# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2016

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# 
# This file contains crystal structure data downloaded from the 
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# Crystallographic Data Centre (CCDC).
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# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
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# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
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data_spider-15007
_database_code_depnum_ccdc_archive 'CCDC 1402797'
_audit_update_record             
;
2015-05-25 deposited with the CCDC.
2016-01-12 downloaded from the CCDC.
;

_vrf_PLAT415_spider-15007        
;
PROBLEM: Short Inter D-H..H-X  
RESPONSE: The short distances associated with this alert involve H8B, which 
is the minor component of the disordered ethylene glycol ligand. There 
may be a complementing orientation of the parent complex, which accommodates 
the disorder. The low occupancy of this disorder implies any complement
conformation would also have a low site occupancy.  The model reported here
was found to be satisfactory.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H22 N2 O8 Ti'
_chemical_formula_sum            'C18 H22 N2 O8 Ti'
_chemical_formula_weight         442.27

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

_shelx_space_group_comment       
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;

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

_cell_length_a                   10.9669(3)
_cell_length_b                   14.7049(4)
_cell_length_c                   13.0353(9)
_cell_angle_alpha                90
_cell_angle_beta                 113.016(8)
_cell_angle_gamma                90
_cell_volume                     1934.82(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    15332
_cell_measurement_theta_min      3.1
_cell_measurement_theta_max      25.4

_exptl_crystal_description       Block
_exptl_crystal_colour            Colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.518
_exptl_crystal_F_000             920
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.492
_shelx_estimated_absorpt_T_min   0.930
_shelx_estimated_absorpt_T_max   0.962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.824
_exptl_absorpt_correction_T_max  0.962
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private Communication'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Sealed Tube'
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID imaging plate'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10
_diffrn_reflns_number            21555
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.104
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3533
_reflns_number_gt                2877
_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       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;
Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H., 
OLEX2: A complete structure solution, refinement and analysis program
(2009). J. Appl. Cryst., 42, 339-341.
;
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'
_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. 

 The hydrogen atoms were first found in the difference map, then generated 
 geometrically and refined as riding atoms with C-H distances = 0.95- 0.99 
 Å and Uiso(H) = 1.2 times Ueq(C) for CH and CH2 groups and Uiso(H) 
 = 1.5 times Ueq(C) for CH3 groups.
 
 Hydrogen atoms H2 and H6 are freely refining and a part of refined hydrogen
 bonding interactions between N2...O6_$1, O6...O3, O8A...O1, and N1...O5_$2, 
 where $1 and $2 denotes the symmetry operation -X,1-Y,-Z and 1-X,1-Y,1-Z.
 The O8A and H8A bond distance required the use of a similarity restraint to
 aid in convergence. Atoms H8a is semi-freely refining.  H8b was geometrically 
 placed, fixed and riding on O8b.

 Atoms C17, C18 and O8 are disordered over two positions. The major and minor
 positions are denoted with the suffixes "a" and "b".  The site occupancies 
 were freely refined and subsequently fixed at their converged values of 0.7
 and 0.3. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0495P)²+1.6092P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3533
_refine_ls_number_parameters     305
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0384
_refine_ls_wR_factor_ref         0.1021
_refine_ls_wR_factor_gt          0.0943
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.056
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.38015(4) 0.50713(3) 0.26592(3) 0.01399(14) Uani 1 1 d . . . . .
O1 O 0.54099(15) 0.53034(10) 0.39968(13) 0.0159(3) Uani 1 1 d . . . . .
O2 O 0.33124(15) 0.62159(10) 0.33843(13) 0.0171(4) Uani 1 1 d . . . . .
H2 H 0.152(3) 0.5968(17) 0.001(2) 0.014(6) Uiso 1 1 d . . . . .
O3 O 0.21455(14) 0.52448(10) 0.13173(12) 0.0152(3) Uani 1 1 d . . . . .
O4 O 0.42957(15) 0.60527(11) 0.17513(13) 0.0183(4) Uani 1 1 d . . . . .
O5 O 0.28091(15) 0.43269(10) 0.32009(13) 0.0156(3) Uani 1 1 d . . . . .
O6 O 0.01085(17) 0.41335(12) 0.13039(14) 0.0207(4) Uani 1 1 d D . . . .
H6 H 0.067(3) 0.438(2) 0.124(3) 0.037(10) Uiso 1 1 d D . . . .
O7 O 0.47048(15) 0.42119(11) 0.22915(13) 0.0183(4) Uani 1 1 d . . . . .
O8A O 0.7539(2) 0.45501(18) 0.3581(3) 0.0297(6) Uani 0.7 1 d D . P A 1
H8A H 0.710(4) 0.470(3) 0.384(4) 0.044 Uiso 0.7 1 d D U P . .
O8B O 0.6164(9) 0.4839(6) 0.1008(8) 0.061(2) Uani 0.3 1 d . U P B 2
H8B H 0.6617 0.5272 0.0924 0.092 Uiso 0.3 1 calc R U P B 2
N1 N 0.53512(19) 0.60313(13) 0.46376(16) 0.0155(4) Uani 1 1 d . . . . .
H1 H 0.598(3) 0.6046(19) 0.533(3) 0.033(8) Uiso 1 1 d . . . . .
N2 N 0.22044(19) 0.59097(13) 0.05991(16) 0.0147(4) Uani 1 1 d . . . . .
C1 C 0.4222(2) 0.64731(15) 0.42937(18) 0.0160(5) Uani 1 1 d . . . . .
C2 C 0.4068(2) 0.72608(15) 0.49433(19) 0.0160(5) Uani 1 1 d . . . . .
C3 C 0.5078(2) 0.75360(16) 0.5933(2) 0.0192(5) Uani 1 1 d . . . . .
H3 H 0.5892 0.7212 0.6213 0.023 Uiso 1 1 calc R U . . .
C4 C 0.4898(2) 0.82820(16) 0.6510(2) 0.0205(5) Uani 1 1 d . . . . .
H4 H 0.5591 0.8470 0.7183 0.025 Uiso 1 1 calc R U . . .
C5 C 0.3700(2) 0.87554(16) 0.6104(2) 0.0209(5) Uani 1 1 d . . . . .
H5 H 0.3573 0.9263 0.6502 0.025 Uiso 1 1 calc R U . . .
C6 C 0.2698(2) 0.84820(16) 0.5116(2) 0.0204(5) Uani 1 1 d . . . . .
H6A H 0.1884 0.8806 0.4838 0.025 Uiso 1 1 calc R U . . .
C7 C 0.2872(2) 0.77407(16) 0.45324(19) 0.0185(5) Uani 1 1 d . . . . .
H7 H 0.2181 0.7559 0.3855 0.022 Uiso 1 1 calc R U . . .
C8 C 0.3344(2) 0.63241(15) 0.08697(18) 0.0143(5) Uani 1 1 d . . . . .
C9 C 0.3514(2) 0.70853(15) 0.02028(18) 0.0140(5) Uani 1 1 d . . . . .
C10 C 0.4785(2) 0.74404(15) 0.04775(19) 0.0170(5) Uani 1 1 d . . . . .
H10 H 0.5518 0.7181 0.1070 0.020 Uiso 1 1 calc R U . . .
C11 C 0.4975(2) 0.81717(16) -0.0114(2) 0.0206(5) Uani 1 1 d . . . . .
H11 H 0.5840 0.8411 0.0073 0.025 Uiso 1 1 calc R U . . .
C12 C 0.3909(2) 0.85576(16) -0.0981(2) 0.0210(5) Uani 1 1 d . . . . .
H12 H 0.4045 0.9060 -0.1381 0.025 Uiso 1 1 calc R U . . .
C13 C 0.2642(2) 0.82069(16) -0.1260(2) 0.0199(5) Uani 1 1 d . . . . .
H13 H 0.1914 0.8466 -0.1856 0.024 Uiso 1 1 calc R U . . .
C14 C 0.2442(2) 0.74788(15) -0.06676(19) 0.0166(5) Uani 1 1 d . . . . .
H14 H 0.1574 0.7246 -0.0853 0.020 Uiso 1 1 calc R U . . .
C15 C 0.1553(2) 0.43781(16) 0.3276(2) 0.0194(5) Uani 1 1 d . . . . .
H15A H 0.1237 0.5015 0.3165 0.023 Uiso 1 1 calc R U . . .
H15B H 0.1640 0.4185 0.4030 0.023 Uiso 1 1 calc R U . . .
C16 C 0.0553(2) 0.37787(17) 0.24132(19) 0.0214(5) Uani 1 1 d . . . . .
H16A H 0.0954 0.3173 0.2430 0.026 Uiso 1 1 calc R U . . .
H16B H -0.0222 0.3696 0.2614 0.026 Uiso 1 1 calc R U . . .
C17A C 0.5712(5) 0.3986(4) 0.1935(4) 0.0207(11) Uani 0.7 1 d . . P A 1
H17A H 0.5855 0.4497 0.1499 0.025 Uiso 0.7 1 calc R U P A 1
H17B H 0.5443 0.3447 0.1442 0.025 Uiso 0.7 1 calc R U P A 1
C18A C 0.6991(3) 0.3782(2) 0.2919(3) 0.0157(7) Uani 0.7 1 d . . P A 1
H18A H 0.6821 0.3309 0.3386 0.019 Uiso 0.7 1 calc R U P A 1
H18B H 0.7643 0.3535 0.2640 0.019 Uiso 0.7 1 calc R U P A 1
C17B C 0.5995(14) 0.3794(10) 0.2362(12) 0.030(3) Uani 0.3 1 d . U P B 2
H17C H 0.6467 0.3530 0.3113 0.036 Uiso 0.3 1 calc R U P B 2
H17D H 0.5810 0.3297 0.1809 0.036 Uiso 0.3 1 calc R U P B 2
C18B C 0.6817(12) 0.4467(8) 0.2152(10) 0.049(3) Uani 0.3 1 d . U P B 2
H18C H 0.7676 0.4190 0.2242 0.059 Uiso 0.3 1 calc R U P B 2
H18D H 0.6995 0.4966 0.2701 0.059 Uiso 0.3 1 calc R U P B 2


