5 C4 H4A 109.4 . . ?
N1 C4 H4B 109.4 . . ?
C5 C4 H4B 109.4 . . ?
H4A C4 H4B 108.0 . . ?
C4 C5 S1 111.5(3) . . ?
C4 C5 H5A 109.3 . . ?
S1 C5 H5A 109.3 . . ?
C4 C5 H5B 109.3 . . ?
S1 C5 H5B 109.3 . . ?
H5A C5 H5B 108.0 . . ?
S1 C6 H6A 109.5 . . ?
S1 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
S1 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C12 C7 C8 119.5(4) . . ?
C12 C7 C1 118.6(4) . . ?
C8 C7 C1 121.7(4) . . ?
C9 C8 C7 119.4(4) . . ?
C9 C8 H8 120.3 . . ?
C7 C8 H8 120.3 . . ?
C10 C9 C8 120.4(5) . . ?
C10 C9 H9 119.8 . . ?
C8 C9 H9 119.8 . . ?
C9 C10 C11 121.0(4) . . ?
C9 C10 C13 120.6(5) . . ?
C11 C10 C13 118.5(5) . . ?
C12 C11 C10 118.7(4) . . ?
C12 C11 H11 120.7 . . ?
C10 C11 H11 120.7 . . ?
C11 C12 C7 121.0(4) . . ?
C11 C12 H12 119.5 . . ?
C7 C12 H12 119.5 . . ?
F1 C13 F3' 115.1(15) . . ?
F1 C13 F2' 67.1(10) . . ?
F3' C13 F2' 112.1(11) . . ?
F1 C13 F3 110.1(15) . . ?
F3' C13 F3 19.5(16) . . ?
F2' C13 F3 129.0(10) . . ?
F1 C13 F2 109.0(11) . . ?
F3' C13 F2 77.4(12) . . ?
F2' C13 F2 46.2(7) . . ?
F3 C13 F2 96.8(12) . . ?
F1 C13 F1' 32.4(9) . . ?
F3' C13 F1' 103.0(14) . . ?
F2' C13 F1' 99.5(10) . . ?
F3 C13 F1' 89.5(14) . . ?
F2 C13 F1' 138.3(9) . . ?
F1 C13 C10 119.8(9) . . ?
F3' C13 C10 118.2(12) . . ?
F2' C13 C10 113.4(6) . . ?
F3 C13 C10 110.8(11) . . ?
F2 C13 C10 107.8(6) . . ?
F1' C13 C10 108.2(7) . . ?
C19 C14 C15 119.9(4) . . ?
C19 C14 C3 118.1(4) . . ?
C15 C14 C3 122.0(4) . . ?
C16 C15 C14 119.5(4) . . ?
C16 C15 H15 120.3 . . ?
C14 C15 H15 120.3 . . ?
C17 C16 C15 119.7(4) . . ?
C17 C16 H16 120.2 . . ?
C15 C16 H16 120.2 . . ?
C16 C17 C18 121.1(4) . . ?
C16 C17 C20 121.3(4) . . ?
C18 C17 C20 117.4(4) . . ?
C19 C18 C17 118.5(4) . . ?
C19 C18 H18 120.7 . . ?
C17 C18 H18 120.7 . . ?
C14 C19 C18 121.0(4) . . ?
C14 C19 H19 119.5 . . ?
C18 C19 H19 119.5 . . ?
F6 C20 F5 106.5(4) . . ?
F6 C20 F4 105.8(4) . . ?
F5 C20 F4 106.3(4) . . ?
F6 C20 C17 112.8(4) . . ?
F5 C20 C17 113.4(4) . . ?
F4 C20 C17 111.6(4) . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        27.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.829
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.111
####################################################################### 
# 
# 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_cd211516
_database_code_depnum_ccdc_archive 'CCDC 1887510'
_audit_update_record             
;
2018-12-27 deposited with the CCDC.	2019-05-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H22 Cl3 N O S Ti'
_chemical_formula_weight         478.70

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/n

loop_
_symmetry_equiv_pos_as_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                   11.7525(6)
_cell_length_b                   13.7868(8)
_cell_length_c                   15.8335(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 99.7010(10)
_cell_angle_gamma                90.00
_cell_volume                     2528.8(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4412
_cell_measurement_theta_min      4.719
_cell_measurement_theta_max      51.651

