# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_shelxl
_database_code_depnum_ccdc_archive 'CCDC 1031337'
_audit_update_record             
;
2014-10-27 deposited with the CCDC.
2015-08-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C33 H39 N5 O12 S2 Ti, 2(C3 H6 O)'
_chemical_formula_sum            'C39 H51 N5 O14 S2 Ti '
_chemical_formula_weight         925.86

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'
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   'C 2/c'

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

_cell_length_a                   38.9176(16)
_cell_length_b                   10.0754(5)
_cell_length_c                   21.8768(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 93.133(3)
_cell_angle_gamma                90.00
_cell_volume                     8565.3(6)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    37924
_cell_measurement_theta_min      1.85
_cell_measurement_theta_max      27.22

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.200
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3888
_exptl_absorpt_coefficient_mu    0.370
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.7069
_exptl_absorpt_correction_T_max  0.8801
_exptl_absorpt_process_details   
;
'X-SHAPE 2.07 (03-Aug-2005) Stoe & Cie, Darmstadt, Germany'
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            58758
_diffrn_reflns_av_R_equivalents  0.1041
_diffrn_reflns_av_sigmaI/netI    0.0594
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         1.86
_diffrn_reflns_theta_max         26.91
_reflns_number_total             9115
_reflns_number_gt                6945
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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)+(0.0390P)²+2.9339P] 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         9115
_refine_ls_number_parameters     556
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0436
_refine_ls_wR_factor_ref         0.0901
_refine_ls_wR_factor_gt          0.0835
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_restrained_S_all      1.022
_refine_ls_shift/su_max          0.003
_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 0.108189(9) 0.55269(4) 0.340336(18) 0.01296(9) Uani 1 1 d . . .
S1 S 0.030686(13) 0.92134(5) 0.07087(3) 0.01650(12) Uani 1 1 d . . .
S2 S 0.239425(13) 0.01064(5) 0.34692(3) 0.01823(12) Uani 1 1 d . . .
O1 O 0.01033(4) 0.45705(16) 0.39686(8) 0.0210(3) Uani 1 1 d . . .
O2 O 0.05920(3) 0.48062(14) 0.34790(7) 0.0154(3) Uani 1 1 d . . .
O3 O 0.16501(4) 0.78269(16) 0.46756(8) 0.0243(4) Uani 1 1 d . . .
O4 O 0.14517(4) 0.66073(15) 0.38719(7) 0.0180(3) Uani 1 1 d . . .
O5 O 0.26371(4) 0.06299(17) 0.30613(8) 0.0242(4) Uani 1 1 d . . .
O6 O 0.22585(4) -0.12014(16) 0.33752(8) 0.0260(4) Uani 1 1 d . . .
O7 O 0.05099(4) 1.03108(15) 0.05182(8) 0.0215(3) Uani 1 1 d . . .
O8 O 0.02398(4) 0.81053(15) 0.03077(7) 0.0207(3) Uani 1 1 d . . .
O9 O 0.27910(4) 0.05460(19) 0.53976(9) 0.0346(4) Uani 1 1 d . . .
O10 O -0.06719(4) 1.06905(15) 0.13970(8) 0.0228(3) Uani 1 1 d . . .
O11 O 0.12559(3) 0.38879(14) 0.36580(7) 0.0159(3) Uani 1 1 d . . .
O12 O 0.09239(4) 0.70746(14) 0.30142(7) 0.0154(3) Uani 1 1 d . . .
N1 N 0.09000(4) 0.60526(17) 0.43037(8) 0.0145(4) Uani 1 1 d . . .
N2 N 0.15727(4) 0.54646(17) 0.28274(8) 0.0147(4) Uani 1 1 d . . .
N3 N 0.08993(4) 0.46435(17) 0.24324(8) 0.0144(4) Uani 1 1 d . . .
N4 N 0.25866(4) 0.01144(18) 0.41569(9) 0.0180(4) Uani 1 1 d . . .
N5 N -0.00675(4) 0.98155(17) 0.08718(9) 0.0164(4) Uani 1 1 d . . .
C1 C 0.15169(5) 0.3023(2) 0.35985(10) 0.0155(4) Uani 1 1 d . . .
C2 C 0.14692(5) 0.1697(2) 0.37479(11) 0.0189(5) Uani 1 1 d . . .
H2 H 0.1258 0.1417 0.3879 0.023 Uiso 1 1 calc R . .
C3 C 0.17345(5) 0.0788(2) 0.37031(11) 0.0183(4) Uani 1 1 d . . .
H3 H 0.1705 -0.0096 0.3811 0.022 Uiso 1 1 calc R . .
C4 C 0.20485(5) 0.1235(2) 0.34914(11) 0.0173(4) Uani 1 1 d . . .
C5 C 0.20922(5) 0.2549(2) 0.33213(10) 0.0172(4) Uani 1 1 d . . .
H5 H 0.2300 0.2817 0.3172 0.021 Uiso 1 1 calc R . .
C6 C 0.18296(5) 0.3470(2) 0.33712(10) 0.0162(4) Uani 1 1 d . . .
C7 C 0.18766(5) 0.4896(2) 0.31974(10) 0.0164(4) Uani 1 1 d . . .
H7A H 0.2080 0.4972 0.2962 0.020 Uiso 1 1 calc R . .
H7B H 0.1916 0.5418 0.3567 0.020 Uiso 1 1 calc R . .
C8 C 0.07803(5) 0.7564(2) 0.24907(10) 0.0148(4) Uani 1 1 d . . .
C9 C 0.08249(5) 0.8907(2) 0.23479(10) 0.0175(4) Uani 1 1 d . . .
H9 H 0.0947 0.9457 0.2622 0.021 Uiso 1 1 calc R . .
C10 C 0.06881(5) 0.9415(2) 0.18022(11) 0.0184(4) Uani 1 1 d . . .
H10 H 0.0720 1.0303 0.1705 0.022 Uiso 1 1 calc R . .