_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 O7 1.7831(16) . ?
Ti1 O5 1.8661(16) . ?
Ti1 O1 1.9654(16) . ?
Ti1 O3 1.9847(15) . ?
Ti1 O4 2.0685(16) . ?
Ti1 O2 2.1001(16) . ?
O1 N1 1.375(2) . ?
O2 C1 1.273(3) . ?
O3 N2 1.372(2) . ?
O4 C8 1.277(3) . ?
O5 C15 1.421(3) . ?
O6 C16 1.432(3) . ?
O6 H6 0.75(3) . ?
O7 C17A 1.396(6) . ?
O7 C17B 1.513(15) . ?
O8A C18A 1.405(4) . ?
O8A H8A 0.73(3) . ?
O8B C18B 1.484(14) . ?
O8B H8B 0.8400 . ?
N1 C1 1.312(3) . ?
N1 H1 0.90(3) . ?
N2 C8 1.309(3) . ?
N2 H2 0.84(3) . ?
C1 C2 1.483(3) . ?
C2 C3 1.391(3) . ?
C2 C7 1.399(3) . ?
C3 C4 1.388(3) . ?
C3 H3 0.9500 . ?
C4 C5 1.395(3) . ?
C4 H4 0.9500 . ?
C5 C6 1.385(3) . ?
C5 H5 0.9500 . ?
C6 C7 1.385(3) . ?
C6 H6A 0.9500 . ?
C7 H7 0.9500 . ?
C8 C9 1.473(3) . ?
C9 C10 1.398(3) . ?
C9 C14 1.400(3) . ?
C10 C11 1.386(3) . ?
C10 H10 0.9500 . ?
C11 C12 1.390(3) . ?
C11 H11 0.9500 . ?
C12 C13 1.390(3) . ?
C12 H12 0.9500 . ?
C13 C14 1.386(3) . ?
C13 H13 0.9500 . ?
C14 H14 0.9500 . ?
C15 C16 1.510(3) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17A C18A 1.515(5) . ?
C17A H17A 0.9900 . ?
C17A H17B 0.9900 . ?
C18A H18A 0.9900 . ?
C18A H18B 0.9900 . ?
C17B C18B 1.435(18) . ?
C17B H17C 0.9900 . ?
C17B H17D 0.9900 . ?
C18B H18C 0.9900 . ?
C18B H18D 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O7 Ti1 O5 98.83(7) . . ?
O7 Ti1 O1 87.78(7) . . ?
O5 Ti1 O1 102.71(7) . . ?
O7 Ti1 O3 105.50(7) . . ?
O5 Ti1 O3 86.61(6) . . ?
O1 Ti1 O3 162.58(7) . . ?
O7 Ti1 O4 92.48(7) . . ?
O5 Ti1 O4 161.41(7) . . ?
O1 Ti1 O4 92.37(6) . . ?
O3 Ti1 O4 76.13(6) . . ?
O7 Ti1 O2 162.84(7) . . ?
O5 Ti1 O2 90.60(7) . . ?
O1 Ti1 O2 76.12(6) . . ?
O3 Ti1 O2 89.25(6) . . ?
O4 Ti1 O2 82.44(7) . . ?
N1 O1 Ti1 115.80(12) . . ?
C1 O2 Ti1 114.34(14) . . ?
N2 O3 Ti1 114.96(12) . . ?
C8 O4 Ti1 115.34(14) . . ?
C15 O5 Ti1 136.04(14) . . ?
C16 O6 H6 109(3) . . ?
C17A O7 Ti1 148.6(3) . . ?
C17B O7 Ti1 151.3(6) . . ?
C18A O8A H8A 109(4) . . ?
C18B O8B H8B 109.5 . . ?
C1 N1 O1 116.11(18) . . ?
C1 N1 H1 126.1(19) . . ?
O1 N1 H1 115.2(19) . . ?
C8 N2 O3 116.26(18) . . ?
C8 N2 H2 127.8(17) . . ?
O3 N2 H2 115.7(17) . . ?
O2 C1 N1 117.6(2) . . ?
O2 C1 C2 122.8(2) . . ?
N1 C1 C2 119.7(2) . . ?
C3 C2 C7 119.7(2) . . ?
C3 C2 C1 121.9(2) . . ?
C7 C2 C1 118.3(2) . . ?
C4 C3 C2 120.1(2) . . ?
C4 C3 H3 119.9 . . ?
C2 C3 H3 119.9 . . ?
C3 C4 C5 120.1(2) . . ?
C3 C4 H4 120.0 . . ?
C5 C4 H4 120.0 . . ?
C6 C5 C4 119.7(2) . . ?
C6 C5 H5 120.2 . . ?
C4 C5 H5 120.2 . . ?
C7 C6 C5 120.6(2) . . ?
C7 C6 H6A 119.7 . . ?
C5 C6 H6A 119.7 . . ?
C6 C7 C2 119.8(2) . . ?
C6 C7 H7 120.1 . . ?
C2 C7 H7 120.1 . . ?
O4 C8 N2 117.1(2) . . ?
O4 C8 C9 121.4(2) . . ?
N2 C8 C9 121.5(2) . . ?
C10 C9 C14 119.4(2) . . ?
C10 C9 C8 118.5(2) . . ?
C14 C9 C8 122.2(2) . . ?
C11 C10 C9 119.9(2) . . ?
C11 C10 H10 120.0 . . ?
C9 C10 H10 120.0 . . ?
C10 C11 C12 120.5(2) . . ?
C10 C11 H11 119.8 . . ?
C12 C11 H11 119.8 . . ?
C13 C12 C11 119.9(2) . . ?
C13 C12 H12 120.1 . . ?
C11 C12 H12 120.1 . . ?
C14 C13 C12 120.0(2) . . ?
C14 C13 H13 120.0 . . ?
C12 C13 H13 120.0 . . ?
C13 C14 C9 120.3(2) . . ?
C13 C14 H14 119.8 . . ?
C9 C14 H14 119.8 . . ?
O5 C15 C16 111.02(19) . . ?
O5 C15 H15A 109.4 . . ?
C16 C15 H15A 109.4 . . ?
O5 C15 H15B 109.4 . . ?
C16 C15 H15B 109.4 . . ?
H15A C15 H15B 108.0 . . ?
O6 C16 C15 113.65(19) . . ?
O6 C16 H16A 108.8 . . ?
C15 C16 H16A 108.8 . . ?
O6 C16 H16B 108.8 . . ?
C15 C16 H16B 108.8 . . ?
H16A C16 H16B 107.7 . . ?
O7 C17A C18A 110.9(4) . . ?
O7 C17A H17A 109.5 . . ?
C18A C17A H17A 109.5 . . ?
O7 C17A H17B 109.5 . . ?
C18A C17A H17B 109.5 . . ?
H17A C17A H17B 108.1 . . ?
O8A C18A C17A 113.2(3) . . ?
O8A C18A H18A 108.9 . . ?
C17A C18A H18A 108.9 . . ?
O8A C18A H18B 108.9 . . ?
C17A C18A H18B 108.9 . . ?
H18A C18A H18B 107.8 . . ?
C18B C17B O7 110.5(10) . . ?
C18B C17B H17C 109.5 . . ?
O7 C17B H17C 109.5 . . ?
C18B C17B H17D 109.5 . . ?
O7 C17B H17D 109.5 . . ?
H17C C17B H17D 108.1 . . ?
C17B C18B O8B 110.7(10) . . ?
C17B C18B H18C 109.5 . . ?
O8B C18B H18C 109.5 . . ?
C17B C18B H18D 109.5 . . ?
O8B C18B H18D 109.5 . . ?
H18C C18B H18D 108.1 . . ?