_exptl_crystal_description       prismatic
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.307
_exptl_crystal_size_mid          0.269
_exptl_crystal_size_min          0.211
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             984
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.77999
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4969
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0308
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.97
_diffrn_reflns_theta_max         25.99
_reflns_number_total             4969
_reflns_number_gt                3870
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0638P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4969
_refine_ls_number_parameters     247
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0382
_refine_ls_wR_factor_ref         0.1062
_refine_ls_wR_factor_gt          0.1016
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_restrained_S_all      1.055
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.000 0.500 1.000 233 49 ' '
2 0.500 0.000 0.500 233 49 ' '
_platon_squeeze_details          
;
;




loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.54603(3) 0.29419(3) 0.17939(2) 0.04184(12) Uani 1 1 d . . .
S1 S 0.65491(5) 0.45097(4) 0.23461(4) 0.05499(17) Uani 1 1 d . . .
Cl1 Cl 0.40064(6) 0.33077(6) 0.25161(5) 0.0818(2) Uani 1 1 d . . .
Cl2 Cl 0.45994(5) 0.37678(4) 0.05951(4) 0.05847(17) Uani 1 1 d . . .
Cl3 Cl 0.66531(5) 0.23627(5) 0.30092(4) 0.06277(18) Uani 1 1 d . . .
N1 N 0.69763(13) 0.28370(11) 0.12009(10) 0.0398(4) Uani 1 1 d . . .
O1 O 0.51516(11) 0.17210(10) 0.13823(9) 0.0462(3) Uani 1 1 d . . .
C1 C 0.57935(16) 0.09565(14) 0.12501(12) 0.0396(4) Uani 1 1 d . . .
C2 C 0.68923(16) 0.10969(14) 0.11154(13) 0.0418(4) Uani 1 1 d . . .
H2 H 0.7322 0.0543 0.1052 0.050 Uiso 1 1 calc R . .
C3 C 0.74586(16) 0.20121(14) 0.10608(12) 0.0391(4) Uani 1 1 d . . .
C4 C 0.75204(18) 0.37630(15) 0.10334(14) 0.0489(5) Uani 1 1 d . . .
H4A H 0.6998 0.4134 0.0614 0.059 Uiso 1 1 calc R . .
H4B H 0.8219 0.3639 0.0801 0.059 Uiso 1 1 calc R . .
C5 C 0.78103(19) 0.43380(18) 0.18521(17) 0.0585(6) Uani 1 1 d . . .
H5A H 0.8119 0.4965 0.1728 0.070 Uiso 1 1 calc R . .
H5B H 0.8399 0.3999 0.2246 0.070 Uiso 1 1 calc R . .
C6 C 0.5896(2) 0.55462(18) 0.1783(2) 0.0800(8) Uani 1 1 d . . .
H6A H 0.6356 0.6110 0.1953 0.120 Uiso 1 1 calc R . .
H6B H 0.5136 0.5638 0.1915 0.120 Uiso 1 1 calc R . .
H6C H 0.5845 0.5447 0.1178 0.120 Uiso 1 1 calc R . .
C7 C 0.52207(16) 0.00163(14) 0.12681(12) 0.0392(4) Uani 1 1 d . . .
C8 C 0.42648(17) -0.00784(15) 0.16668(14) 0.0481(5) Uani 1 1 d . . .
H8 H 0.3988 0.0461 0.1921 0.058 Uiso 1 1 calc R . .
C9 C 0.37206(18) -0.09551(16) 0.16926(16) 0.0536(5) Uani 1 1 d . . .
H9 H 0.3085 -0.1000 0.1970 0.064 Uiso 1 1 calc R . .
C10 C 0.40949(18) -0.17756(15) 0.13161(13) 0.0465(5) Uani 1 1 d . . .
C11 C 0.50573(19) -0.16823(16) 0.09199(15) 0.0520(5) Uani 1 1 d . . .
H11 H 0.5334 -0.2221 0.0665 0.062 Uiso 1 1 calc R . .
C12 C 0.56075(18) -0.08031(15) 0.08993(14) 0.0485(5) Uani 1 1 d . . .
H12 H 0.6252 -0.0759 0.0632 0.058 Uiso 1 1 calc R . .
C13 C 0.3471(2) -0.27213(16) 0.13152(17) 0.0625(6) Uani 1 1 d . . .
H13A H 0.3727 -0.3053 0.1846 0.094 Uiso 1 1 calc R . .
H13B H 0.3628 -0.3114 0.0848 0.094 Uiso 1 1 calc R . .
H13C H 0.2655 -0.2604 0.1252 0.094 Uiso 1 1 calc R . .
C14 C 0.86451(16) 0.19347(15) 0.08474(13) 0.0414(4) Uani 1 1 d . . .
C15 C 0.88384(18) 0.14530(17) 0.01230(14) 0.0518(5) Uani 1 1 d . . .
H15 H 0.8219 0.1192 -0.0251 0.062 Uiso 1 1 calc R . .
C16 C 0.9943(2) 0.1354(2) -0.00540(16) 0.0613(6) Uani 1 1 d . . .
H16 H 1.0055 0.1041 -0.0554 0.074 Uiso 1 1 calc R . .
C17 C 1.08831(18) 0.17109(18) 0.04963(16) 0.0570(6) Uani 1 1 d . . .
C18 C 1.06881(19) 0.21785(18) 0.12249(16) 0.0586(6) Uani 1 1 d . . .
H18 H 1.1313 0.2420 0.1607 0.070 Uiso 1 1 calc R . .
C19 C 0.95879(18) 0.22987(17) 0.14035(14) 0.0521(5) Uani 1 1 d . . .
H19 H 0.9478 0.2624 0.1898 0.063 Uiso 1 1 calc R . .
C20 C 1.2089(2) 0.1593(3) 0.0294(2) 0.0884(10) Uani 1 1 d . . .
H20A H 1.2598 0.2049 0.0624 0.133 Uiso 1 1 calc R . .
H20B H 1.2077 0.1709 -0.0306 0.133 Uiso 1 1 calc R . .
H20C H 1.2357 0.0945 0.0434 0.133 Uiso 1 1 calc R . .