C11 C 0.05012(5) 0.8581(2) 0.13957(10) 0.0166(4) Uani 1 1 d . . .
C12 C 0.04574(5) 0.7245(2) 0.15318(10) 0.0160(4) Uani 1 1 d . . .
H12 H 0.0334 0.6701 0.1256 0.019 Uiso 1 1 calc R . .
C13 C 0.05966(5) 0.6721(2) 0.20750(10) 0.0156(4) Uani 1 1 d . . .
C14 C 0.05649(5) 0.5260(2) 0.22020(10) 0.0165(4) Uani 1 1 d . . .
H14A H 0.0484 0.4812 0.1829 0.020 Uiso 1 1 calc R . .
H14B H 0.0395 0.5128 0.2504 0.020 Uiso 1 1 calc R . .
C15 C 0.15154(5) 0.4636(2) 0.22680(10) 0.0158(4) Uani 1 1 d . . .
H15A H 0.1537 0.3704 0.2375 0.019 Uiso 1 1 calc R . .
H15B H 0.1688 0.4842 0.1980 0.019 Uiso 1 1 calc R . .
C16 C 0.11623(5) 0.4901(2) 0.19770(10) 0.0160(4) Uani 1 1 d . . .
H16A H 0.1147 0.5815 0.1840 0.019 Uiso 1 1 calc R . .
H16B H 0.1121 0.4329 0.1624 0.019 Uiso 1 1 calc R . .
C17 C 0.16696(5) 0.6834(2) 0.26430(10) 0.0176(4) Uani 1 1 d . . .
H17A H 0.1875 0.6799 0.2418 0.026 Uiso 1 1 calc R . .
H17B H 0.1711 0.7371 0.3002 0.026 Uiso 1 1 calc R . .
H17C H 0.1486 0.7214 0.2390 0.026 Uiso 1 1 calc R . .
C18 C 0.08380(5) 0.3187(2) 0.24708(11) 0.0181(4) Uani 1 1 d . . .
H18A H 0.0762 0.2857 0.2075 0.027 Uiso 1 1 calc R . .
H18B H 0.0665 0.3017 0.2757 0.027 Uiso 1 1 calc R . .
H18C H 0.1048 0.2750 0.2605 0.027 Uiso 1 1 calc R . .
C19 C 0.23871(5) -0.0449(2) 0.46494(11) 0.0239(5) Uani 1 1 d . . .
H19A H 0.2282 -0.1281 0.4517 0.029 Uiso 1 1 calc R . .
H19B H 0.2206 0.0160 0.4754 0.029 Uiso 1 1 calc R . .
C20 C 0.26350(6) -0.0676(3) 0.52010(13) 0.0329(6) Uani 1 1 d . . .
H20A H 0.2512 -0.1057 0.5532 0.040 Uiso 1 1 calc R . .
H20B H 0.2812 -0.1299 0.5094 0.040 Uiso 1 1 calc R . .
C21 C 0.29845(6) 0.1083(3) 0.49243(12) 0.0296(6) Uani 1 1 d . . .
H21A H 0.3164 0.0462 0.4827 0.036 Uiso 1 1 calc R . .
H21B H 0.3094 0.1900 0.5066 0.036 Uiso 1 1 calc R . .
C22 C 0.27588(6) 0.1364(2) 0.43505(12) 0.0228(5) Uani 1 1 d . . .
H22A H 0.2589 0.2034 0.4434 0.027 Uiso 1 1 calc R . .
H22B H 0.2898 0.1691 0.4028 0.027 Uiso 1 1 calc R . .
C23 C -0.00712(5) 1.1079(2) 0.12055(11) 0.0205(5) Uani 1 1 d . . .
H23A H 0.0084 1.1707 0.1029 0.025 Uiso 1 1 calc R . .
H23B H 0.0003 1.0942 0.1631 0.025 Uiso 1 1 calc R . .
C24 C -0.04348(6) 1.1612(2) 0.11599(12) 0.0236(5) Uani 1 1 d . . .
H24A H -0.0444 1.2438 0.1386 0.028 Uiso 1 1 calc R . .
H24B H -0.0501 1.1798 0.0735 0.028 Uiso 1 1 calc R . .
C25 C -0.03200(5) 0.8855(2) 0.10885(11) 0.0198(5) Uani 1 1 d . . .
H25A H -0.0259 0.8604 0.1509 0.024 Uiso 1 1 calc R . .
H25B H -0.0321 0.8060 0.0838 0.024 Uiso 1 1 calc R . .
C26 C -0.06718(5) 0.9497(2) 0.10465(11) 0.0215(5) Uani 1 1 d . . .
H26A H -0.0737 0.9696 0.0622 0.026 Uiso 1 1 calc R . .
H26B H -0.0840 0.8886 0.1197 0.026 Uiso 1 1 calc R . .
C30 C 0.14339(5) 0.7124(2) 0.44123(10) 0.0172(4) Uani 1 1 d . . .
C31 C 0.11034(5) 0.6763(2) 0.46965(10) 0.0161(4) Uani 1 1 d . . .
C32 C 0.10014(5) 0.7108(2) 0.52709(11) 0.0195(5) Uani 1 1 d . . .
H32 H 0.1145 0.7601 0.5538 0.023 Uiso 1 1 calc R . .
C33 C 0.06785(5) 0.6698(2) 0.54378(11) 0.0200(5) Uani 1 1 d . . .
H33 H 0.0604 0.6907 0.5823 0.024 Uiso 1 1 calc R . .
C34 C 0.04663(5) 0.5975(2) 0.50281(11) 0.0191(5) Uani 1 1 d . . .
H34 H 0.0249 0.5701 0.5132 0.023 Uiso 1 1 calc R . .
C35 C 0.05873(5) 0.5675(2) 0.44626(10) 0.0152(4) Uani 1 1 d . . .
