# Supplementary Material (ESI) for Metallomics
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               Metallomics

_journal_coden_Cambridge         1400

_publ_contact_author_name        'Matthias Tacke'
_publ_contact_author_email       MATTHIAS.TACKE@UCD.IE

_publ_section_title              
;
Pseudo-Halide Derivatives of Titanocene Y: Synthesis and Cytotoxicity Studies
;
loop_
_publ_author_name
'Matthias Tacke'
'James Claffey'
'Anthony Deally'
'Brendan Gleeson'
'Megan Hogan'
'Luis Miguel Menendez Mendez'
;
H.Muller-Bunz
;
'Siddappa Patil'
'Denise Wallis'

# Attachment 'tac62pub.cif'

data_tac62(2b)
_database_code_depnum_ccdc_archive 'CCDC 735708'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C28 H26 N2 O4 Ti'
_chemical_formula_sum            'C28 H26 N2 O4 Ti'
_chemical_formula_weight         502.41
_chemical_absolute_configuration ad

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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'C 2'

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

_cell_length_a                   25.394(2)
_cell_length_b                   7.3361(7)
_cell_length_c                   6.3130(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.110(2)
_cell_angle_gamma                90.00
_cell_volume                     1164.32(19)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5808
_cell_measurement_theta_min      2.89
_cell_measurement_theta_max      30.51

_exptl_crystal_description       lath
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             524
_exptl_absorpt_coefficient_mu    0.407
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8670
_exptl_absorpt_correction_T_max  0.9879
_exptl_absorpt_process_details   
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) for selected reflections was 0.043 before and 0.027 after
correction. The Ratio of minimum to maximum transmission is 0.877624.
The \l/2 correction factor is 0.0015
;

_exptl_special_details           
;
All hydrogen atoms were located in the difference fourier map and allowed
to refine freely. C-H bond lengths were restrained to be their default
values (0.95 \%A for aromatic, 0.99 \%A for CH~2~ groups and 0.98 \%A for
methyl groups) using DFIX. They range from 0.92(2) to 0.97(2) \%A.
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12207
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_sigmaI/netI    0.0314
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         1.62
_diffrn_reflns_theta_max         30.51
_reflns_number_total             3346
_reflns_number_gt                3261
_reflns_threshold_expression     I>2\s(I)

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

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0492P)^2^+0.2503P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.048(19)
_refine_ls_number_reflns         3346
_refine_ls_number_parameters     211
_refine_ls_number_restraints     14
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0363
_refine_ls_wR_factor_ref         0.0838
_refine_ls_wR_factor_gt          0.0832
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_restrained_S_all      1.083
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti Ti 0.5000 0.46090(4) 0.0000 0.01329(10) Uani 1 2 d S . .
C1 C 0.41170(6) 0.4994(2) 0.0886(3) 0.0183(3) Uani 1 1 d . . .
C2 C 0.44265(7) 0.4169(2) 0.2655(3) 0.0201(4) Uani 1 1 d D . .
H2 H 0.4514(8) 0.476(4) 0.401(3) 0.027(5) Uiso 1 1 d D . .
C3 C 0.46016(7) 0.2445(3) 0.2021(3) 0.0251(4) Uani 1 1 d D . .
H3 H 0.4798(9) 0.159(3) 0.287(4) 0.037(7) Uiso 1 1 d D . .
C4 C 0.43837(8) 0.2192(3) -0.0145(3) 0.0269(4) Uani 1 1 d D . .
H4 H 0.4420(9) 0.114(3) -0.100(3) 0.027(6) Uiso 1 1 d D . .
C5 C 0.40906(7) 0.3754(3) -0.0835(3) 0.0238(4) Uani 1 1 d D . .
H5 H 0.3895(8) 0.399(3) -0.217(3) 0.017(5) Uiso 1 1 d D . .
C6 C 0.38437(7) 0.6805(2) 0.0882(3) 0.0225(3) Uani 1 1 d D . .
H6A H 0.3778(8) 0.724(3) -0.056(3) 0.018(5) Uiso 1 1 d D . .
H6B H 0.4084(9) 0.764(3) 0.165(4) 0.037(7) Uiso 1 1 d D . .
C7 C 0.33087(7) 0.6626(2) 0.1663(3) 0.0186(3) Uani 1 1 d . . .
C8 C 0.32199(7) 0.7369(2) 0.3600(3) 0.0195(3) Uani 1 1 d D . .
H8 H 0.3503(7) 0.796(3) 0.437(3) 0.020(6) Uiso 1 1 d D . .
C9 C 0.27297(7) 0.7244(2) 0.4318(3) 0.0196(3) Uani 1 1 d D . .
H9 H 0.2663(9) 0.787(3) 0.559(3) 0.029(6) Uiso 1 1 d D . .
C10 C 0.23137(6) 0.6365(2) 0.3062(3) 0.0174(3) Uani 1 1 d . . .
O1 O 0.18102(5) 0.61746(17) 0.3573(2) 0.0205(3) Uani 1 1 d . . .
C13 C 0.17097(7) 0.6984(3) 0.5535(3) 0.0232(4) Uani 1 1 d D . .
H13A H 0.1333(7) 0.685(4) 0.561(4) 0.035(7) Uiso 1 1 d D . .
H13B H 0.1951(9) 0.643(3) 0.667(3) 0.026(6) Uiso 1 1 d D . .
H13C H 0.1744(9) 0.831(2) 0.559(4) 0.030(6) Uiso 1 1 d D . .
C11 C 0.23964(7) 0.5576(2) 0.1124(3) 0.0202(3) Uani 1 1 d D . .
H11 H 0.2108(7) 0.497(3) 0.025(3) 0.018(5) Uiso 1 1 d D . .
C12 C 0.28870(7) 0.5707(2) 0.0445(3) 0.0210(3) Uani 1 1 d D . .
H12 H 0.2908(8) 0.518(3) -0.087(3) 0.020(5) Uiso 1 1 d D . .
N N 0.52529(6) 0.6500(2) 0.2228(2) 0.0220(3) Uani 1 1 d . . .
C14 C 0.53997(6) 0.7830(2) 0.3184(3) 0.0178(3) Uani 1 1 d . . .
O2 O 0.55488(5) 0.91669(17) 0.4161(2) 0.0248(3) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ti 0.01640(18) 0.00987(17) 0.01433(17) 0.000 0.00473(13) 0.000
C1 0.0166(7) 0.0159(8) 0.0236(7) -0.0004(5) 0.0070(6) -0.0003(5)
C2 0.0199(7) 0.0212(10) 0.0207(7) 0.0021(6) 0.0084(6) 0.0003(6)
C3 0.0255(9) 0.0162(8) 0.0370(10) 0.0083(7) 0.0157(7) 0.0026(7)
C4 0.0261(9) 0.0166(8) 0.0410(10) -0.0083(8) 0.0154(8) -0.0061(7)
C5 0.0202(8) 0.0259(10) 0.0256(9) -0.0061(7) 0.0042(7) -0.0069(7)
C6 0.0213(8) 0.0174(8) 0.0301(9) 0.0033(7) 0.0082(7) 0.0014(6)
C7 0.0189(7) 0.0121(7) 0.0253(8) 0.0030(6) 0.0047(6) 0.0027(6)
C8 0.0179(8) 0.0143(8) 0.0254(9) -0.0013(7) -0.0008(6) 0.0008(6)
C9 0.0204(8) 0.0156(8) 0.0228(8) -0.0026(6) 0.0030(6) 0.0026(6)
C10 0.0178(7) 0.0117(7) 0.0223(8) 0.0037(6) 0.0021(6) 0.0024(6)
O1 0.0167(5) 0.0197(6) 0.0254(6) -0.0010(5) 0.0043(5) 0.0005(4)
C13 0.0208(8) 0.0229(9) 0.0264(9) -0.0007(7) 0.0053(7) 0.0043(7)
C11 0.0219(8) 0.0156(8) 0.0219(8) 0.0004(6) -0.0009(6) -0.0010(6)
C12 0.0271(9) 0.0166(8) 0.0196(8) 0.0005(6) 0.0044(7) 0.0010(6)
N 0.0241(7) 0.0206(8) 0.0224(7) -0.0025(6) 0.0066(6) -0.0036(6)
C14 0.0184(7) 0.0170(7) 0.0188(8) 0.0029(6) 0.0053(6) 0.0016(6)
O2 0.0261(6) 0.0178(7) 0.0302(6) -0.0046(5) 0.0032(5) -0.0022(4)