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
O7 Ti1 O5 C15 -151.2(2) . . . . ?
O1 Ti1 O5 C15 119.1(2) . . . . ?
O3 Ti1 O5 C15 -46.0(2) . . . . ?
O4 Ti1 O5 C15 -24.4(3) . . . . ?
O2 Ti1 O5 C15 43.2(2) . . . . ?
O5 Ti1 O7 C17A -172.0(4) . . . . ?
O1 Ti1 O7 C17A -69.5(4) . . . . ?
O3 Ti1 O7 C17A 99.1(4) . . . . ?
O4 Ti1 O7 C17A 22.8(4) . . . . ?
O2 Ti1 O7 C17A -49.4(5) . . . . ?
O5 Ti1 O7 C17B -125.2(11) . . . . ?
O1 Ti1 O7 C17B -22.7(11) . . . . ?
O3 Ti1 O7 C17B 145.9(11) . . . . ?
O4 Ti1 O7 C17B 69.6(11) . . . . ?
O2 Ti1 O7 C17B -2.6(12) . . . . ?
Ti1 O1 N1 C1 1.3(2) . . . . ?
Ti1 O3 N2 C8 1.9(2) . . . . ?
Ti1 O2 C1 N1 2.9(3) . . . . ?
Ti1 O2 C1 C2 -179.26(16) . . . . ?
O1 N1 C1 O2 -2.8(3) . . . . ?
O1 N1 C1 C2 179.27(18) . . . . ?
O2 C1 C2 C3 -179.6(2) . . . . ?
N1 C1 C2 C3 -1.8(3) . . . . ?
O2 C1 C2 C7 -0.3(3) . . . . ?
N1 C1 C2 C7 177.5(2) . . . . ?
C7 C2 C3 C4 0.1(3) . . . . ?
C1 C2 C3 C4 179.4(2) . . . . ?
C2 C3 C4 C5 0.4(3) . . . . ?
C3 C4 C5 C6 -0.6(4) . . . . ?
C4 C5 C6 C7 0.3(4) . . . . ?
C5 C6 C7 C2 0.2(3) . . . . ?
C3 C2 C7 C6 -0.4(3) . . . . ?
C1 C2 C7 C6 -179.7(2) . . . . ?
Ti1 O4 C8 N2 -4.9(3) . . . . ?
Ti1 O4 C8 C9 173.65(15) . . . . ?
O3 N2 C8 O4 2.1(3) . . . . ?
O3 N2 C8 C9 -176.45(18) . . . . ?
O4 C8 C9 C10 7.5(3) . . . . ?
N2 C8 C9 C10 -174.1(2) . . . . ?
O4 C8 C9 C14 -170.5(2) . . . . ?
N2 C8 C9 C14 8.0(3) . . . . ?
C14 C9 C10 C11 -0.4(3) . . . . ?
C8 C9 C10 C11 -178.3(2) . . . . ?
C9 C10 C11 C12 0.1(3) . . . . ?
C10 C11 C12 C13 -0.2(4) . . . . ?
C11 C12 C13 C14 0.6(3) . . . . ?
C12 C13 C14 C9 -0.9(3) . . . . ?
C10 C9 C14 C13 0.7(3) . . . . ?
C8 C9 C14 C13 178.6(2) . . . . ?
Ti1 O5 C15 C16 104.6(2) . . . . ?
O5 C15 C16 O6 -73.8(3) . . . . ?
Ti1 O7 C17A C18A 94.3(5) . . . . ?
O7 C17A C18A O8A -67.2(5) . . . . ?
Ti1 O7 C17B C18B -50.2(17) . . . . ?
O7 C17B C18B O8B -62.2(13) . . . . ?