_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 1.8194(14) . ?
Ti1 N1 2.1542(15) . ?
Ti1 Cl1 2.2671(7) . ?
Ti1 Cl2 2.2969(7) . ?
Ti1 Cl3 2.3230(7) . ?
Ti1 S1 2.5878(7) . ?
S1 C6 1.788(3) . ?
S1 C5 1.804(2) . ?
N1 C3 1.306(2) . ?
N1 C4 1.472(2) . ?
O1 C1 1.333(2) . ?
C1 C2 1.358(3) . ?
C1 C7 1.463(3) . ?
C2 C3 1.436(3) . ?
C2 H2 0.9300 . ?
C3 C14 1.493(3) . ?
C4 C5 1.509(3) . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C5 H5A 0.9700 . ?
C5 H5B 0.9700 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C7 C12 1.383(3) . ?
C7 C8 1.384(3) . ?
C8 C9 1.371(3) . ?
C8 H8 0.9300 . ?
C9 C10 1.385(3) . ?
C9 H9 0.9300 . ?
C10 C11 1.389(3) . ?
C10 C13 1.496(3) . ?
C11 C12 1.377(3) . ?
C11 H11 0.9300 . ?
C12 H12 0.9300 . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 C15 1.377(3) . ?
C14 C19 1.388(3) . ?
C15 C16 1.381(3) . ?
C15 H15 0.9300 . ?
C16 C17 1.377(3) . ?
C16 H16 0.9300 . ?
C17 C18 1.374(3) . ?
C17 C20 1.514(3) . ?
C18 C19 1.379(3) . ?
C18 H18 0.9300 . ?
C19 H19 0.9300 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?