_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
Ti N 2.0149(15) . ?
Ti C3 2.3528(18) . ?
Ti C4 2.3583(18) . ?
Ti C5 2.3794(18) . ?
Ti C2 2.3924(16) . ?
Ti C1 2.4030(15) . ?
C1 C2 1.409(2) . ?
C1 C5 1.412(2) . ?
C1 C6 1.498(2) . ?
C2 C3 1.416(3) . ?
C2 H2 0.956(16) . ?
C3 C4 1.413(3) . ?
C3 H3 0.925(17) . ?
C4 C5 1.402(3) . ?
C4 H4 0.953(16) . ?
C5 H5 0.934(15) . ?
C6 C7 1.515(2) . ?
C6 H6A 0.960(15) . ?
C6 H6B 0.947(17) . ?
C7 C8 1.386(2) . ?
C7 C12 1.400(2) . ?
C8 C9 1.387(2) . ?
C8 H8 0.920(16) . ?
C9 C10 1.387(2) . ?
C9 H9 0.960(16) . ?
C10 O1 1.369(2) . ?
C10 C11 1.396(2) . ?
O1 C13 1.428(2) . ?
C13 H13A 0.968(16) . ?
C13 H13B 0.964(16) . ?
C13 H13C 0.974(17) . ?
C11 C12 1.377(2) . ?
C11 H11 0.961(14) . ?
C12 H12 0.924(15) . ?
N C14 1.179(2) . ?
C14 O2 1.192(2) . ?

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
N Ti N 92.97(9) . 2_655 ?
N Ti C3 101.83(7) . . ?
N Ti C3 136.37(6) 2_655 . ?
C3 Ti C3 95.15(9) 2_655 . ?
N Ti C4 133.57(6) . . ?
N Ti C4 110.25(7) 2_655 . ?
C3 Ti C4 78.79(6) 2_655 . ?
C3 Ti C4 34.91(7) . . ?
C4 Ti C4 82.49(10) 2_655 . ?
N Ti C5 122.69(6) . . ?
N Ti C5 79.80(7) 2_655 . ?
C3 Ti C5 100.38(7) 2_655 . ?
C3 Ti C5 57.60(7) . . ?
C4 Ti C5 115.37(7) 2_655 . ?
C4 Ti C5 34.42(7) . . ?
C5 Ti C5 149.43(10) 2_655 . ?
N Ti C2 76.68(6) . . ?
N Ti C2 114.60(6) 2_655 . ?
C3 Ti C2 129.77(6) 2_655 . ?
C3 Ti C2 34.72(6) . . ?
C4 Ti C2 109.73(6) 2_655 . ?
C4 Ti C2 57.27(6) . . ?
C5 Ti C2 118.48(6) 2_655 . ?
C5 Ti C2 56.76(6) . . ?
C2 Ti C2 164.48(8) . 2_655 ?
N Ti C1 88.43(6) . . ?
N Ti C1 82.26(6) 2_655 . ?
C3 Ti C1 133.82(6) 2_655 . ?
C3 Ti C1 57.75(6) . . ?
C4 Ti C1 135.68(6) 2_655 . ?
C4 Ti C1 57.42(6) . . ?
C5 Ti C1 152.60(6) 2_655 . ?
C5 Ti C1 34.33(6) . . ?
C2 Ti C1 34.17(6) . . ?
C2 Ti C1 149.22(6) 2_655 . ?
C1 Ti C1 166.48(8) 2_655 . ?
C2 C1 C5 107.07(15) . . ?
C2 C1 C6 126.08(15) . . ?
C5 C1 C6 126.77(16) . . ?
C2 C1 Ti 72.50(9) . . ?
C5 C1 Ti 71.92(9) . . ?
C6 C1 Ti 123.44(11) . . ?
C1 C2 C3 108.80(16) . . ?
C1 C2 Ti 73.33(9) . . ?
C3 C2 Ti 71.11(10) . . ?
C1 C2 H2 123.2(16) . . ?
C3 C2 H2 127.9(16) . . ?
Ti C2 H2 118.5(13) . . ?
C4 C3 C2 107.16(16) . . ?
C4 C3 Ti 72.76(10) . . ?
C2 C3 Ti 74.17(10) . . ?
C4 C3 H3 125.2(17) . . ?
C2 C3 H3 127.4(17) . . ?
Ti C3 H3 122.3(17) . . ?
C5 C4 C3 108.15(16) . . ?
C5 C4 Ti 73.61(10) . . ?
C3 C4 Ti 72.33(10) . . ?
C5 C4 H4 125.1(14) . . ?
C3 C4 H4 126.7(14) . . ?
Ti C4 H4 120.8(14) . . ?
C4 C5 C1 108.79(17) . . ?
C4 C5 Ti 71.96(10) . . ?
C1 C5 Ti 73.75(9) . . ?
C4 C5 H5 128.8(14) . . ?
C1 C5 H5 122.4(14) . . ?
Ti C5 H5 121.9(13) . . ?
C1 C6 C7 111.04(14) . . ?
C1 C6 H6A 108.5(13) . . ?
C7 C6 H6A 107.1(12) . . ?
C1 C6 H6B 107.8(17) . . ?
C7 C6 H6B 115.5(16) . . ?
H6A C6 H6B 107(2) . . ?
C8 C7 C12 117.83(16) . . ?
C8 C7 C6 121.21(16) . . ?
C12 C7 C6 120.96(16) . . ?
C7 C8 C9 121.86(16) . . ?
C7 C8 H8 116.2(14) . . ?
C9 C8 H8 121.9(14) . . ?
C8 C9 C10 119.35(16) . . ?
C8 C9 H9 120.9(14) . . ?
C10 C9 H9 119.4(14) . . ?
O1 C10 C9 125.03(16) . . ?
O1 C10 C11 115.14(15) . . ?
C9 C10 C11 119.82(16) . . ?
C10 O1 C13 116.65(14) . . ?
O1 C13 H13A 107.3(16) . . ?
O1 C13 H13B 107.3(14) . . ?
H13A C13 H13B 117(2) . . ?
O1 C13 H13C 115.0(14) . . ?
H13A C13 H13C 100(2) . . ?
H13B C13 H13C 110(2) . . ?
C12 C11 C10 119.87(16) . . ?
C12 C11 H11 120.3(12) . . ?
C10 C11 H11 119.8(12) . . ?
C11 C12 C7 121.24(16) . . ?
C11 C12 H12 114.7(13) . . ?
C7 C12 H12 124.0(13) . . ?
C14 N Ti 166.70(14) . . ?
N C14 O2 179.6(2) . . ?