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
N2 H2 O6 0.84(3) 1.94(3) 2.770(3) 169(2) 3_565
O6 H6 O3 0.75(3) 2.03(3) 2.762(2) 167(3) .
O8A H8A O1 0.73(3) 2.13(4) 2.822(3) 158(5) .
N1 H1 O5 0.90(3) 1.94(3) 2.800(2) 162(3) 3_666

_refine_diff_density_max         0.538
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.069

####################################################################### 
# 
# 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_spider-15003
_database_code_depnum_ccdc_archive 'CCDC 1402798'
_audit_update_record             
;
2015-05-25 deposited with the CCDC.
2016-01-12 downloaded from the CCDC.
;

_vrf_PLAT605_spider-15003        
;
PROBLEM: VERY LARGE Solvent Accessible VOID(S) in Structure 
RESPONSE: See the "_refine_special_details" and "_platon_squeeze_details"
of the .cif.
;

_vrf_PLAT869_spider-15003        
;
PROBLEM: ALERTS Related to the use of SQUEEZE Suppressed  
RESPONSE: See the "_refine_special_details" and "_platon_squeeze_details"
of the .cif.
;

_vrf_PLAT083_spider-15003        
;
PROBLEM: SHELXL Second Parameter in WGHT Unusually Large
RESPONSE: Multiple attempts were made to determine if the reflection 
list contained twined components.  No satisfactory twin law could be 
found.  However, the weak scattering may be contributing to the large
error associated with the reflections.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C42 H36 N6 O15 Ti3, 6(C2 H6 O S)'
_chemical_formula_sum            'C54 H72 N6 O21 S6 Ti3'
_chemical_formula_weight         1477.23

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'

_space_group_crystal_system      trigonal
_space_group_IT_number           167
_space_group_name_H-M_alt        'R -3 c :H'
_space_group_name_Hall           '-R 3 2"c'

_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'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+5/6'
'x-y+2/3, -y+1/3, -z+5/6'
'-x+2/3, -x+y+1/3, -z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+7/6'
'x-y+1/3, -y+2/3, -z+7/6'
'-x+1/3, -x+y+2/3, -z+7/6'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z-1/6'
'-x+y+2/3, y+1/3, z-1/6'
'x+2/3, x-y+1/3, z-1/6'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+1/6'
'-x+y+1/3, y+2/3, z+1/6'
'x+1/3, x-y+2/3, z+1/6'

_cell_length_a                   15.7049(9)
_cell_length_b                   15.7049(9)
_cell_length_c                   53.457(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     11418.5(15)
_cell_formula_units_Z            6
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    34435
_cell_measurement_theta_min      3.0
_cell_measurement_theta_max      27.6

_exptl_crystal_description       Block
_exptl_crystal_colour            Colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_F_000             4608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    0.538
_shelx_estimated_absorpt_T_min   0.924
_shelx_estimated_absorpt_T_max   0.924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.714
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private Communication'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Sealed Tube'
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID imaging plate'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10
_diffrn_reflns_number            59502
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_av_R_equivalents  0.1488
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -64
_diffrn_reflns_limit_l_max       64
_diffrn_reflns_theta_min         3.091
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2324
_reflns_number_gt                1682
_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. 
  
 Structure factors included contributions from the .fab file. 
  
 _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       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;
Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H., 
OLEX2: A complete structure solution, refinement and analysis program
(2009). J. Appl. Cryst., 42, 339-341.
;
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'
_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. 

 The hydrogen atoms were first found in the difference map, then generated 
 geometrically and refined as riding atoms with C-H distances = 0.95- 0.99 
 Å and Uiso(H) = 1.2 times Ueq(C) for CH groups and Uiso(H) 
 = 1.5 times Ueq(C) for CH3 groups. The only exception is H1.  The Uiso
 is freely refining, but the distance to N1 was fixed near a value of 0.90Å.

 One DMSO solvent was modeled as disordered over a major and minor position,
 denoted by the atom label suffixes "a" and "b", respectively. The site 
 occupancy factors were freely refined and subsequently fixed at their 
 converged values 0.64 and 0.36.  A RIGU restraint was used to aid in the 
 convergence of the DMSO model.