C36 C 0.04002(5) 0.4953(2) 0.39394(10) 0.0163(4) Uani 1 1 d . . .
O21 O 0.14721(4) 0.73455(18) 0.10893(8) 0.0312(4) Uani 1 1 d . . .
O20 O 0.13941(5) 0.1638(2) 0.16370(11) 0.0466(5) Uani 1 1 d . . .
C61 C 0.13141(5) 0.7724(2) 0.06279(11) 0.0218(5) Uani 1 1 d . . .
C51 C 0.16912(7) 0.1305(3) 0.16273(13) 0.0330(6) Uani 1 1 d . . .
C62 C 0.10828(6) 0.6807(2) 0.02515(12) 0.0259(5) Uani 1 1 d . . .
H62A H 0.1092 0.5935 0.0429 0.039 Uiso 1 1 calc R . .
H62B H 0.1158 0.6766 -0.0159 0.039 Uiso 1 1 calc R . .
H62C H 0.0851 0.7133 0.0244 0.039 Uiso 1 1 calc R . .
C60 C 0.13408(7) 0.9128(2) 0.04060(12) 0.0294(5) Uani 1 1 d . . .
H60A H 0.1126 0.9578 0.0454 0.044 Uiso 1 1 calc R . .
H60B H 0.1392 0.9127 -0.0018 0.044 Uiso 1 1 calc R . .
H60C H 0.1521 0.9578 0.0641 0.044 Uiso 1 1 calc R . .
C52 C 0.19254(9) 0.2126(4) 0.12629(19) 0.0675(11) Uani 1 1 d . . .
H52A H 0.1975 0.1661 0.0895 0.101 Uiso 1 1 calc R . .
H52B H 0.2136 0.2289 0.1500 0.101 Uiso 1 1 calc R . .
H52C H 0.1816 0.2956 0.1159 0.101 Uiso 1 1 calc R . .
C50 C 0.18220(13) 0.0086(4) 0.1942(2) 0.0842(16) Uani 1 1 d . . .
H50A H 0.1688 -0.0094 0.2288 0.126 Uiso 1 1 calc R . .
H50B H 0.2058 0.0212 0.2079 0.126 Uiso 1 1 calc R . .
H50C H 0.1805 -0.0650 0.1663 0.126 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 O11 1.8586(15) . ?
Ti1 O12 1.8648(15) . ?
Ti1 O4 2.0361(15) . ?
Ti1 O2 2.0551(14) . ?
Ti1 N1 2.1941(18) . ?
Ti1 N2 2.3457(17) . ?
Ti1 N3 2.3757(18) . ?
S1 O7 1.4341(16) . ?
S1 O8 1.4350(16) . ?
S1 N5 1.6355(17) . ?
S1 C11 1.764(2) . ?
S2 O6 1.4304(17) . ?
S2 O5 1.4353(17) . ?
S2 N4 1.6434(19) . ?
S2 C4 1.764(2) . ?
O1 C36 1.223(2) . ?
O2 C36 1.295(3) . ?
O3 C30 1.220(3) . ?
O4 C30 1.297(3) . ?
O9 C21 1.420(3) . ?
O9 C20 1.429(3) . ?
O10 C26 1.426(3) . ?
O10 C24 1.427(3) . ?
O11 C1 1.350(2) . ?
O12 C8 1.341(3) . ?
N1 C35 1.339(3) . ?
N1 C31 1.343(3) . ?
N2 C15 1.488(3) . ?
N2 C17 1.492(3) . ?
N2 C7 1.509(3) . ?
N3 C18 1.489(3) . ?
N3 C16 1.490(3) . ?
N3 C14 1.504(2) . ?
N4 C19 1.475(3) . ?
N4 C22 1.477(3) . ?
N5 C23 1.468(3) . ?
N5 C25 1.476(3) . ?
C1 C2 1.390(3) . ?
C1 C6 1.413(3) . ?
C2 C3 1.388(3) . ?
C3 C4 1.404(3) . ?
C4 C5 1.389(3) . ?
C5 C6 1.389(3) . ?
C6 C7 1.500(3) . ?
C8 C9 1.401(3) . ?
C8 C13 1.410(3) . ?
C9 C10 1.379(3) . ?
C10 C11 1.398(3) . ?
C11 C12 1.391(3) . ?
C12 C13 1.384(3) . ?
C13 C14 1.504(3) . ?
C15 C16 1.506(3) . ?
C19 C20 1.521(3) . ?
C21 C22 1.519(3) . ?
C23 C24 1.511(3) . ?
C25 C26 1.513(3) . ?
C30 C31 1.503(3) . ?
C31 C32 1.383(3) . ?
C32 C33 1.390(3) . ?
C33 C34 1.391(3) . ?
C34 C35 1.381(3) . ?
C35 C36 1.509(3) . ?
O21 C61 1.214(3) . ?
O20 C51 1.205(3) . ?
C61 C60 1.502(3) . ?
C61 C62 1.504(3) . ?
C51 C50 1.485(4) . ?
C51 C52 1.493(4) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O11 Ti1 O12 170.21(7) . . ?
O11 Ti1 O4 95.06(6) . . ?
O12 Ti1 O4 89.38(6) . . ?
O11 Ti1 O2 89.21(6) . . ?
O12 Ti1 O2 92.75(6) . . ?
O4 Ti1 O2 141.42(6) . . ?
O11 Ti1 N1 94.33(7) . . ?
O12 Ti1 N1 95.36(7) . . ?
O4 Ti1 N1 70.91(6) . . ?
O2 Ti1 N1 70.53(6) . . ?
O11 Ti1 N2 80.98(6) . . ?
O12 Ti1 N2 92.01(6) . . ?
O4 Ti1 N2 73.19(6) . . ?
O2 Ti1 N2 145.08(6) . . ?
N1 Ti1 N2 143.21(6) . . ?
O11 Ti1 N3 91.22(6) . . ?
O12 Ti1 N3 80.22(6) . . ?