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
N Ti C1 C2 -68.29(10) . . . . ?
N Ti C1 C2 -161.50(11) 2_655 . . . ?
C3 Ti C1 C2 99.50(12) 2_655 . . . ?
C3 Ti C1 C2 36.77(10) . . . . ?
C4 Ti C1 C2 49.60(14) 2_655 . . . ?
C4 Ti C1 C2 78.40(11) . . . . ?
C5 Ti C1 C2 -4.24(18) 2_655 . . . ?
C5 Ti C1 C2 115.26(15) . . . . ?
C2 Ti C1 C2 151.55(16) 2_655 . . . ?
C1 Ti C1 C2 -114.63(9) 2_655 . . . ?
N Ti C1 C5 176.45(12) . . . . ?
N Ti C1 C5 83.24(11) 2_655 . . . ?
C3 Ti C1 C5 -15.76(15) 2_655 . . . ?
C3 Ti C1 C5 -78.49(12) . . . . ?
C4 Ti C1 C5 -65.66(14) 2_655 . . . ?
C4 Ti C1 C5 -36.86(12) . . . . ?
C5 Ti C1 C5 -119.5(2) 2_655 . . . ?
C2 Ti C1 C5 -115.26(15) . . . . ?
C2 Ti C1 C5 36.29(17) 2_655 . . . ?
C1 Ti C1 C5 130.11(11) 2_655 . . . ?
N Ti C1 C6 53.84(14) . . . . ?
N Ti C1 C6 -39.38(14) 2_655 . . . ?
C3 Ti C1 C6 -138.37(14) 2_655 . . . ?
C3 Ti C1 C6 158.90(17) . . . . ?
C4 Ti C1 C6 171.72(13) 2_655 . . . ?
C4 Ti C1 C6 -159.47(17) . . . . ?
C5 Ti C1 C6 117.88(17) 2_655 . . . ?
C5 Ti C1 C6 -122.62(19) . . . . ?
C2 Ti C1 C6 122.12(18) . . . . ?
C2 Ti C1 C6 -86.33(17) 2_655 . . . ?
C1 Ti C1 C6 7.49(13) 2_655 . . . ?
C5 C1 C2 C3 1.39(19) . . . . ?
C6 C1 C2 C3 178.29(16) . . . . ?
Ti C1 C2 C3 -62.68(12) . . . . ?
C5 C1 C2 Ti 64.07(11) . . . . ?
C6 C1 C2 Ti -119.03(16) . . . . ?
N Ti C2 C1 107.38(10) . . . . ?
N Ti C2 C1 20.23(11) 2_655 . . . ?
C3 Ti C2 C1 -112.19(11) 2_655 . . . ?
C3 Ti C2 C1 -117.25(15) . . . . ?
C4 Ti C2 C1 -145.58(10) 2_655 . . . ?
C4 Ti C2 C1 -78.88(11) . . . . ?
C5 Ti C2 C1 177.78(10) 2_655 . . . ?
C5 Ti C2 C1 -37.57(10) . . . . ?
C2 Ti C2 C1 -114.35(9) 2_655 . . . ?
C1 Ti C2 C1 155.46(14) 2_655 . . . ?
N Ti C2 C3 -135.37(12) . . . . ?
N Ti C2 C3 137.48(11) 2_655 . . . ?
C3 Ti C2 C3 5.07(18) 2_655 . . . ?
C4 Ti C2 C3 -28.33(13) 2_655 . . . ?
C4 Ti C2 C3 38.37(12) . . . . ?
C5 Ti C2 C3 -64.97(13) 2_655 . . . ?
C5 Ti C2 C3 79.68(12) . . . . ?
C2 Ti C2 C3 2.91(10) 2_655 . . . ?
C1 Ti C2 C3 -87.28(15) 2_655 . . . ?
C1 Ti C2 C3 117.25(15) . . . . ?
C1 C2 C3 C4 -1.69(19) . . . . ?
Ti C2 C3 C4 -65.79(12) . . . . ?
C1 C2 C3 Ti 64.10(12) . . . . ?
N Ti C3 C4 158.46(11) . . . . ?
N Ti C3 C4 51.20(14) 2_655 . . . ?
C3 Ti C3 C4 -61.94(10) 2_655 . . . ?
C4 Ti C3 C4 -92.93(14) 2_655 . . . ?
C5 Ti C3 C4 -119.91(11) 2_655 . . . ?
C5 Ti C3 C4 37.09(11) . . . . ?
C2 Ti C3 C4 114.15(16) . . . . ?
C2 Ti C3 C4 -64.84(13) 2_655 . . . ?
C1 Ti C3 C4 -110.95(12) 2_655 . . . ?
C1 Ti C3 C4 77.97(11) . . . . ?
N Ti C3 C2 44.31(12) . . . . ?
N Ti C3 C2 -62.95(15) 2_655 . . . ?
C3 Ti C3 C2 -176.09(14) 2_655 . . . ?
C4 Ti C3 C2 152.91(12) 2_655 . . . ?
C4 Ti C3 C2 -114.15(16) . . . . ?
C5 Ti C3 C2 125.94(11) 2_655 . . . ?
C5 Ti C3 C2 -77.06(11) . . . . ?
C2 Ti C3 C2 -178.99(4) 2_655 . . . ?