 The program SQUEEZE was used to compensate for the contribution of 
 disordered solvents contained in voids within the crystal lattice from
 the diffraction intensities. This procedure was applied to the data file 
 and the submitted model is based on the solvent removed data. Based on
 the total electron density found in the voids (401.4 e/Å³), it is 
 likely that ~10 DMSO molecules are present in the unit cell.
 See "_platon_squeeze_details" in this .cif for more information.  
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0925P)²+75.9534P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2324
_refine_ls_number_parameters     172
_refine_ls_number_restraints     37
_refine_ls_R_factor_all          0.1024
_refine_ls_R_factor_gt           0.0744
_refine_ls_wR_factor_ref         0.1986
_refine_ls_wR_factor_gt          0.1801
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.054
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.54045(7) 0.3333 0.5833 0.0363(4) Uani 1 2 d S T P . .
O1 O 0.5252(2) 0.3557(2) 0.54806(6) 0.0446(8) Uani 1 1 d . . . . .
O2 O 0.3877(2) 0.2397(2) 0.57635(6) 0.0438(8) Uani 1 1 d . . . . .
O3 O 0.6667 0.4354(3) 0.5833 0.0353(10) Uani 1 2 d S T P . .
N1 N 0.4289(3) 0.3213(3) 0.54101(8) 0.0467(10) Uani 1 1 d D . . . .
C1 C 0.3604(4) 0.2623(3) 0.55643(10) 0.0436(11) Uani 1 1 d . . . . .
C2 C 0.2554(4) 0.2272(4) 0.55124(11) 0.0529(14) Uani 1 1 d . . . . .
C3 C 0.2218(5) 0.2379(5) 0.52861(13) 0.0724(18) Uani 1 1 d . . . . .
H3 H 0.2663 0.2682 0.5151 0.087 Uiso 1 1 calc R U . . .
C4 C 0.1202(5) 0.2033(6) 0.52539(15) 0.083(2) Uani 1 1 d . . . . .
H4 H 0.0967 0.2115 0.5097 0.099 Uiso 1 1 calc R U . . .
C5 C 0.0577(5) 0.1597(5) 0.54391(15) 0.081(2) Uani 1 1 d . . . . .
H5 H -0.0105 0.1345 0.5412 0.097 Uiso 1 1 calc R U . . .
C6 C 0.0894(4) 0.1503(5) 0.56700(15) 0.0759(19) Uani 1 1 d . . . . .
H6 H 0.0437 0.1207 0.5803 0.091 Uiso 1 1 calc R U . . .
C7 C 0.1884(4) 0.1838(4) 0.57104(13) 0.0652(16) Uani 1 1 d . . . . .
H7 H 0.2107 0.1774 0.5871 0.078 Uiso 1 1 calc R U . . .
S1A S 0.4244(6) 0.4313(8) 0.47507(14) 0.0483(16) Uani 0.36 1 d . U P A 2
S1B S 0.4348(5) 0.4179(5) 0.47037(12) 0.116(3) Uani 0.64 1 d . U P A 1
O4 O 0.4095(3) 0.3458(3) 0.49137(7) 0.0687(11) Uani 1 1 d . U . . .
C8A C 0.3232(12) 0.4577(15) 0.4826(4) 0.071(4) Uani 0.36 1 d . U P A 2
H8AA H 0.3316 0.4831 0.4997 0.106 Uiso 0.36 1 calc R U P A 2
H8AB H 0.2595 0.3971 0.4812 0.106 Uiso 0.36 1 calc R U P A 2
H8AC H 0.3256 0.5068 0.4709 0.106 Uiso 0.36 1 calc R U P A 2
C8B C 0.3227(9) 0.4034(9) 0.4620(3) 0.103(4) Uani 0.64 1 d . U P A 1
H8BA H 0.2802 0.3364 0.4558 0.155 Uiso 0.64 1 calc R U P A 1
H8BB H 0.3319 0.4508 0.4489 0.155 Uiso 0.64 1 calc R U P A 1
H8BC H 0.2919 0.4146 0.4766 0.155 Uiso 0.64 1 calc R U P A 1
C9A C 0.3741(15) 0.3872(15) 0.4448(3) 0.072(5) Uani 0.36 1 d . U P A 2
H9AA H 0.4229 0.3822 0.4344 0.108 Uiso 0.36 1 calc R U P A 2
H9AB H 0.3567 0.4329 0.4370 0.108 Uiso 0.36 1 calc R U P A 2
H9AC H 0.3152 0.3223 0.4463 0.108 Uiso 0.36 1 calc R U P A 2
C9B C 0.4467(15) 0.3631(15) 0.4447(3) 0.154(6) Uani 0.64 1 d . U P A 1
H9BA H 0.5159 0.3820 0.4425 0.232 Uiso 0.64 1 calc R U P A 1
H9BB H 0.4242 0.3838 0.4301 0.232 Uiso 0.64 1 calc R U P A 1
H9BC H 0.4069 0.2916 0.4466 0.232 Uiso 0.64 1 calc R U P A 1
H1 H 0.424(4) 0.339(4) 0.5258(5) 0.056(16) Uiso 1 1 d 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 O3 1.8223(16) . ?
Ti1 O3 1.8224(16) 2_655 ?
Ti1 O1 1.955(3) 17 ?
Ti1 O1 1.955(3) . ?
Ti1 O2 2.128(3) 17 ?
Ti1 O2 2.128(3) . ?
O1 N1 1.379(5) . ?
O2 C1 1.263(6) . ?
O3 Ti1 1.8223(16) 3_665 ?
N1 C1 1.304(7) . ?
N1 H1 0.87(2) . ?
C1 C2 1.480(7) . ?
C2 C3 1.363(8) . ?
C2 C7 1.405(8) . ?
C3 C4 1.417(9) . ?
C3 H3 0.9500 . ?
C4 C5 1.319(10) . ?
C4 H4 0.9500 . ?
C5 C6 1.366(10) . ?
C5 H5 0.9500 . ?
C6 C7 1.386(8) . ?
C6 H6 0.9500 . ?
C7 H7 0.9500 . ?
S1A O4 1.517(11) . ?
S1A C9A 1.782(18) . ?
S1A C8A 1.877(18) . ?
S1B O4 1.500(7) . ?
S1B C9B 1.68(2) . ?
S1B C8B 1.718(13) . ?
C8A H8AA 0.9800 . ?
C8A H8AB 0.9800 . ?
C8A H8AC 0.9800 . ?
C8B H8BA 0.9800 . ?
C8B H8BB 0.9800 . ?
C8B H8BC 0.9800 . ?
C9A H9AA 0.9800 . ?
C9A H9AB 0.9800 . ?
C9A H9AC 0.9800 . ?
C9B H9BA 0.9800 . ?
C9B H9BB 0.9800 . ?
C9B H9BC 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 Ti1 O3 99.2(3) . 2_655 ?
O3 Ti1 O1 104.86(10) . 17 ?
O3 Ti1 O1 91.10(10) 2_655 17 ?
O3 Ti1 O1 91.10(10) . . ?
O3 Ti1 O1 104.87(10) 2_655 . ?
O1 Ti1 O1 155.4(2) 17 . ?
O3 Ti1 O2 92.93(15) . 17 ?
O3 Ti1 O2 164.21(14) 2_655 17 ?
O1 Ti1 O2 75.98(13) 17 17 ?
O1 Ti1 O2 84.81(14) . 17 ?
O3 Ti1 O2 164.21(14) . . ?
O3 Ti1 O2 92.93(15) 2_655 . ?
O1 Ti1 O2 84.81(14) 17 . ?
O1 Ti1 O2 75.97(14) . . ?
O2 Ti1 O2 77.11(17) 17 . ?
N1 O1 Ti1 113.7(3) . . ?
C1 O2 Ti1 112.2(3) . . ?
Ti1 O3 Ti1 140.8(3) 3_665 . ?
C1 N1 O1 117.3(4) . . ?
C1 N1 H1 130(4) . . ?
O1 N1 H1 112(4) . . ?
O2 C1 N1 117.2(4) . . ?
O2 C1 C2 121.7(5) . . ?
N1 C1 C2 121.1(5) . . ?
C3 C2 C7 119.1(6) . . ?
C3 C2 C1 123.2(6) . . ?
C7 C2 C1 117.6(5) . . ?
C2 C3 C4 119.4(6) . . ?
C2 C3 H3 120.3 . . ?
C4 C3 H3 120.3 . . ?
C5 C4 C3 120.7(7) . . ?
C5 C4 H4 119.6 . . ?
C3 C4 H4 119.6 . . ?
C4 C5 C6 121.2(7) . . ?
C4 C5 H5 119.4 . . ?
C6 C5 H5 119.4 . . ?
C5 C6 C7 120.0(7) . . ?
C5 C6 H6 120.0 . . ?
C7 C6 H6 120.0 . . ?
C6 C7 C2 119.5(6) . . ?
C6 C7 H7 120.3 . . ?
C2 C7 H7 120.3 . . ?
O4 S1A C9A 109.6(9) . . ?
O4 S1A C8A 107.4(6) . . ?
C9A S1A C8A 91.2(10) . . ?
O4 S1B C9B 106.3(8) . . ?
O4 S1B C8B 103.1(6) . . ?
C9B S1B C8B 95.1(9) . . ?
S1A C8A H8AA 109.5 . . ?
S1A C8A H8AB 109.5 . . ?
H8AA C8A H8AB 109.5 . . ?
S1A C8A H8AC 109.5 . . ?
H8AA C8A H8AC 109.5 . . ?
H8AB C8A H8AC 109.5 . . ?
S1B C8B H8BA 109.5 . . ?
S1B C8B H8BB 109.5 . . ?
H8BA C8B H8BB 109.5 . . ?
S1B C8B H8BC 109.5 . . ?
H8BA C8B H8BC 109.5 . . ?
H8BB C8B H8BC 109.5 . . ?
S1A C9A H9AA 109.5 . . ?
S1A C9A H9AB 109.5 . . ?
H9AA C9A H9AB 109.5 . . ?
S1A C9A H9AC 109.5 . . ?
H9AA C9A H9AC 109.5 . . ?
H9AB C9A H9AC 109.5 . . ?
S1B C9B H9BA 109.5 . . ?
S1B C9B H9BB 109.5 . . ?
H9BA C9B H9BB 109.5 . . ?
S1B C9B H9BC 109.5 . . ?
H9BA C9B H9BC 109.5 . . ?
H9BB C9B H9BC 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
O3 Ti1 O3 Ti1 -0.003(0) 2_655 . . 3_665 ?
O1 Ti1 O3 Ti1 93.62(11) 17 . . 3_665 ?
O1 Ti1 O3 Ti1 -105.26(10) . . . 3_665 ?
O2 Ti1 O3 Ti1 169.89(9) 17 . . 3_665 ?
O2 Ti1 O3 Ti1 -139.9(4) . . . 3_665 ?
Ti1 O1 N1 C1 -13.5(5) . . . . ?
Ti1 O2 C1 N1 14.4(5) . . . . ?
Ti1 O2 C1 C2 -162.8(3) . . . . ?
O1 N1 C1 O2 -1.5(6) . . . . ?
O1 N1 C1 C2 175.8(4) . . . . ?
O2 C1 C2 C3 -170.1(5) . . . . ?
N1 C1 C2 C3 12.7(8) . . . . ?
O2 C1 C2 C7 11.9(7) . . . . ?
N1 C1 C2 C7 -165.2(5) . . . . ?
C7 C2 C3 C4 -1.2(9) . . . . ?
C1 C2 C3 C4 -179.1(6) . . . . ?
C2 C3 C4 C5 -1.0(11) . . . . ?
C3 C4 C5 C6 2.7(12) . . . . ?
C4 C5 C6 C7 -2.2(11) . . . . ?
C5 C6 C7 C2 -0.1(9) . . . . ?
C3 C2 C7 C6 1.7(8) . . . . ?
C1 C2 C7 C6 179.8(5) . . . . ?