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 84.91(6) . . ?
O1 Ti1 Cl1 105.35(5) . . ?
N1 Ti1 Cl1 169.66(5) . . ?
O1 Ti1 Cl2 97.42(5) . . ?
N1 Ti1 Cl2 87.40(5) . . ?
Cl1 Ti1 Cl2 92.41(3) . . ?
O1 Ti1 Cl3 91.99(5) . . ?
N1 Ti1 Cl3 84.84(5) . . ?
Cl1 Ti1 Cl3 93.42(3) . . ?
Cl2 Ti1 Cl3 167.22(3) . . ?
O1 Ti1 S1 162.03(4) . . ?
N1 Ti1 S1 78.77(4) . . ?
Cl1 Ti1 S1 90.89(3) . . ?
Cl2 Ti1 S1 89.37(2) . . ?
Cl3 Ti1 S1 79.18(2) . . ?
C6 S1 C5 101.75(14) . . ?
C6 S1 Ti1 110.66(10) . . ?
C5 S1 Ti1 98.02(8) . . ?
C3 N1 C4 120.70(16) . . ?
C3 N1 Ti1 123.16(13) . . ?
C4 N1 Ti1 115.89(12) . . ?
C1 O1 Ti1 134.73(12) . . ?
O1 C1 C2 119.37(17) . . ?
O1 C1 C7 115.03(16) . . ?
C2 C1 C7 125.60(18) . . ?
C1 C2 C3 126.68(18) . . ?
C1 C2 H2 116.7 . . ?
C3 C2 H2 116.7 . . ?
N1 C3 C2 122.42(17) . . ?
N1 C3 C14 123.32(18) . . ?
C2 C3 C14 114.26(17) . . ?
N1 C4 C5 110.06(18) . . ?
N1 C4 H4A 109.6 . . ?
C5 C4 H4A 109.6 . . ?
N1 C4 H4B 109.6 . . ?
C5 C4 H4B 109.6 . . ?
H4A C4 H4B 108.2 . . ?
C4 C5 S1 110.99(15) . . ?
C4 C5 H5A 109.4 . . ?
S1 C5 H5A 109.4 . . ?
C4 C5 H5B 109.4 . . ?
S1 C5 H5B 109.4 . . ?
H5A C5 H5B 108.0 . . ?
S1 C6 H6A 109.5 . . ?
S1 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
S1 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C12 C7 C8 117.72(18) . . ?
C12 C7 C1 122.03(17) . . ?
C8 C7 C1 120.25(17) . . ?
C9 C8 C7 121.00(19) . . ?
C9 C8 H8 119.5 . . ?
C7 C8 H8 119.5 . . ?
C8 C9 C10 121.58(19) . . ?
C8 C9 H9 119.2 . . ?
C10 C9 H9 119.2 . . ?
C9 C10 C11 117.44(19) . . ?
C9 C10 C13 121.4(2) . . ?
C11 C10 C13 121.1(2) . . ?
C12 C11 C10 120.9(2) . . ?
C12 C11 H11 119.5 . . ?
C10 C11 H11 119.5 . . ?
C11 C12 C7 121.33(19) . . ?
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 118.48(18) . . ?
C15 C14 C3 120.96(18) . . ?
C19 C14 C3 120.46(19) . . ?
C14 C15 C16 120.6(2) . . ?
C14 C15 H15 119.7 . . ?
C16 C15 H15 119.7 . . ?
C17 C16 C15 121.2(2) . . ?
C17 C16 H16 119.4 . . ?
C15 C16 H16 119.4 . . ?
C18 C17 C16 118.0(2) . . ?
C18 C17 C20 121.5(2) . . ?
C16 C17 C20 120.5(2) . . ?
C17 C18 C19 121.6(2) . . ?
C17 C18 H18 119.2 . . ?
C19 C18 H18 119.2 . . ?
C18 C19 C14 120.1(2) . . ?
C18 C19 H19 119.9 . . ?
C14 C19 H19 119.9 . . ?
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 . . ?