C1 Ti C3 C2 134.90(10) 2_655 . . . ?
C1 Ti C3 C2 -36.18(10) . . . . ?
C2 C3 C4 C5 1.3(2) . . . . ?
Ti C3 C4 C5 -65.41(13) . . . . ?
C2 C3 C4 Ti 66.75(12) . . . . ?
N Ti C4 C5 86.02(14) . . . . ?
N Ti C4 C5 -29.28(13) 2_655 . . . ?
C3 Ti C4 C5 -127.89(12) 2_655 . . . ?
C3 Ti C4 C5 115.75(16) . . . . ?
C4 Ti C4 C5 -163.09(15) 2_655 . . . ?
C5 Ti C4 C5 -173.58(6) 2_655 . . . ?
C2 Ti C4 C5 77.60(12) . . . . ?
C2 Ti C4 C5 -111.89(11) 2_655 . . . ?
C1 Ti C4 C5 -138.92(11) 2_655 . . . ?
C1 Ti C4 C5 36.76(10) . . . . ?
N Ti C4 C3 -29.74(15) . . . . ?
N Ti C4 C3 -145.03(10) 2_655 . . . ?
C3 Ti C4 C3 116.36(12) 2_655 . . . ?
C4 Ti C4 C3 81.15(12) 2_655 . . . ?
C5 Ti C4 C3 70.67(12) 2_655 . . . ?
C5 Ti C4 C3 -115.75(16) . . . . ?
C2 Ti C4 C3 -38.15(10) . . . . ?
C2 Ti C4 C3 132.35(10) 2_655 . . . ?
C1 Ti C4 C3 105.33(12) 2_655 . . . ?
C1 Ti C4 C3 -79.00(11) . . . . ?
C3 C4 C5 C1 -0.5(2) . . . . ?
Ti C4 C5 C1 -65.06(12) . . . . ?
C3 C4 C5 Ti 64.57(13) . . . . ?
C2 C1 C5 C4 -0.6(2) . . . . ?
C6 C1 C5 C4 -177.43(16) . . . . ?
Ti C1 C5 C4 63.91(13) . . . . ?
C2 C1 C5 Ti -64.46(11) . . . . ?
C6 C1 C5 Ti 118.67(16) . . . . ?
N Ti C5 C4 -120.81(12) . . . . ?
N Ti C5 C4 152.22(12) 2_655 . . . ?
C3 Ti C5 C4 51.91(12) 2_655 . . . ?
C3 Ti C5 C4 -37.63(11) . . . . ?
C4 Ti C5 C4 18.61(16) 2_655 . . . ?
C5 Ti C5 C4 11.46(10) 2_655 . . . ?
C2 Ti C5 C4 -79.21(12) . . . . ?
C2 Ti C5 C4 83.55(13) 2_655 . . . ?
C1 Ti C5 C4 86.26(17) 2_655 . . . ?
C1 Ti C5 C4 -116.60(16) . . . . ?
N Ti C5 C1 -4.21(14) . . . . ?
N Ti C5 C1 -91.18(11) 2_655 . . . ?
C3 Ti C5 C1 168.51(11) 2_655 . . . ?
C3 Ti C5 C1 78.97(11) . . . . ?
C4 Ti C5 C1 135.21(11) 2_655 . . . ?
C4 Ti C5 C1 116.60(16) . . . . ?
C5 Ti C5 C1 128.06(11) 2_655 . . . ?
C2 Ti C5 C1 37.39(10) . . . . ?
C2 Ti C5 C1 -159.85(10) 2_655 . . . ?
C1 Ti C5 C1 -157.14(14) 2_655 . . . ?
C2 C1 C6 C7 -83.8(2) . . . . ?
C5 C1 C6 C7 92.5(2) . . . . ?
Ti C1 C6 C7 -175.84(11) . . . . ?
C1 C6 C7 C8 111.63(18) . . . . ?
C1 C6 C7 C12 -68.6(2) . . . . ?
C12 C7 C8 C9 -1.0(3) . . . . ?
C6 C7 C8 C9 178.87(16) . . . . ?
C7 C8 C9 C10 -0.6(3) . . . . ?
C8 C9 C10 O1 -178.96(15) . . . . ?
C8 C9 C10 C11 1.8(3) . . . . ?
C9 C10 O1 C13 1.4(2) . . . . ?
C11 C10 O1 C13 -179.31(14) . . . . ?
O1 C10 C11 C12 179.22(15) . . . . ?
C9 C10 C11 C12 -1.4(2) . . . . ?
C10 C11 C12 C7 -0.1(3) . . . . ?
C8 C7 C12 C11 1.3(3) . . . . ?
C6 C7 C12 C11 -178.53(16) . . . . ?
N Ti N C14 -19.9(6) 2_655 . . . ?
C3 Ti N C14 90.7(6) 2_655 . . . ?
C3 Ti N C14 -158.7(6) . . . . ?
C4 Ti N C14 119.1(6) 2_655 . . . ?
C4 Ti N C14 -141.8(6) . . . . ?
C5 Ti N C14 102.8(6) 2_655 . . . ?
C5 Ti N C14 -99.7(6) . . . . ?
C2 Ti N C14 -134.5(6) . . . . ?
C2 Ti N C14 56.8(6) 2_655 . . . ?
C1 Ti N C14 68.1(6) 2_655 . . . ?
C1 Ti N C14 -102.1(6) . . . . ?