O4 Ti1 N3 144.99(6) . . ?
O2 Ti1 N3 72.91(6) . . ?
N1 Ti1 N3 142.91(6) . . ?
N2 Ti1 N3 73.88(6) . . ?
O7 S1 O8 120.46(10) . . ?
O7 S1 N5 106.80(9) . . ?
O8 S1 N5 106.71(9) . . ?
O7 S1 C11 107.98(10) . . ?
O8 S1 C11 107.16(10) . . ?
N5 S1 C11 107.07(10) . . ?
O6 S2 O5 119.99(10) . . ?
O6 S2 N4 106.40(10) . . ?
O5 S2 N4 106.56(9) . . ?
O6 S2 C4 108.74(10) . . ?
O5 S2 C4 108.03(10) . . ?
N4 S2 C4 106.36(10) . . ?
C36 O2 Ti1 126.82(13) . . ?
C30 O4 Ti1 126.99(13) . . ?
C21 O9 C20 110.0(2) . . ?
C26 O10 C24 109.51(17) . . ?
C1 O11 Ti1 143.92(14) . . ?
C8 O12 Ti1 144.02(14) . . ?
C35 N1 C31 119.85(19) . . ?
C35 N1 Ti1 120.45(14) . . ?
C31 N1 Ti1 119.69(13) . . ?
C15 N2 C17 108.97(17) . . ?
C15 N2 C7 107.82(15) . . ?
C17 N2 C7 107.09(15) . . ?
C15 N2 Ti1 111.53(11) . . ?
C17 N2 Ti1 110.23(12) . . ?
C7 N2 Ti1 111.06(12) . . ?
C18 N3 C16 109.09(16) . . ?
C18 N3 C14 106.71(15) . . ?
C16 N3 C14 108.51(16) . . ?
C18 N3 Ti1 111.08(13) . . ?
C16 N3 Ti1 110.48(12) . . ?
C14 N3 Ti1 110.85(12) . . ?
C19 N4 C22 111.54(19) . . ?
C19 N4 S2 115.79(14) . . ?
C22 N4 S2 116.32(15) . . ?
C23 N5 C25 112.60(17) . . ?
C23 N5 S1 117.61(14) . . ?
C25 N5 S1 116.32(14) . . ?
O11 C1 C2 119.11(18) . . ?
O11 C1 C6 119.72(19) . . ?
C2 C1 C6 121.14(19) . . ?
C3 C2 C1 120.55(19) . . ?
C2 C3 C4 118.4(2) . . ?
C5 C4 C3 121.04(19) . . ?
C5 C4 S2 120.15(16) . . ?
C3 C4 S2 118.77(16) . . ?
C6 C5 C4 120.94(19) . . ?
C5 C6 C1 117.84(19) . . ?
C5 C6 C7 121.27(18) . . ?
C1 C6 C7 120.89(18) . . ?
C6 C7 N2 113.36(16) . . ?
O12 C8 C9 119.62(19) . . ?
O12 C8 C13 120.16(18) . . ?
C9 C8 C13 120.17(19) . . ?
C10 C9 C8 120.3(2) . . ?
C9 C10 C11 119.4(2) . . ?
C12 C11 C10 120.7(2) . . ?
C12 C11 S1 118.70(17) . . ?
C10 C11 S1 120.58(16) . . ?
C13 C12 C11 120.5(2) . . ?
C12 C13 C8 118.97(19) . . ?
C12 C13 C14 120.03(19) . . ?
C8 C13 C14 120.94(19) . . ?
C13 C14 N3 112.84(16) . . ?
N2 C15 C16 109.90(16) . . ?
N3 C16 C15 109.32(17) . . ?
N4 C19 C20 107.52(18) . . ?
O9 C20 C19 110.5(2) . . ?
O9 C21 C22 111.58(19) . . ?
N4 C22 C21 108.12(19) . . ?
N5 C23 C24 108.07(18) . . ?
O10 C24 C23 111.50(18) . . ?
N5 C25 C26 108.42(17) . . ?
O10 C26 C25 110.80(18) . . ?
O3 C30 O4 126.4(2) . . ?
O3 C30 C31 121.9(2) . . ?
O4 C30 C31 111.70(18) . . ?
N1 C31 C32 121.81(19) . . ?
N1 C31 C30 110.61(19) . . ?
C32 C31 C30 127.56(19) . . ?
C31 C32 C33 118.2(2) . . ?
C32 C33 C34 120.0(2) . . ?
C35 C34 C33 118.19(19) . . ?
N1 C35 C34 122.0(2) . . ?
N1 C35 C36 110.35(18) . . ?
C34 C35 C36 127.65(18) . . ?
O1 C36 O2 126.3(2) . . ?
O1 C36 C35 122.0(2) . . ?
O2 C36 C35 111.72(17) . . ?
O21 C61 C60 121.6(2) . . ?
O21 C61 C62 121.6(2) . . ?
C60 C61 C62 116.9(2) . . ?
O20 C51 C50 121.8(3) . . ?
O20 C51 C52 118.0(3) . . ?
C50 C51 C52 120.1(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
O11 Ti1 O2 C36 96.64(16) . . . . ?
O12 Ti1 O2 C36 -92.96(16) . . . . ?
O4 Ti1 O2 C36 -0.5(2) . . . . ?
N1 Ti1 O2 C36 1.76(15) . . . . ?
N2 Ti1 O2 C36 169.57(15) . . . . ?
N3 Ti1 O2 C36 -171.84(17) . . . . ?
O11 Ti1 O4 C30 -94.83(17) . . . . ?
O12 Ti1 O4 C30 93.91(17) . . . . ?
O2 Ti1 O4 C30 0.3(2) . . . . ?
N1 Ti1 O4 C30 -1.98(16) . . . . ?
N2 Ti1 O4 C30 -173.81(18) . . . . ?
N3 Ti1 O4 C30 165.75(15) . . . . ?
