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

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

data_5k
_database_code_depnum_ccdc_archive 'CCDC 1880612'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H18 Cl N3 O'
_chemical_formula_sum            'C14 H18 Cl N3 O'
_chemical_formula_weight         279.76

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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                   9.1264(5)
_cell_length_b                   15.3834(8)
_cell_length_c                   11.2882(5)
_cell_angle_alpha                90
_cell_angle_beta                 111.447(5)
_cell_angle_gamma                90
_cell_volume                     1475.07(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2221
_cell_measurement_theta_min      4.1920
_cell_measurement_theta_max      69.5360

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_F_000             592
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.19
_exptl_absorpt_coefficient_mu    2.260
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.66840
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5422
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         5.098
_diffrn_reflns_theta_max         70.073
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2741
_reflns_number_gt                2151
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0689P)²+0.3275P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_extinction_coef       0.0076(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2741
_refine_ls_number_parameters     181
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0468
_refine_ls_wR_factor_ref         0.1382
_refine_ls_wR_factor_gt          0.1235
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_restrained_S_all      0.996
_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
Cl1 Cl 0.63360(10) 0.18039(6) 0.57860(5) 0.0960(3) Uani 1 1 d . . . . .
O1 O 0.69086(17) 0.26266(10) 0.13714(13) 0.0568(4) Uani 1 1 d . . . . .
N1 N 0.52145(17) 0.17391(10) -0.01224(13) 0.0392(4) Uani 1 1 d . . . . .
N2 N 0.35389(18) 0.07424(11) 0.04045(15) 0.0463(4) Uani 1 1 d . . . . .
N3 N 0.32301(18) 0.09579(11) -0.16831(15) 0.0436(4) Uani 1 1 d . . . . .
C1 C 0.7658(3) 0.17318(18) -0.0612(2) 0.0665(7) Uani 1 1 d . . . . .
H1A H 0.824866 0.208032 0.011017 0.100 Uiso 1 1 calc R U . . .
H1B H 0.805330 0.182127 -0.128267 0.100 Uiso 1 1 calc R U . . .
H1C H 0.776132 0.112948 -0.037318 0.100 Uiso 1 1 calc R U . . .
C2 C 0.5935(2) 0.19915(13) -0.10723(17) 0.0466(5) Uani 1 1 d . . . . .
H2 H 0.539641 0.164801 -0.183991 0.056 Uiso 1 1 calc R U . . .
C3 C 0.5639(3) 0.29355(16) -0.1460(2) 0.0640(6) Uani 1 1 d . . . . .
H3A H 0.453661 0.306026 -0.170580 0.096 Uiso 1 1 calc R U . . .
H3B H 0.596323 0.304615 -0.216487 0.096 Uiso 1 1 calc R U . . .
H3C H 0.622824 0.329936 -0.075617 0.096 Uiso 1 1 calc R U . . .
C4 C 0.5895(2) 0.20570(13) 0.11136(17) 0.0426(4) Uani 1 1 d . . . . .
C5 C 0.5348(2) 0.16549(12) 0.20434(17) 0.0434(4) Uani 1 1 d . . . . .
C6 C 0.5995(3) 0.19180(14) 0.33203(18) 0.0527(5) Uani 1 1 d . . . . .
H6 H 0.674100 0.236017 0.357068 0.063 Uiso 1 1 calc R U . . .
C7 C 0.5508(3) 0.15107(17) 0.41924(19) 0.0597(6) Uani 1 1 d . . . . .
C8 C 0.4377(3) 0.08570(18) 0.3825(2) 0.0674(7) Uani 1 1 d . . . . .
H8 H 0.403784 0.059974 0.442521 0.081 Uiso 1 1 calc R U . . .
C9 C 0.3760(3) 0.05903(16) 0.2578(2) 0.0597(6) Uani 1 1 d . . . . .
H9 H 0.302342 0.014326 0.234073 0.072 Uiso 1 1 calc R U . . .
C10 C 0.4241(2) 0.09926(13) 0.16548(18) 0.0453(5) Uani 1 1 d . . . . .
C11 C 0.3983(2) 0.11337(12) -0.04265(17) 0.0381(4) Uani 1 1 d . . . . .
C12 C 0.1991(2) 0.03025(14) -0.2127(2) 0.0515(5) Uani 1 1 d . . . . .
H12 H 0.235798 -0.022400 -0.161459 0.062 Uiso 1 1 calc R U . . .
C13 C 0.0467(3) 0.0592(2) -0.1999(3) 0.0907(9) Uani 1 1 d . . . . .
H13A H 0.066242 0.074012 -0.112864 0.136 Uiso 1 1 calc R U . . .
H13B H -0.028753 0.012813 -0.225924 0.136 Uiso 1 1 calc R U . . .
H13C H 0.006173 0.109053 -0.252945 0.136 Uiso 1 1 calc R U . . .
C14 C 0.1776(3) 0.00937(16) -0.3491(2) 0.0696(7) Uani 1 1 d . . . . .
H14A H 0.140783 0.060168 -0.400926 0.104 Uiso 1 1 calc R U . . .
H14B H 0.101929 -0.036565 -0.379948 0.104 Uiso 1 1 calc R U . . .
H14C H 0.276402 -0.008710 -0.353032 0.104 Uiso 1 1 calc R U . . .
H3D H 0.323(3) 0.1375(16) -0.219(2) 0.060(7) Uiso 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cl1 C7 1.737(2) . ?
O1 C4 1.229(2) . ?
N1 C4 1.392(2) . ?
N1 C11 1.402(2) . ?
N1 C2 1.500(2) . ?
N2 C11 1.298(2) . ?
N2 C10 1.375(2) . ?
N3 C11 1.358(2) . ?
N3 C12 1.460(2) . ?
C1 C2 1.518(3) . ?
C2 C3 1.512(3) . ?
C4 C5 1.455(3) . ?
C5 C10 1.389(3) . ?
C5 C6 1.403(3) . ?
C6 C7 1.371(3) . ?
C7 C8 1.391(4) . ?
C8 C9 1.374(3) . ?
C9 C10 1.413(3) . ?
C12 C14 1.515(3) . ?
C12 C13 1.517(3) . ?