_diffrn_measured_fraction_theta_max 0.967
_diffrn_reflns_theta_full        29.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.066

#===END

data_tac69(2c)
_database_code_depnum_ccdc_archive 'CCDC 735709'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C28 H26 N2 O2 S2 Ti'
_chemical_formula_sum            'C28 H26 N2 O2 S2 Ti'
_chemical_formula_weight         534.53

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'
S S 0.1246 0.1234 '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                   14.6085(10)
_cell_length_b                   7.9381(6)
_cell_length_c                   21.7937(15)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.048(1)
_cell_angle_gamma                90.00
_cell_volume                     2502.4(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    170(2)
_cell_measurement_reflns_used    4948
_cell_measurement_theta_min      2.82
_cell_measurement_theta_max      30.07

_exptl_crystal_description       plate
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.50
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1112
_exptl_absorpt_coefficient_mu    0.538
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7687
_exptl_absorpt_correction_T_max  0.9482
_exptl_absorpt_process_details   
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) for selected reflections was 0.048 before and 0.021 after
correction. The Ratio of minimum to maximum transmission is 0.810714.
The \l/2 correction factor is 0.0015
;

_exptl_special_details           
;
All hydrogen atoms were located in the difference fourier map and allowed
to refine freely. C-H bond lengths range from 0.89(2) to 0.98(2) \%A.
;

_diffrn_ambient_temperature      170(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12083
_diffrn_reflns_av_R_equivalents  0.0219
_diffrn_reflns_av_sigmaI/netI    0.0192
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         1.89
_diffrn_reflns_theta_max         28.00
_reflns_number_total             3009
_reflns_number_gt                2692
_reflns_threshold_expression     I>2\s(I)

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

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0564P)^2^+1.0840P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3009
_refine_ls_number_parameters     211
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0351
_refine_ls_wR_factor_ref         0.0914
_refine_ls_wR_factor_gt          0.0883
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.049
_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
Ti Ti 0.0000 0.52726(4) 0.2500 0.02096(11) Uani 1 2 d S . .
C1 C -0.03937(10) 0.49826(19) 0.13685(6) 0.0283(3) Uani 1 1 d . . .
C2 C 0.05212(10) 0.55592(18) 0.15073(6) 0.0272(3) Uani 1 1 d . . .
H2 H 0.1042(13) 0.497(2) 0.1438(8) 0.031(4) Uiso 1 1 d . . .
C3 C 0.05145(11) 0.71395(19) 0.18063(7) 0.0298(3) Uani 1 1 d . . .
H3 H 0.1021(12) 0.771(2) 0.1953(8) 0.034(5) Uiso 1 1 d . . .
C4 C -0.04165(11) 0.75540(19) 0.18427(7) 0.0327(3) Uani 1 1 d . . .
H4 H -0.0593(13) 0.858(2) 0.2011(9) 0.044(5) Uiso 1 1 d . . .
C5 C -0.09688(11) 0.6216(2) 0.15910(7) 0.0320(3) Uani 1 1 d . . .
H5 H -0.1629(14) 0.615(2) 0.1579(9) 0.040(5) Uiso 1 1 d . . .
C6 C -0.07234(12) 0.3411(2) 0.10169(8) 0.0375(4) Uani 1 1 d . . .
H6A H -0.1014(13) 0.271(3) 0.1281(10) 0.048(5) Uiso 1 1 d . . .
H6B H -0.1197(14) 0.376(3) 0.0703(9) 0.045(5) Uiso 1 1 d . . .
C7 C 0.00220(11) 0.24489(19) 0.07593(7) 0.0336(3) Uani 1 1 d . . .
C8 C 0.05906(12) 0.1321(2) 0.11248(7) 0.0369(4) Uani 1 1 d . . .
H8 H 0.0502(12) 0.121(2) 0.1556(8) 0.036(5) Uiso 1 1 d . . .
C9 C 0.12869(13) 0.0458(2) 0.08948(7) 0.0390(4) Uani 1 1 d . . .
H9 H 0.1677(16) -0.028(3) 0.1130(10) 0.055(6) Uiso 1 1 d . . .
C10 C 0.14325(12) 0.0680(2) 0.02837(7) 0.0363(3) Uani 1 1 d . . .
O O 0.21334(10) -0.02472(17) 0.00989(6) 0.0501(3) Uani 1 1 d . . .
C13 C 0.23210(16) -0.0036(3) -0.05176(10) 0.0508(5) Uani 1 1 d . . .
H13A H 0.1777(16) -0.018(3) -0.0809(11) 0.052(6) Uiso 1 1 d . . .
H13B H 0.2790(16) -0.083(3) -0.0549(11) 0.060(7) Uiso 1 1 d . . .
H13C H 0.2556(17) 0.109(3) -0.0572(12) 0.072(7) Uiso 1 1 d . . .
C11 C 0.08698(12) 0.1786(2) -0.00905(7) 0.0381(4) Uani 1 1 d . . .
H11 H 0.0993(13) 0.197(2) -0.0515(9) 0.045(5) Uiso 1 1 d . . .
C12 C 0.01789(12) 0.2649(2) 0.01488(7) 0.0364(3) Uani 1 1 d . . .
H12 H -0.0201(13) 0.337(3) -0.0111(9) 0.040(5) Uiso 1 1 d . . .
N N -0.09926(8) 0.34902(15) 0.24565(5) 0.0282(3) Uani 1 1 d . . .
C14 C -0.14818(9) 0.23203(17) 0.23971(6) 0.0251(3) Uani 1 1 d . . .
S S -0.21473(3) 0.06976(5) 0.232531(19) 0.03532(12) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ti 0.02398(18) 0.01907(17) 0.02025(17) 0.000 0.00451(12) 0.000
C1 0.0337(7) 0.0321(7) 0.0188(6) 0.0018(5) 0.0029(5) -0.0027(6)
C2 0.0330(7) 0.0288(7) 0.0212(6) 0.0007(5) 0.0084(5) -0.0018(6)
C3 0.0394(8) 0.0258(7) 0.0252(7) 0.0027(5) 0.0086(6) -0.0054(6)
C4 0.0464(8) 0.0261(7) 0.0267(7) 0.0071(6) 0.0091(6) 0.0075(6)
C5 0.0318(7) 0.0375(8) 0.0264(7) 0.0091(6) 0.0029(5) 0.0048(6)
C6 0.0406(8) 0.0444(9) 0.0270(7) -0.0071(7) 0.0030(6) -0.0112(7)
C7 0.0470(8) 0.0297(7) 0.0235(7) -0.0051(6) 0.0031(6) -0.0128(6)
C8 0.0561(10) 0.0344(8) 0.0197(7) 0.0005(6) 0.0030(6) -0.0111(7)
C9 0.0532(10) 0.0338(8) 0.0282(8) 0.0032(6) -0.0005(7) -0.0054(7)
C10 0.0472(9) 0.0318(8) 0.0299(7) -0.0046(6) 0.0050(6) -0.0089(7)
O 0.0564(8) 0.0533(8) 0.0419(7) -0.0019(6) 0.0107(6) 0.0041(6)
C13 0.0559(12) 0.0549(12) 0.0445(11) -0.0138(9) 0.0178(9) -0.0124(10)
C11 0.0584(10) 0.0350(8) 0.0211(7) -0.0005(6) 0.0062(6) -0.0080(7)
C12 0.0540(9) 0.0308(8) 0.0232(7) 0.0005(6) 0.0014(6) -0.0042(7)
N 0.0293(6) 0.0272(6) 0.0279(6) 0.0008(5) 0.0037(5) -0.0028(5)
C14 0.0238(6) 0.0274(7) 0.0242(6) 0.0013(5) 0.0042(5) 0.0032(5)
S 0.0322(2) 0.0304(2) 0.0430(2) -0.00162(15) 0.00419(16) -0.00916(14)