O4 Ti1 O11 C1 -70.8(2) . . . . ?
O2 Ti1 O11 C1 147.6(2) . . . . ?
N1 Ti1 O11 C1 -142.0(2) . . . . ?
N2 Ti1 O11 C1 1.2(2) . . . . ?
N3 Ti1 O11 C1 74.7(2) . . . . ?
O4 Ti1 O12 C8 147.0(2) . . . . ?
O2 Ti1 O12 C8 -71.6(2) . . . . ?
N1 Ti1 O12 C8 -142.3(2) . . . . ?
N2 Ti1 O12 C8 73.8(2) . . . . ?
N3 Ti1 O12 C8 0.6(2) . . . . ?
O11 Ti1 N1 C35 -86.86(15) . . . . ?
O12 Ti1 N1 C35 91.80(15) . . . . ?
O4 Ti1 N1 C35 179.28(16) . . . . ?
O2 Ti1 N1 C35 0.77(14) . . . . ?
N2 Ti1 N1 C35 -167.58(13) . . . . ?
N3 Ti1 N1 C35 10.9(2) . . . . ?
O11 Ti1 N1 C31 93.43(15) . . . . ?
O12 Ti1 N1 C31 -87.91(15) . . . . ?
O4 Ti1 N1 C31 -0.43(14) . . . . ?
O2 Ti1 N1 C31 -178.94(16) . . . . ?
N2 Ti1 N1 C31 12.7(2) . . . . ?
N3 Ti1 N1 C31 -168.77(13) . . . . ?
O11 Ti1 N2 C15 80.06(13) . . . . ?
O12 Ti1 N2 C15 -93.07(13) . . . . ?
O4 Ti1 N2 C15 178.18(14) . . . . ?
O2 Ti1 N2 C15 4.63(19) . . . . ?
N1 Ti1 N2 C15 165.22(12) . . . . ?
N3 Ti1 N2 C15 -13.86(12) . . . . ?
O11 Ti1 N2 C17 -158.75(14) . . . . ?
O12 Ti1 N2 C17 28.11(14) . . . . ?
O4 Ti1 N2 C17 -60.63(13) . . . . ?
O2 Ti1 N2 C17 125.82(14) . . . . ?
N1 Ti1 N2 C17 -73.60(17) . . . . ?
N3 Ti1 N2 C17 107.33(14) . . . . ?
O11 Ti1 N2 C7 -40.23(13) . . . . ?
O12 Ti1 N2 C7 146.63(13) . . . . ?
O4 Ti1 N2 C7 57.89(13) . . . . ?
O2 Ti1 N2 C7 -115.66(14) . . . . ?
N1 Ti1 N2 C7 44.92(18) . . . . ?
N3 Ti1 N2 C7 -134.15(14) . . . . ?
O11 Ti1 N3 C18 25.37(13) . . . . ?
O12 Ti1 N3 C18 -159.40(13) . . . . ?
O4 Ti1 N3 C18 125.99(14) . . . . ?
O2 Ti1 N3 C18 -63.43(12) . . . . ?
N1 Ti1 N3 C18 -73.46(16) . . . . ?
N2 Ti1 N3 C18 105.62(13) . . . . ?
O11 Ti1 N3 C16 -95.84(13) . . . . ?
O12 Ti1 N3 C16 79.39(13) . . . . ?
O4 Ti1 N3 C16 4.78(18) . . . . ?
O2 Ti1 N3 C16 175.36(14) . . . . ?
N1 Ti1 N3 C16 165.33(12) . . . . ?
N2 Ti1 N3 C16 -15.59(12) . . . . ?
O11 Ti1 N3 C14 143.84(13) . . . . ?
O12 Ti1 N3 C14 -40.93(13) . . . . ?
O4 Ti1 N3 C14 -115.55(14) . . . . ?
O2 Ti1 N3 C14 55.04(12) . . . . ?
N1 Ti1 N3 C14 45.00(17) . . . . ?
N2 Ti1 N3 C14 -135.92(13) . . . . ?
O6 S2 N4 C19 -48.06(18) . . . . ?
O5 S2 N4 C19 -177.19(16) . . . . ?
C4 S2 N4 C19 67.74(18) . . . . ?
O6 S2 N4 C22 178.00(15) . . . . ?
O5 S2 N4 C22 48.88(17) . . . . ?
C4 S2 N4 C22 -66.19(17) . . . . ?
O7 S1 N5 C23 -41.29(19) . . . . ?
O8 S1 N5 C23 -171.34(16) . . . . ?
C11 S1 N5 C23 74.18(18) . . . . ?
O7 S1 N5 C25 -179.24(16) . . . . ?
O8 S1 N5 C25 50.71(18) . . . . ?
C11 S1 N5 C25 -63.77(18) . . . . ?
Ti1 O11 C1 C2 -158.85(18) . . . . ?
Ti1 O11 C1 C6 19.5(4) . . . . ?
O11 C1 C2 C3 -178.7(2) . . . . ?
C6 C1 C2 C3 3.0(3) . . . . ?
C1 C2 C3 C4 -1.4(3) . . . . ?
C2 C3 C4 C5 -1.0(3) . . . . ?
C2 C3 C4 S2 176.85(17) . . . . ?
O6 S2 C4 C5 -152.83(18) . . . . ?
O5 S2 C4 C5 -21.1(2) . . . . ?
N4 S2 C4 C5 93.0(2) . . . . ?
O6 S2 C4 C3 29.3(2) . . . . ?
O5 S2 C4 C3 161.04(18) . . . . ?
N4 S2 C4 C3 -84.89(19) . . . . ?
C3 C4 C5 C6 1.7(3) . . . . ?
S2 C4 C5 C6 -176.05(17) . . . . ?
C4 C5 C6 C1 -0.2(3) . . . . ?
C4 C5 C6 C7 179.1(2) . . . . ?
O11 C1 C6 C5 179.56(19) . . . . ?