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
N1 H1 O4 0.87(2) 1.86(2) 2.720(6) 166(5) .

_refine_diff_density_max         0.750
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.079



####################################################################### 
# 
# 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_spider-15013
_database_code_depnum_ccdc_archive 'CCDC 1402799'
_audit_update_record             
;
2015-05-25 deposited with the CCDC.
2016-01-12 downloaded from the CCDC.
;

_vrf_THETM01_spider-15013        
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The overall quality of the data was poor due to crystal quality.
The dichloromethane solvent molecules in the crystal lattice caused 
the crystals to dissolve and crack while screening. This fact
affected the material's crystallinity. The crystal was also very small, 
which exacerbated the already weak diffraction. A high resolution cut-off 
of 0.95 angstroms was applied to the data.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C32 H32 N4 O10 Ti2, 4(C H2 Cl2)'
_chemical_formula_sum            'C36 H40 Cl8 N4 O10 Ti2'
_chemical_formula_weight         1068.12

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'
Cl Cl 0.1484 0.1585 '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           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;

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

_cell_length_a                   12.1927(9)
_cell_length_b                   10.0654(8)
_cell_length_c                   19.3484(15)
_cell_angle_alpha                90
_cell_angle_beta                 102.042(7)
_cell_angle_gamma                90
_cell_volume                     2322.3(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    25218
_cell_measurement_theta_min      3.0
_cell_measurement_theta_max      25.7

_exptl_crystal_description       Block
_exptl_crystal_colour            Colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.528
_exptl_crystal_F_000             1088
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.860
_shelx_estimated_absorpt_T_min   0.847
_shelx_estimated_absorpt_T_max   0.966
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.648
_exptl_absorpt_correction_T_max  0.966
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private Communication'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Sealed Tube'
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID imaging plate'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10
_diffrn_reflns_number            31353
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_av_R_equivalents  0.1328
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.990
_diffrn_reflns_theta_max         21.964
_diffrn_reflns_theta_full        21.965
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2831
_reflns_number_gt                2258
_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       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r15 (Rigaku, 2011)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;
Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H., 
OLEX2: A complete structure solution, refinement and analysis program
(2009). J. Appl. Cryst., 42, 339-341.
;
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'
_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. 