_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
Ti N 2.0188(12) . ?
Ti C3 2.3161(14) . ?
Ti C4 2.3361(14) . ?
Ti C5 2.3883(14) . ?
Ti C2 2.4027(13) . ?
Ti C1 2.4633(14) . ?
C1 C2 1.405(2) . ?
C1 C5 1.419(2) . ?
C1 C6 1.507(2) . ?
C2 C3 1.414(2) . ?
C2 H2 0.925(19) . ?
C3 C4 1.412(2) . ?
C3 H3 0.886(18) . ?
C4 C5 1.398(2) . ?
C4 H4 0.94(2) . ?
C5 H5 0.96(2) . ?
C6 C7 1.502(2) . ?
C6 H6A 0.95(2) . ?
C6 H6B 0.94(2) . ?
C7 C12 1.391(2) . ?
C7 C8 1.393(2) . ?
C8 C9 1.378(3) . ?
C8 H8 0.971(18) . ?
C9 C10 1.389(2) . ?
C9 H9 0.92(2) . ?
C10 O 1.367(2) . ?
C10 C11 1.387(2) . ?
O C13 1.418(2) . ?
C13 H13A 0.95(2) . ?
C13 H13B 0.94(2) . ?
C13 H13C 0.97(3) . ?
C11 C12 1.381(2) . ?
C11 H11 0.98(2) . ?
C12 H12 0.93(2) . ?
N C14 1.1678(18) . ?
C14 S 1.6082(14) . ?

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
N Ti N 91.00(7) . 2 ?
N Ti C3 135.59(5) . . ?
N Ti C3 100.52(5) 2 . ?
C3 Ti C3 100.44(7) . 2 ?
N Ti C4 113.00(5) . . ?
N Ti C4 134.10(5) 2 . ?
C3 Ti C4 35.34(5) . . ?
C3 Ti C4 79.85(5) 2 . ?
C4 Ti C4 78.36(8) . 2 ?
N Ti C5 80.94(5) . . ?
N Ti C5 126.67(5) 2 . ?
C3 Ti C5 57.77(5) . . ?
C3 Ti C5 97.58(5) 2 . ?
C4 Ti C5 34.41(6) . . ?
C4 Ti C5 109.80(6) 2 . ?
C5 Ti C5 143.44(8) . 2 ?
N Ti C2 109.89(5) . . ?
N Ti C2 78.03(5) 2 . ?
C3 Ti C2 34.82(5) . . ?
C3 Ti C2 134.41(5) 2 . ?
C4 Ti C2 57.50(5) . . ?
C4 Ti C2 112.99(5) 2 . ?
C5 Ti C2 56.57(5) . . ?
C5 Ti C2 119.44(5) 2 . ?
C2 Ti C2 169.13(7) . 2 ?
N Ti C1 79.74(5) . . ?
N Ti C1 92.70(5) 2 . ?
C3 Ti C1 57.18(5) . . ?
C3 Ti C1 131.42(5) 2 . ?
C4 Ti C1 56.93(5) . . ?
C4 Ti C1 133.68(5) 2 . ?
C5 Ti C1 33.97(5) . . ?
C5 Ti C1 152.61(5) 2 . ?
C2 Ti C1 33.54(5) . . ?
C2 Ti C1 148.35(5) 2 . ?
C1 Ti C1 169.27(7) . 2 ?
C2 C1 C5 107.00(13) . . ?
C2 C1 C6 127.28(14) . . ?
C5 C1 C6 125.62(14) . . ?
C2 C1 Ti 70.87(8) . . ?
C5 C1 Ti 70.12(8) . . ?
C6 C1 Ti 126.83(10) . . ?
C1 C2 C3 108.69(13) . . ?
C1 C2 Ti 75.60(8) . . ?
C3 C2 Ti 69.24(8) . . ?
C1 C2 H2 125.3(11) . . ?
C3 C2 H2 125.9(11) . . ?
Ti C2 H2 118.1(11) . . ?
C4 C3 C2 107.54(14) . . ?
C4 C3 Ti 73.10(8) . . ?
C2 C3 Ti 75.94(8) . . ?
C4 C3 H3 128.6(11) . . ?
C2 C3 H3 123.8(12) . . ?
Ti C3 H3 114.9(11) . . ?
C5 C4 C3 107.96(14) . . ?
C5 C4 Ti 74.83(8) . . ?
C3 C4 Ti 71.56(8) . . ?
C5 C4 H4 129.3(12) . . ?
C3 C4 H4 122.8(12) . . ?
Ti C4 H4 119.4(12) . . ?
C4 C5 C1 108.74(13) . . ?
C4 C5 Ti 70.75(8) . . ?
C1 C5 Ti 75.91(8) . . ?
C4 C5 H5 125.1(12) . . ?
C1 C5 H5 126.1(12) . . ?
Ti C5 H5 118.6(11) . . ?
C7 C6 C1 114.47(13) . . ?
C7 C6 H6A 109.7(12) . . ?
C1 C6 H6A 108.6(12) . . ?
C7 C6 H6B 112.0(12) . . ?
C1 C6 H6B 105.9(12) . . ?
H6A C6 H6B 105.7(17) . . ?
C12 C7 C8 117.11(15) . . ?
C12 C7 C6 121.65(15) . . ?
C8 C7 C6 121.24(14) . . ?
C9 C8 C7 121.52(14) . . ?
C9 C8 H8 121.0(11) . . ?
C7 C8 H8 117.4(11) . . ?
C8 C9 C10 120.39(16) . . ?
C8 C9 H9 123.0(14) . . ?
C10 C9 H9 116.6(14) . . ?
O C10 C11 125.07(15) . . ?
O C10 C9 115.83(16) . . ?
C11 C10 C9 119.10(16) . . ?
C10 O C13 117.88(16) . . ?
O C13 H13A 111.4(13) . . ?
O C13 H13B 103.3(15) . . ?
H13A C13 H13B 114.7(19) . . ?
O C13 H13C 110.0(15) . . ?
H13A C13 H13C 108(2) . . ?
H13B C13 H13C 109.4(19) . . ?
C12 C11 C10 119.76(15) . . ?
C12 C11 H11 121.7(11) . . ?
C10 C11 H11 118.5(11) . . ?
C11 C12 C7 122.11(16) . . ?
C11 C12 H12 118.8(12) . . ?
C7 C12 H12 119.1(12) . . ?
C14 N Ti 170.72(11) . . ?
N C14 S 179.12(14) . . ?