C2 C1 C6 C5 -2.2(3) . . . . ?
O11 C1 C6 C7 0.3(3) . . . . ?
C2 C1 C6 C7 178.6(2) . . . . ?
C5 C6 C7 N2 136.0(2) . . . . ?
C1 C6 C7 N2 -44.8(3) . . . . ?
C15 N2 C7 C6 -57.8(2) . . . . ?
C17 N2 C7 C6 -174.98(17) . . . . ?
Ti1 N2 C7 C6 64.62(19) . . . . ?
Ti1 O12 C8 C9 -156.17(17) . . . . ?
Ti1 O12 C8 C13 21.4(3) . . . . ?
O12 C8 C9 C10 177.93(19) . . . . ?
C13 C8 C9 C10 0.4(3) . . . . ?
C8 C9 C10 C11 0.7(3) . . . . ?
C9 C10 C11 C12 -1.1(3) . . . . ?
C9 C10 C11 S1 177.26(16) . . . . ?
O7 S1 C11 C12 -151.88(16) . . . . ?
O8 S1 C11 C12 -20.74(19) . . . . ?
N5 S1 C11 C12 93.44(18) . . . . ?
O7 S1 C11 C10 29.7(2) . . . . ?
O8 S1 C11 C10 160.86(17) . . . . ?
N5 S1 C11 C10 -84.96(18) . . . . ?
C10 C11 C12 C13 0.4(3) . . . . ?
S1 C11 C12 C13 -177.96(16) . . . . ?
C11 C12 C13 C8 0.6(3) . . . . ?
C11 C12 C13 C14 -176.56(18) . . . . ?
O12 C8 C13 C12 -178.57(18) . . . . ?
C9 C8 C13 C12 -1.0(3) . . . . ?
O12 C8 C13 C14 -1.4(3) . . . . ?
C9 C8 C13 C14 176.12(18) . . . . ?
C12 C13 C14 N3 132.8(2) . . . . ?
C8 C13 C14 N3 -44.3(3) . . . . ?
C18 N3 C14 C13 -173.86(18) . . . . ?
C16 N3 C14 C13 -56.4(2) . . . . ?
Ti1 N3 C14 C13 65.06(19) . . . . ?
C17 N2 C15 C16 -80.26(19) . . . . ?
C7 N2 C15 C16 163.84(16) . . . . ?
Ti1 N2 C15 C16 41.65(19) . . . . ?
C18 N3 C16 C15 -79.6(2) . . . . ?
C14 N3 C16 C15 164.51(17) . . . . ?
Ti1 N3 C16 C15 42.80(18) . . . . ?
N2 C15 C16 N3 -56.7(2) . . . . ?
C22 N4 C19 C20 -58.2(2) . . . . ?
S2 N4 C19 C20 165.78(17) . . . . ?
C21 O9 C20 C19 -61.7(3) . . . . ?
N4 C19 C20 O9 59.8(3) . . . . ?
C20 O9 C21 C22 60.4(3) . . . . ?
C19 N4 C22 C21 56.7(2) . . . . ?
S2 N4 C22 C21 -167.51(16) . . . . ?
O9 C21 C22 N4 -57.1(3) . . . . ?
C25 N5 C23 C24 -55.1(2) . . . . ?
S1 N5 C23 C24 165.45(15) . . . . ?
C26 O10 C24 C23 -61.8(2) . . . . ?
N5 C23 C24 O10 57.7(3) . . . . ?
C23 N5 C25 C26 55.5(2) . . . . ?
S1 N5 C25 C26 -164.50(15) . . . . ?
C24 O10 C26 C25 61.6(2) . . . . ?
N5 C25 C26 O10 -57.8(2) . . . . ?
Ti1 O4 C30 O3 -175.94(17) . . . . ?
Ti1 O4 C30 C31 3.7(3) . . . . ?
C35 N1 C31 C32 0.9(3) . . . . ?
Ti1 N1 C31 C32 -179.42(16) . . . . ?
C35 N1 C31 C30 -177.54(18) . . . . ?
Ti1 N1 C31 C30 2.2(2) . . . . ?
O3 C30 C31 N1 176.2(2) . . . . ?
O4 C30 C31 N1 -3.4(2) . . . . ?
O3 C30 C31 C32 -2.1(3) . . . . ?
O4 C30 C31 C32 178.3(2) . . . . ?
N1 C31 C32 C33 0.1(3) . . . . ?
C30 C31 C32 C33 178.2(2) . . . . ?
C31 C32 C33 C34 -0.8(3) . . . . ?
C32 C33 C34 C35 0.6(3) . . . . ?
C31 N1 C35 C34 -1.1(3) . . . . ?
Ti1 N1 C35 C34 179.20(15) . . . . ?
C31 N1 C35 C36 177.15(17) . . . . ?
Ti1 N1 C35 C36 -2.6(2) . . . . ?
C33 C34 C35 N1 0.4(3) . . . . ?
C33 C34 C35 C36 -177.5(2) . . . . ?
Ti1 O2 C36 O1 176.49(16) . . . . ?
Ti1 O2 C36 C35 -3.6(2) . . . . ?
N1 C35 C36 O1 -176.43(19) . . . . ?
C34 C35 C36 O1 1.7(3) . . . . ?
N1 C35 C36 O2 3.6(2) . . . . ?
C34 C35 C36 O2 -178.3(2) . . . . ?

_diffrn_measured_fraction_theta_max 0.984
_diffrn_reflns_theta_full        26.91
_diffrn_measured_fraction_theta_full 0.984
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.058
####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1410575'
_audit_update_record             
;
2015-07-05 deposited with the CCDC.