 The hydrogen atoms were first found in the difference map, then generated 
 geometrically and refined as riding atoms with C-H distances = 0.95- 0.99 
 Å and Uiso(H) = 1.2 times Ueq(C) for CH and CH2 groups and Uiso(H) 
 = 1.5 times Ueq(C) for CH3 groups.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1367P)²+13.4010P] 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         2831
_refine_ls_number_parameters     273
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1033
_refine_ls_R_factor_gt           0.0886
_refine_ls_wR_factor_ref         0.2587
_refine_ls_wR_factor_gt          0.2478
_refine_ls_goodness_of_fit_ref   1.124
_refine_ls_restrained_S_all      1.124
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.51929(13) 0.88262(15) 0.46917(7) 0.0269(5) Uani 1 1 d . . . . .
O1 O 0.3994(5) 0.9807(5) 0.4818(3) 0.0273(14) Uani 1 1 d . . . . .
O2 O 0.5655(5) 0.9514(6) 0.3828(3) 0.0299(14) Uani 1 1 d . . . . .
O3 O 0.4309(5) 0.7696(6) 0.3863(3) 0.0308(14) Uani 1 1 d . . . . .
O4 O 0.6540(4) 0.7567(5) 0.4895(3) 0.0259(13) Uani 1 1 d . . . . .
O5 O 0.4837(5) 0.7536(6) 0.5386(3) 0.0311(14) Uani 1 1 d . . . . .
N1 N 0.5202(6) 0.8906(7) 0.3204(3) 0.0261(17) Uani 1 1 d . . . . .
N2 N 0.5642(6) 0.6612(7) 0.5638(4) 0.0295(17) Uani 1 1 d . . . . .
C1 C 0.5466(8) 0.9520(9) 0.2587(4) 0.035(2) Uani 1 1 d . . . . .
H1A H 0.5296 1.0471 0.2588 0.053 Uiso 1 1 calc R U . . .
H1B H 0.5017 0.9109 0.2162 0.053 Uiso 1 1 calc R U . . .
H1C H 0.6264 0.9397 0.2591 0.053 Uiso 1 1 calc R U . . .
C2 C 0.4496(7) 0.7948(9) 0.3251(4) 0.027(2) Uani 1 1 d . . . . .
C3 C 0.3956(7) 0.7153(9) 0.2628(4) 0.030(2) Uani 1 1 d . . . . .
C4 C 0.4583(8) 0.6496(9) 0.2198(4) 0.035(2) Uani 1 1 d . . . . .
H4 H 0.5375 0.6592 0.2292 0.043 Uiso 1 1 calc R U . . .
C5 C 0.4060(8) 0.5718(9) 0.1646(5) 0.040(2) Uani 1 1 d . . . . .
H5 H 0.4490 0.5255 0.1367 0.048 Uiso 1 1 calc R U . . .
C6 C 0.2901(8) 0.5608(9) 0.1496(5) 0.039(2) Uani 1 1 d . . . . .
H6 H 0.2536 0.5091 0.1104 0.047 Uiso 1 1 calc R U . . .
C7 C 0.2286(8) 0.6237(9) 0.1906(5) 0.037(2) Uani 1 1 d . . . . .
H7 H 0.1493 0.6151 0.1795 0.044 Uiso 1 1 calc R U . . .
C8 C 0.2783(7) 0.7001(9) 0.2480(4) 0.032(2) Uani 1 1 d . . . . .
H8 H 0.2342 0.7414 0.2770 0.038 Uiso 1 1 calc R U . . .
C9 C 0.5403(8) 0.5839(9) 0.6221(5) 0.040(2) Uani 1 1 d . . . . .
H9A H 0.5074 0.6416 0.6532 0.060 Uiso 1 1 calc R U . . .
H9B H 0.6100 0.5451 0.6489 0.060 Uiso 1 1 calc R U . . .
H9C H 0.4874 0.5127 0.6037 0.060 Uiso 1 1 calc R U . . .
C10 C 0.6545(7) 0.6667(9) 0.5367(4) 0.030(2) Uani 1 1 d . . . . .
C11 C 0.7509(7) 0.5753(8) 0.5562(4) 0.029(2) Uani 1 1 d . . . . .
C12 C 0.8580(8) 0.6271(9) 0.5590(4) 0.034(2) Uani 1 1 d . . . . .
H12 H 0.8666 0.7187 0.5495 0.040 Uiso 1 1 calc R U . . .
C13 C 0.9492(8) 0.5487(10) 0.5750(5) 0.039(2) Uani 1 1 d . . . . .
H13 H 1.0215 0.5853 0.5767 0.047 Uiso 1 1 calc R U . . .
C14 C 0.9382(9) 0.4141(10) 0.5890(5) 0.042(2) Uani 1 1 d . . . . .
H14 H 1.0026 0.3587 0.6000 0.050 Uiso 1 1 calc R U . . .
C15 C 0.8334(9) 0.3624(10) 0.5868(5) 0.046(3) Uani 1 1 d . . . . .
H15 H 0.8257 0.2710 0.5970 0.055 Uiso 1 1 calc R U . . .
C16 C 0.7384(8) 0.4418(9) 0.5699(5) 0.036(2) Uani 1 1 d . . . . .
H16 H 0.6660 0.4050 0.5677 0.043 Uiso 1 1 calc R U . . .
Cl1 Cl 0.8608(2) 0.8511(3) 0.31524(14) 0.0557(8) Uani 1 1 d . . . . .
Cl2 Cl 0.7465(2) 0.6156(3) 0.35272(15) 0.0543(8) Uani 1 1 d . . . . .
C17 C 0.7947(9) 0.7764(10) 0.3784(5) 0.049(3) Uani 1 1 d . . . . .
H17A H 0.8484 0.7718 0.4244 0.058 Uiso 1 1 calc R U . . .
H17B H 0.7305 0.8321 0.3847 0.058 Uiso 1 1 calc R U . . .
Cl3 Cl 0.1101(2) 0.9001(3) 0.52749(14) 0.0556(8) Uani 1 1 d . . . . .
Cl4 Cl 0.2401(3) 0.7652(3) 0.65185(15) 0.0657(9) Uani 1 1 d . . . . .
C18 C 0.2402(8) 0.8273(11) 0.5682(5) 0.044(2) Uani 1 1 d . . . . .
H18A H 0.2576 0.7542 0.5380 0.052 Uiso 1 1 calc R U . . .
H18B H 0.3001 0.8948 0.5718 0.052 Uiso 1 1 calc R U . . .