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
N Ti C1 C2 -153.98(9) . . . . ?
N Ti C1 C2 -63.45(9) 2 . . . ?
C3 Ti C1 C2 37.33(9) . . . . ?
C3 Ti C1 C2 110.98(10) 2 . . . ?
C4 Ti C1 C2 79.73(10) . . . . ?
C4 Ti C1 C2 62.41(11) 2 . . . ?
C5 Ti C1 C2 117.04(13) . . . . ?
C5 Ti C1 C2 11.95(16) 2 . . . ?
C2 Ti C1 C2 160.06(13) 2 . . . ?
C1 Ti C1 C2 -108.27(8) 2 . . . ?
N Ti C1 C5 88.97(9) . . . . ?
N Ti C1 C5 179.51(9) 2 . . . ?
C3 Ti C1 C5 -79.72(10) . . . . ?
C3 Ti C1 C5 -6.06(12) 2 . . . ?
C4 Ti C1 C5 -37.31(9) . . . . ?
C4 Ti C1 C5 -54.63(12) 2 . . . ?
C5 Ti C1 C5 -105.09(17) 2 . . . ?
C2 Ti C1 C5 -117.04(13) . . . . ?
C2 Ti C1 C5 43.01(14) 2 . . . ?
C1 Ti C1 C5 134.68(9) 2 . . . ?
N Ti C1 C6 -31.22(13) . . . . ?
N Ti C1 C6 59.31(13) 2 . . . ?
C3 Ti C1 C6 160.09(15) . . . . ?
C3 Ti C1 C6 -126.25(13) 2 . . . ?
C4 Ti C1 C6 -157.51(15) . . . . ?
C4 Ti C1 C6 -174.83(12) 2 . . . ?
C5 Ti C1 C6 -120.20(17) . . . . ?
C5 Ti C1 C6 134.72(14) 2 . . . ?
C2 Ti C1 C6 122.76(17) . . . . ?
C2 Ti C1 C6 -77.18(16) 2 . . . ?
C1 Ti C1 C6 14.49(13) 2 . . . ?
C5 C1 C2 C3 -0.61(16) . . . . ?
C6 C1 C2 C3 176.01(14) . . . . ?
Ti C1 C2 C3 -61.76(10) . . . . ?
C5 C1 C2 Ti 61.15(10) . . . . ?
C6 C1 C2 Ti -122.23(15) . . . . ?
N Ti C2 C1 27.32(10) . . . . ?
N Ti C2 C1 114.02(9) 2 . . . ?
C3 Ti C2 C1 -116.82(13) . . . . ?
C3 Ti C2 C1 -101.44(10) 2 . . . ?
C4 Ti C2 C1 -77.89(10) . . . . ?
C4 Ti C2 C1 -135.87(9) 2 . . . ?
C5 Ti C2 C1 -36.61(9) . . . . ?
C5 Ti C2 C1 -173.72(9) 2 . . . ?
C2 Ti C2 C1 -108.28(8) 2 . . . ?
C1 Ti C2 C1 160.32(13) 2 . . . ?
N Ti C2 C3 144.14(9) . . . . ?
N Ti C2 C3 -129.17(10) 2 . . . ?
C3 Ti C2 C3 15.37(15) 2 . . . ?
C4 Ti C2 C3 38.93(9) . . . . ?
C4 Ti C2 C3 -19.05(11) 2 . . . ?
C5 Ti C2 C3 80.21(10) . . . . ?
C5 Ti C2 C3 -56.90(11) 2 . . . ?
C2 Ti C2 C3 8.54(8) 2 . . . ?
C1 Ti C2 C3 116.82(13) . . . . ?
C1 Ti C2 C3 -82.86(13) 2 . . . ?
C1 C2 C3 C4 -0.98(16) . . . . ?
Ti C2 C3 C4 -66.83(10) . . . . ?
C1 C2 C3 Ti 65.86(10) . . . . ?
N Ti C3 C4 61.69(12) . . . . ?
N Ti C3 C4 164.11(9) 2 . . . ?
C3 Ti C3 C4 -55.27(8) 2 . . . ?
C4 Ti C3 C4 -84.15(11) 2 . . . ?
C5 Ti C3 C4 37.16(9) . . . . ?
C5 Ti C3 C4 -113.77(10) 2 . . . ?
C2 Ti C3 C4 113.63(13) . . . . ?
C2 Ti C3 C4 -64.13(12) 2 . . . ?
C1 Ti C3 C4 77.70(10) . . . . ?
C1 Ti C3 C4 -110.36(10) 2 . . . ?
N Ti C3 C2 -51.94(12) . . . . ?
N Ti C3 C2 50.48(10) 2 . . . ?
C3 Ti C3 C2 -168.90(11) 2 . . . ?
C4 Ti C3 C2 -113.63(13) . . . . ?
C4 Ti C3 C2 162.22(10) 2 . . . ?
C5 Ti C3 C2 -76.46(10) . . . . ?
C5 Ti C3 C2 132.61(9) 2 . . . ?
C2 Ti C3 C2 -177.75(3) 2 . . . ?
C1 Ti C3 C2 -35.93(8) . . . . ?
C1 Ti C3 C2 136.01(9) 2 . . . ?
C2 C3 C4 C5 2.21(16) . . . . ?