2015-08-20 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          449
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H25 N3 O6 Ti'
_chemical_formula_weight         511.38

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'
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                   16.7824(13)
_cell_length_b                   14.9183(9)
_cell_length_c                   8.6437(7)
_cell_angle_alpha                90
_cell_angle_beta                 91.497(6)
_cell_angle_gamma                90
_cell_volume                     2163.3(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    16892
_cell_measurement_theta_min      1.83
_cell_measurement_theta_max      26.69

_exptl_crystal_description       fragment
_exptl_crystal_colour            orange-red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.570
_exptl_crystal_F_000             1064
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.460
_exptl_crystal_size_mid          0.293
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    0.447
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.6640
_exptl_absorpt_correction_T_max  0.9415
_exptl_absorpt_process_details   
;
'X-SHAPE 2.07 (03-Aug-2005) Stoe & Cie, Darmstadt, Germany'
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            14886
_diffrn_reflns_av_unetI/netI     0.1260
_diffrn_reflns_av_R_equivalents  0.1342
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         1.827
_diffrn_reflns_theta_max         26.261
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2181
_reflns_number_gt                1909
_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       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'ORTEP-3 for Windows (Farrugia, 2012)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'

_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)+(0.0564P)²+1.4636P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2181
_refine_ls_number_parameters     161
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0332
_refine_ls_wR_factor_ref         0.0916
_refine_ls_wR_factor_gt          0.0893
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.043
_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
C1 C 0.63086(10) 0.70807(11) 0.4821(2) 0.0192(3) Uani 1 1 d . . . . .
C2 C 0.64775(10) 0.71127(12) 0.6416(2) 0.0213(4) Uani 1 1 d . . . . .
H2 H 0.6183 0.7503 0.7054 0.026 Uiso 1 1 calc R U . . .
C3 C 0.70732(10) 0.65775(12) 0.7069(2) 0.0235(4) Uani 1 1 d . . . . .
H3 H 0.7192 0.6609 0.8148 0.028 Uiso 1 1 calc R U . . .
C4 C 0.74969(10) 0.59933(12) 0.6139(2) 0.0230(4) Uani 1 1 d . . . . .
H4 H 0.7896 0.5615 0.6585 0.028 Uiso 1 1 calc R U . . .
C5 C 0.73335(10) 0.59682(12) 0.4565(2) 0.0232(4) Uani 1 1 d . . . . .
H5 H 0.7623 0.5566 0.3938 0.028 Uiso 1 1 calc R U . . .
C6 C 0.67556(9) 0.65169(12) 0.3875(2) 0.0200(4) Uani 1 1 d . . . . .
C7 C 0.66019(10) 0.64950(12) 0.2154(2) 0.0212(4) Uani 1 1 d . . . . .
H7A H 0.6801 0.7057 0.1694 0.025 Uiso 1 1 calc R U . . .
H7B H 0.6902 0.5990 0.1706 0.025 Uiso 1 1 calc R U . . .
C8 C 0.54484(10) 0.55639(11) 0.2499(2) 0.0213(4) Uani 1 1 d . . . . .
H8A H 0.5663 0.5536 0.3575 0.026 Uiso 1 1 calc R U . . .
H8B H 0.5640 0.5031 0.1937 0.026 Uiso 1 1 calc R U . . .
C9 C 0.56720(11) 0.62832(12) 0.0035(2) 0.0240(4) Uani 1 1 d . . . . .
H9A H 0.6010 0.5784 -0.0280 0.036 Uiso 1 1 calc R U . . .
H9B H 0.5848 0.6836 -0.0465 0.036 Uiso 1 1 calc R U . . .
H9C H 0.5117 0.6159 -0.0275 0.036 Uiso 1 1 calc R U . . .
C10 C 0.55277(9) 0.95695(11) 0.16534(19) 0.0185(3) Uani 1 1 d . . . . .
C11 C 0.60465(10) 0.89324(11) 0.07903(19) 0.0194(3) Uani 1 1 d . . . . .
C12 C 0.5000 1.09620(17) 0.2500 0.0251(5) Uani 1 2 d S T P . .
H12 H 0.5000 1.1599 0.2500 0.030 Uiso 1 2 calc R U P . .
C13 C 0.55435(10) 1.05007(12) 0.1617(2) 0.0225(4) Uani 1 1 d . . . . .
H13 H 0.5916 1.0812 0.1006 0.027 Uiso 1 1 calc R U . . .
N1 N 0.57330(8) 0.63908(10) 0.17370(16) 0.0190(3) Uani 1 1 d . . . . .
N2 N 0.5000 0.91270(13) 0.2500 0.0168(4) Uani 1 2 d S T P . .
O1 O 0.57050(7) 0.75706(8) 0.41990(14) 0.0189(3) Uani 1 1 d . . . . .
O2 O 0.58532(7) 0.81057(8) 0.10518(14) 0.0198(3) Uani 1 1 d . . . . .
O3 O 0.65741(7) 0.91909(9) -0.00433(15) 0.0262(3) Uani 1 1 d . . . . .
Ti1 Ti 0.5000 0.76669(3) 0.2500 0.01570(14) Uani 1 2 d S T P . .


_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
C1 O1 1.349(2) . ?
C1 C2 1.401(2) . ?
C1 C6 1.404(2) . ?
C2 C3 1.388(2) . ?
C3 C4 1.393(3) . ?
C4 C5 1.382(3) . ?
C5 C6 1.391(2) . ?
C6 C7 1.503(2) . ?
C7 N1 1.501(2) . ?
C8 N1 1.483(2) . ?
C8 C8 1.505(3) 2_655 ?
C9 N1 1.480(2) . ?
C10 N2 1.3376(19) . ?
C10 C13 1.390(2) . ?
C10 C11 1.501(2) . ?
C11 O3 1.219(2) . ?
C11 O2 1.297(2) . ?
C12 C13 1.387(2) 2_655 ?
C12 C13 1.387(2) . ?
N1 Ti1 2.3695(14) . ?
N2 C10 1.3377(19) 2_655 ?
N2 Ti1 2.178(2) . ?
O1 Ti1 1.8672(11) . ?
O2 Ti1 2.0345(12) . ?