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
O1 Ti1 S1 C6 129.2(2) . . . . ?
N1 Ti1 S1 C6 104.00(12) . . . . ?
Cl1 Ti1 S1 C6 -75.87(12) . . . . ?
Cl2 Ti1 S1 C6 16.53(12) . . . . ?
Cl3 Ti1 S1 C6 -169.18(12) . . . . ?
O1 Ti1 S1 C5 23.3(2) . . . . ?
N1 Ti1 S1 C5 -1.83(10) . . . . ?
Cl1 Ti1 S1 C5 178.29(9) . . . . ?
Cl2 Ti1 S1 C5 -89.30(9) . . . . ?
Cl3 Ti1 S1 C5 84.99(9) . . . . ?
O1 Ti1 N1 C3 -25.63(16) . . . . ?
Cl1 Ti1 N1 C3 147.5(2) . . . . ?
Cl2 Ti1 N1 C3 -123.32(15) . . . . ?
Cl3 Ti1 N1 C3 66.84(15) . . . . ?
S1 Ti1 N1 C3 146.80(16) . . . . ?
O1 Ti1 N1 C4 160.20(14) . . . . ?
Cl1 Ti1 N1 C4 -26.6(4) . . . . ?
Cl2 Ti1 N1 C4 62.51(14) . . . . ?
Cl3 Ti1 N1 C4 -107.33(14) . . . . ?
S1 Ti1 N1 C4 -27.37(13) . . . . ?
N1 Ti1 O1 C1 33.42(18) . . . . ?
Cl1 Ti1 O1 C1 -145.31(17) . . . . ?
Cl2 Ti1 O1 C1 120.12(18) . . . . ?
Cl3 Ti1 O1 C1 -51.22(18) . . . . ?
S1 Ti1 O1 C1 8.7(3) . . . . ?
Ti1 O1 C1 C2 -25.6(3) . . . . ?
Ti1 O1 C1 C7 154.21(14) . . . . ?
O1 C1 C2 C3 -2.9(3) . . . . ?
C7 C1 C2 C3 177.32(19) . . . . ?
C4 N1 C3 C2 -172.24(19) . . . . ?
Ti1 N1 C3 C2 13.9(3) . . . . ?
C4 N1 C3 C14 8.9(3) . . . . ?
Ti1 N1 C3 C14 -164.97(14) . . . . ?
C1 C2 C3 N1 5.1(3) . . . . ?
C1 C2 C3 C14 -175.97(19) . . . . ?
C3 N1 C4 C5 -118.6(2) . . . . ?
Ti1 N1 C4 C5 55.7(2) . . . . ?
N1 C4 C5 S1 -55.2(2) . . . . ?
C6 S1 C5 C4 -83.9(2) . . . . ?
Ti1 S1 C5 C4 29.27(18) . . . . ?
O1 C1 C7 C12 160.16(19) . . . . ?
C2 C1 C7 C12 -20.0(3) . . . . ?
O1 C1 C7 C8 -20.3(3) . . . . ?
C2 C1 C7 C8 159.6(2) . . . . ?
C12 C7 C8 C9 -0.1(3) . . . . ?
C1 C7 C8 C9 -179.7(2) . . . . ?
C7 C8 C9 C10 -0.6(4) . . . . ?
C8 C9 C10 C11 0.9(3) . . . . ?
C8 C9 C10 C13 -177.5(2) . . . . ?
C9 C10 C11 C12 -0.5(3) . . . . ?
C13 C10 C11 C12 178.0(2) . . . . ?
C10 C11 C12 C7 -0.2(3) . . . . ?
C8 C7 C12 C11 0.6(3) . . . . ?
C1 C7 C12 C11 -179.9(2) . . . . ?
N1 C3 C14 C15 -125.5(2) . . . . ?
C2 C3 C14 C15 55.6(3) . . . . ?
N1 C3 C14 C19 58.3(3) . . . . ?
C2 C3 C14 C19 -120.6(2) . . . . ?
C19 C14 C15 C16 -1.4(3) . . . . ?
C3 C14 C15 C16 -177.6(2) . . . . ?
C14 C15 C16 C17 1.6(4) . . . . ?
C15 C16 C17 C18 -0.6(4) . . . . ?
C15 C16 C17 C20 179.8(2) . . . . ?
C16 C17 C18 C19 -0.5(4) . . . . ?
C20 C17 C18 C19 179.0(2) . . . . ?
C17 C18 C19 C14 0.7(4) . . . . ?
C15 C14 C19 C18 0.2(3) . . . . ?
C3 C14 C19 C18 176.5(2) . . . . ?

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
C6 H6A Cl3 0.96 2.90 3.789(3) 154.5 2_655
C11 H11 Cl2 0.93 2.93 3.809(2) 158.2 3_655
C9 H9 Cl1 0.93 2.88 3.772(2) 161.3 2_545

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.99
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.060