Ti C3 C4 C5 -66.55(10) . . . . ?
C2 C3 C4 Ti 68.76(10) . . . . ?
N Ti C4 C5 -22.70(10) . . . . ?
N Ti C4 C5 93.27(11) 2 . . . ?
C3 Ti C4 C5 115.29(13) . . . . ?
C3 Ti C4 C5 -119.90(10) 2 . . . ?
C4 Ti C4 C5 -155.88(12) 2 . . . ?
C5 Ti C4 C5 -170.09(5) 2 . . . ?
C2 Ti C4 C5 76.95(10) . . . . ?
C2 Ti C4 C5 -108.99(9) 2 . . . ?
C1 Ti C4 C5 36.82(9) . . . . ?
C1 Ti C4 C5 -141.13(9) 2 . . . ?
N Ti C4 C3 -137.99(9) . . . . ?
N Ti C4 C3 -22.02(12) 2 . . . ?
C3 Ti C4 C3 124.81(9) 2 . . . ?
C4 Ti C4 C3 88.83(10) 2 . . . ?
C5 Ti C4 C3 -115.29(13) . . . . ?
C5 Ti C4 C3 74.62(10) 2 . . . ?
C2 Ti C4 C3 -38.34(8) . . . . ?
C2 Ti C4 C3 135.72(9) 2 . . . ?
C1 Ti C4 C3 -78.47(9) . . . . ?
C1 Ti C4 C3 103.58(10) 2 . . . ?
C3 C4 C5 C1 -2.62(16) . . . . ?
Ti C4 C5 C1 -67.00(10) . . . . ?
C3 C4 C5 Ti 64.38(10) . . . . ?
C2 C1 C5 C4 2.00(16) . . . . ?
C6 C1 C5 C4 -174.69(14) . . . . ?
Ti C1 C5 C4 63.64(10) . . . . ?
C2 C1 C5 Ti -61.63(10) . . . . ?
C6 C1 C5 Ti 121.67(14) . . . . ?
N Ti C5 C4 158.92(10) . . . . ?
N Ti C5 C4 -116.63(9) 2 . . . ?
C3 Ti C5 C4 -38.19(9) . . . . ?
C3 Ti C5 C4 59.41(10) 2 . . . ?
C4 Ti C5 C4 25.17(13) 2 . . . ?
C5 Ti C5 C4 15.77(8) 2 . . . ?
C2 Ti C5 C4 -79.88(10) . . . . ?
C2 Ti C5 C4 88.26(10) 2 . . . ?
C1 Ti C5 C4 -116.01(13) . . . . ?
C1 Ti C5 C4 80.71(14) 2 . . . ?
N Ti C5 C1 -85.07(9) . . . . ?
N Ti C5 C1 -0.62(11) 2 . . . ?
C3 Ti C5 C1 77.82(9) . . . . ?
C3 Ti C5 C1 175.42(9) 2 . . . ?
C4 Ti C5 C1 116.01(13) . . . . ?
C4 Ti C5 C1 141.18(9) 2 . . . ?
C5 Ti C5 C1 131.79(9) 2 . . . ?
C2 Ti C5 C1 36.13(8) . . . . ?
C2 Ti C5 C1 -155.73(8) 2 . . . ?
C1 Ti C5 C1 -163.28(12) 2 . . . ?
C2 C1 C6 C7 -4.2(2) . . . . ?
C5 C1 C6 C7 171.82(14) . . . . ?
Ti C1 C6 C7 -97.38(15) . . . . ?
C1 C6 C7 C12 -96.71(17) . . . . ?
C1 C6 C7 C8 82.92(19) . . . . ?
C12 C7 C8 C9 0.9(2) . . . . ?
C6 C7 C8 C9 -178.75(15) . . . . ?
C7 C8 C9 C10 -0.8(2) . . . . ?
C8 C9 C10 O -179.29(15) . . . . ?
C8 C9 C10 C11 0.2(2) . . . . ?
C11 C10 O C13 1.8(2) . . . . ?
C9 C10 O C13 -178.71(16) . . . . ?
O C10 C11 C12 179.68(15) . . . . ?
C9 C10 C11 C12 0.2(2) . . . . ?
C10 C11 C12 C7 -0.1(2) . . . . ?
C8 C7 C12 C11 -0.5(2) . . . . ?
C6 C7 C12 C11 179.19(15) . . . . ?
N Ti N C14 -25.9(7) 2 . . . ?
C3 Ti N C14 80.3(7) . . . . ?
C3 Ti N C14 -162.8(7) 2 . . . ?
C4 Ti N C14 113.9(7) . . . . ?
C4 Ti N C14 -150.0(7) 2 . . . ?
C5 Ti N C14 101.1(7) . . . . ?
C5 Ti N C14 -105.3(7) 2 . . . ?
C2 Ti N C14 51.7(7) . . . . ?
C2 Ti N C14 -136.0(7) 2 . . . ?
C1 Ti N C14 66.7(7) . . . . ?
C1 Ti N C14 -105.7(7) 2 . . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        28.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.149
_refine_diff_density_rms         0.068