Ti1 O1 1.8672(11) 2_655 ?
Ti1 O2 2.0345(12) 2_655 ?
Ti1 N1 2.3695(14) 2_655 ?

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 C1 C2 120.29(15) . . ?
O1 C1 C6 119.93(15) . . ?
C2 C1 C6 119.76(15) . . ?
C3 C2 C1 120.38(16) . . ?
C2 C3 C4 119.90(16) . . ?
C5 C4 C3 119.61(16) . . ?
C4 C5 C6 121.63(16) . . ?
C5 C6 C1 118.66(16) . . ?
C5 C6 C7 120.73(15) . . ?
C1 C6 C7 120.60(15) . . ?
N1 C7 C6 112.35(14) . . ?
N1 C8 C8 109.53(11) . 2_655 ?
N2 C10 C13 121.26(16) . . ?
N2 C10 C11 111.13(15) . . ?
C13 C10 C11 127.61(16) . . ?
O3 C11 O2 126.37(16) . . ?
O3 C11 C10 122.24(16) . . ?
O2 C11 C10 111.39(14) . . ?
C13 C12 C13 120.5(2) 2_655 . ?
C12 C13 C10 118.05(17) . . ?
C9 N1 C8 109.64(13) . . ?
C9 N1 C7 106.93(13) . . ?
C8 N1 C7 107.55(13) . . ?
C9 N1 Ti1 109.92(10) . . ?
C8 N1 Ti1 111.67(10) . . ?
C7 N1 Ti1 110.99(10) . . ?
C10 N2 C10 120.9(2) . 2_655 ?
C10 N2 Ti1 119.57(10) . . ?
C10 N2 Ti1 119.57(10) 2_655 . ?
C1 O1 Ti1 143.98(11) . . ?
C11 O2 Ti1 126.62(11) . . ?
O1 Ti1 O1 171.17(7) 2_655 . ?
O1 Ti1 O2 89.00(5) 2_655 . ?
O1 Ti1 O2 93.84(5) . . ?
O1 Ti1 O2 93.84(5) 2_655 2_655 ?
O1 Ti1 O2 89.00(5) . 2_655 ?
O2 Ti1 O2 142.47(7) . 2_655 ?
O1 Ti1 N2 94.42(4) 2_655 . ?
O1 Ti1 N2 94.41(4) . . ?
O2 Ti1 N2 71.23(3) . . ?
O2 Ti1 N2 71.23(3) 2_655 . ?
O1 Ti1 N1 92.41(5) 2_655 . ?
O1 Ti1 N1 80.46(5) . . ?
O2 Ti1 N1 73.05(5) . . ?
O2 Ti1 N1 143.95(5) 2_655 . ?
N2 Ti1 N1 143.46(3) . . ?
O1 Ti1 N1 80.46(5) 2_655 2_655 ?
O1 Ti1 N1 92.41(5) . 2_655 ?
O2 Ti1 N1 143.95(5) . 2_655 ?
O2 Ti1 N1 73.05(5) 2_655 2_655 ?
N2 Ti1 N1 143.46(3) . 2_655 ?
N1 Ti1 N1 73.08(7) . 2_655 ?

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 C1 C2 C3 176.93(15) . . . . ?
C6 C1 C2 C3 -1.3(3) . . . . ?
C1 C2 C3 C4 -1.1(3) . . . . ?
C2 C3 C4 C5 1.6(3) . . . . ?
C3 C4 C5 C6 0.3(3) . . . . ?
C4 C5 C6 C1 -2.6(3) . . . . ?
C4 C5 C6 C7 178.46(16) . . . . ?
O1 C1 C6 C5 -175.10(15) . . . . ?
C2 C1 C6 C5 3.1(2) . . . . ?
O1 C1 C6 C7 3.8(2) . . . . ?
C2 C1 C6 C7 -177.98(15) . . . . ?
C5 C6 C7 N1 129.86(16) . . . . ?
C1 C6 C7 N1 -49.0(2) . . . . ?
N2 C10 C11 O3 -179.34(13) . . . . ?
C13 C10 C11 O3 1.9(3) . . . . ?
N2 C10 C11 O2 0.92(17) . . . . ?
C13 C10 C11 O2 -177.82(15) . . . . ?
C13 C12 C13 C10 -0.32(10) 2_655 . . . ?
N2 C10 C13 C12 0.7(2) . . . . ?
C11 C10 C13 C12 179.29(13) . . . . ?
C8 C8 N1 C9 -80.01(19) 2_655 . . . ?
C8 C8 N1 C7 164.07(16) 2_655 . . . ?
C8 C8 N1 Ti1 42.07(18) 2_655 . . . ?
C6 C7 N1 C9 -174.18(14) . . . . ?
C6 C7 N1 C8 -56.48(17) . . . . ?
C6 C7 N1 Ti1 65.94(15) . . . . ?
C13 C10 N2 C10 -0.34(11) . . . 2_655 ?
C11 C10 N2 C10 -179.17(14) . . . 2_655 ?
C13 C10 N2 Ti1 179.66(11) . . . . ?
C11 C10 N2 Ti1 0.83(14) . . . . ?
C2 C1 O1 Ti1 -158.12(14) . . . . ?
C6 C1 O1 Ti1 20.1(3) . . . . ?
O3 C11 O2 Ti1 177.66(13) . . . . ?
C10 C11 O2 Ti1 -2.61(18) . . . . ?
C1 O1 Ti1 O2 -73.39(19) . . . . ?
C1 O1 Ti1 O2 144.08(18) . . . 2_655 ?
C1 O1 Ti1 N2 -144.83(18) . . . . ?
C1 O1 Ti1 N1 -1.30(18) . . . . ?
C1 O1 Ti1 N1 71.09(18) . . . 2_655 ?

_refine_diff_density_max         0.537
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.072

_shelxl_version_number           2013-4


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: acetone, DCM'