_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O1 1.822(6) . ?
Ti1 O1 1.839(6) 3_676 ?
Ti1 O5 1.981(6) . ?
Ti1 O2 1.996(6) . ?
Ti1 O4 2.046(5) . ?
Ti1 O3 2.075(6) . ?
Ti1 Ti1 2.732(3) 3_676 ?
O1 Ti1 1.839(5) 3_676 ?
O2 N1 1.362(8) . ?
O3 C2 1.277(10) . ?
O4 C10 1.287(10) . ?
O5 N2 1.366(9) . ?
N1 C2 1.309(11) . ?
N1 C1 1.439(11) . ?
N2 C10 1.315(11) . ?
N2 C9 1.450(11) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C2 C3 1.483(12) . ?
C3 C8 1.406(12) . ?
C3 C4 1.407(12) . ?
C4 C5 1.370(13) . ?
C4 H4 0.9500 . ?
C5 C6 1.386(13) . ?
C5 H5 0.9500 . ?
C6 C7 1.357(13) . ?
C6 H6 0.9500 . ?
C7 C8 1.383(13) . ?
C7 H7 0.9500 . ?
C8 H8 0.9500 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C10 C11 1.478(13) . ?
C11 C16 1.384(13) . ?
C11 C12 1.397(13) . ?
C12 C13 1.346(13) . ?
C12 H12 0.9500 . ?
C13 C14 1.393(14) . ?
C13 H13 0.9500 . ?
C14 C15 1.372(15) . ?
C14 H14 0.9500 . ?
C15 C16 1.389(14) . ?
C15 H15 0.9500 . ?
C16 H16 0.9500 . ?
Cl1 C17 1.766(10) . ?
Cl2 C17 1.758(10) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
Cl3 C18 1.776(10) . ?
Cl4 C18 1.734(10) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Ti1 O1 83.5(3) . 3_676 ?
O1 Ti1 O5 88.2(2) . . ?
O1 Ti1 O5 108.2(2) 3_676 . ?
O1 Ti1 O2 107.4(2) . . ?
O1 Ti1 O2 87.5(2) 3_676 . ?
O5 Ti1 O2 159.3(2) . . ?
O1 Ti1 O4 160.7(2) . . ?
O1 Ti1 O4 92.3(2) 3_676 . ?
O5 Ti1 O4 75.2(2) . . ?
O2 Ti1 O4 91.1(2) . . ?
O1 Ti1 O3 95.7(2) . . ?
O1 Ti1 O3 161.1(2) 3_676 . ?
O5 Ti1 O3 90.7(2) . . ?
O2 Ti1 O3 74.6(2) . . ?
O4 Ti1 O3 94.3(2) . . ?
O1 Ti1 Ti1 41.98(17) . 3_676 ?
O1 Ti1 Ti1 41.49(18) 3_676 3_676 ?
O5 Ti1 Ti1 100.91(18) . 3_676 ?
O2 Ti1 Ti1 99.81(18) . 3_676 ?
O4 Ti1 Ti1 131.01(18) . 3_676 ?
O3 Ti1 Ti1 134.64(18) . 3_676 ?
Ti1 O1 Ti1 96.5(3) . 3_676 ?
N1 O2 Ti1 116.9(5) . . ?
C2 O3 Ti1 116.3(5) . . ?
C10 O4 Ti1 117.2(5) . . ?
N2 O5 Ti1 116.4(4) . . ?
C2 N1 O2 114.8(6) . . ?
C2 N1 C1 129.7(7) . . ?
O2 N1 C1 115.0(7) . . ?
C10 N2 O5 115.4(7) . . ?
C10 N2 C9 130.8(7) . . ?
O5 N2 C9 113.4(7) . . ?
N1 C1 H1A 109.5 . . ?
N1 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
N1 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
O3 C2 N1 117.3(7) . . ?
O3 C2 C3 120.8(8) . . ?
N1 C2 C3 121.9(7) . . ?
C8 C3 C4 119.0(8) . . ?
C8 C3 C2 118.9(7) . . ?
C4 C3 C2 122.0(8) . . ?
C5 C4 C3 120.5(9) . . ?
C5 C4 H4 119.8 . . ?
C3 C4 H4 119.8 . . ?
C4 C5 C6 119.8(9) . . ?
C4 C5 H5 120.1 . . ?
C6 C5 H5 120.1 . . ?
C7 C6 C5 120.2(9) . . ?
C7 C6 H6 119.9 . . ?
C5 C6 H6 119.9 . . ?
C6 C7 C8 121.8(9) . . ?
C6 C7 H7 119.1 . . ?
C8 C7 H7 119.1 . . ?
C7 C8 C3 118.7(8) . . ?
C7 C8 H8 120.7 . . ?
C3 C8 H8 120.7 . . ?
N2 C9 H9A 109.5 . . ?
N2 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N2 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
O4 C10 N2 115.6(8) . . ?
O4 C10 C11 120.4(8) . . ?
N2 C10 C11 124.0(8) . . ?
C16 C11 C12 119.6(8) . . ?
C16 C11 C10 122.7(8) . . ?
C12 C11 C10 117.7(8) . . ?
C13 C12 C11 120.7(9) . . ?
C13 C12 H12 119.7 . . ?
C11 C12 H12 119.7 . . ?
C12 C13 C14 120.4(9) . . ?
C12 C13 H13 119.8 . . ?
C14 C13 H13 119.8 . . ?
C15 C14 C13 119.3(9) . . ?
C15 C14 H14 120.3 . . ?
C13 C14 H14 120.3 . . ?
C14 C15 C16 121.0(10) . . ?
C14 C15 H15 119.5 . . ?
C16 C15 H15 119.5 . . ?
C11 C16 C15 119.0(9) . . ?
C11 C16 H16 120.5 . . ?
C15 C16 H16 120.5 . . ?
Cl2 C17 Cl1 111.7(6) . . ?
Cl2 C17 H17A 109.3 . . ?
Cl1 C17 H17A 109.3 . . ?
Cl2 C17 H17B 109.3 . . ?
Cl1 C17 H17B 109.3 . . ?
H17A C17 H17B 107.9 . . ?
Cl4 C18 Cl3 112.9(5) . . ?
Cl4 C18 H18A 109.0 . . ?
Cl3 C18 H18A 109.0 . . ?
Cl4 C18 H18B 109.0 . . ?
Cl3 C18 H18B 109.0 . . ?
H18A C18 H18B 107.8 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Ti1 O1 Ti1 -0.004(2) 3_676 . . 3_676 ?
O5 Ti1 O1 Ti1 108.5(3) . . . 3_676 ?
O2 Ti1 O1 Ti1 -85.3(3) . . . 3_676 ?
O4 Ti1 O1 Ti1 78.1(8) . . . 3_676 ?
O3 Ti1 O1 Ti1 -161.0(2) . . . 3_676 ?
Ti1 O2 N1 C2 1.1(8) . . . . ?
Ti1 O2 N1 C1 173.8(5) . . . . ?
Ti1 O5 N2 C10 -2.3(9) . . . . ?
Ti1 O5 N2 C9 170.8(6) . . . . ?
Ti1 O3 C2 N1 -1.5(9) . . . . ?
Ti1 O3 C2 C3 176.8(6) . . . . ?
O2 N1 C2 O3 0.3(10) . . . . ?
C1 N1 C2 O3 -171.1(8) . . . . ?
O2 N1 C2 C3 -177.9(7) . . . . ?
C1 N1 C2 C3 10.6(13) . . . . ?
O3 C2 C3 C8 53.0(11) . . . . ?
N1 C2 C3 C8 -128.8(9) . . . . ?
O3 C2 C3 C4 -124.0(9) . . . . ?
N1 C2 C3 C4 54.2(12) . . . . ?
C8 C3 C4 C5 -0.1(13) . . . . ?
C2 C3 C4 C5 176.9(8) . . . . ?
C3 C4 C5 C6 1.9(14) . . . . ?
C4 C5 C6 C7 -1.9(14) . . . . ?
C5 C6 C7 C8 0.0(14) . . . . ?
C6 C7 C8 C3 1.8(13) . . . . ?
C4 C3 C8 C7 -1.7(12) . . . . ?
C2 C3 C8 C7 -178.8(8) . . . . ?
Ti1 O4 C10 N2 3.9(9) . . . . ?
Ti1 O4 C10 C11 -177.7(6) . . . . ?
O5 N2 C10 O4 -1.1(10) . . . . ?
C9 N2 C10 O4 -172.7(8) . . . . ?
O5 N2 C10 C11 -179.5(7) . . . . ?
C9 N2 C10 C11 8.9(14) . . . . ?
O4 C10 C11 C16 -140.7(9) . . . . ?
N2 C10 C11 C16 37.6(13) . . . . ?
O4 C10 C11 C12 37.7(11) . . . . ?
N2 C10 C11 C12 -144.0(8) . . . . ?
C16 C11 C12 C13 -0.2(13) . . . . ?
C10 C11 C12 C13 -178.6(8) . . . . ?
C11 C12 C13 C14 0.0(13) . . . . ?
C12 C13 C14 C15 -0.4(14) . . . . ?
C13 C14 C15 C16 0.9(14) . . . . ?
C12 C11 C16 C15 0.7(13) . . . . ?
C10 C11 C16 C15 179.0(8) . . . . ?
C14 C15 C16 C11 -1.0(14) . . . . ?

_refine_diff_density_max         0.998
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.142