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
C4 N1 C11 120.18(15) . . ?
C4 N1 C2 118.29(15) . . ?
C11 N1 C2 121.25(14) . . ?
C11 N2 C10 117.44(16) . . ?
C11 N3 C12 121.89(17) . . ?
N1 C2 C3 112.13(17) . . ?
N1 C2 C1 110.95(16) . . ?
C3 C2 C1 113.91(19) . . ?
O1 C4 N1 120.61(17) . . ?
O1 C4 C5 124.00(17) . . ?
N1 C4 C5 115.38(17) . . ?
C10 C5 C6 121.37(19) . . ?
C10 C5 C4 119.10(17) . . ?
C6 C5 C4 119.48(19) . . ?
C7 C6 C5 118.7(2) . . ?
C6 C7 C8 121.1(2) . . ?
C6 C7 Cl1 119.5(2) . . ?
C8 C7 Cl1 119.42(18) . . ?
C9 C8 C7 120.2(2) . . ?
C8 C9 C10 120.2(2) . . ?
N2 C10 C5 122.81(17) . . ?
N2 C10 C9 118.7(2) . . ?
C5 C10 C9 118.36(19) . . ?
N2 C11 N3 119.34(17) . . ?
N2 C11 N1 124.42(16) . . ?
N3 C11 N1 116.24(16) . . ?
N3 C12 C14 106.94(18) . . ?
N3 C12 C13 112.76(19) . . ?
C14 C12 C13 112.1(2) . . ?

_refine_diff_density_max         0.312
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.039

####################################################################### 
# 
# 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_4a
_database_code_depnum_ccdc_archive 'CCDC 1880614'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C35 H47 N3 O3 Ti'
_chemical_formula_sum            'C35 H47 N3 O3 Ti'
_chemical_formula_weight         605.63

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   9.2296(5)
_cell_length_b                   11.5622(6)
_cell_length_c                   16.0686(7)
_cell_angle_alpha                98.137(4)
_cell_angle_beta                 93.568(4)
_cell_angle_gamma                99.629(4)
_cell_volume                     1667.08(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    7559
_cell_measurement_theta_min      3.9210
_cell_measurement_theta_max      71.0462

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_F_000             648
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.15
_exptl_absorpt_coefficient_mu    2.460
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.87063
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            13316
_diffrn_reflns_av_unetI/netI     0.0419
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.925
_diffrn_reflns_theta_max         71.213
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             6335
_reflns_number_gt                5706
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0589P)²+0.4997P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6335
_refine_ls_number_parameters     391
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0492
_refine_ls_R_factor_gt           0.0433
_refine_ls_wR_factor_ref         0.1205
_refine_ls_wR_factor_gt          0.1161
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.092
_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 0.17421(3) 0.87450(3) 0.24622(2) 0.02211(10) Uani 1 1 d . . . . .
O1 O 0.16096(16) 0.78731(13) 0.14210(9) 0.0347(3) Uani 1 1 d . . . . .
O2 O 0.30422(14) 1.01465(12) 0.24681(8) 0.0282(3) Uani 1 1 d . . . . .
O3 O 0.25536(14) 0.79045(12) 0.32132(8) 0.0288(3) Uani 1 1 d . . . . .
N1 N -0.00252(17) 0.90053(14) 0.27265(10) 0.0265(3) Uani 1 1 d . . . . .
N2 N -0.25461(17) 0.84436(14) 0.30459(10) 0.0260(3) Uani 1 1 d . . . . .
N3 N -0.19977(17) 1.00765(15) 0.24908(11) 0.0293(4) Uani 1 1 d . . . . .
C1 C -0.1406(2) 0.91657(17) 0.27550(12) 0.0252(4) Uani 1 1 d . . . . .
C2 C -0.3824(2) 0.89092(18) 0.29431(13) 0.0302(4) Uani 1 1 d . . . . .
H2 H -0.4752 0.8588 0.3085 0.036 Uiso 1 1 calc R U . . .
C3 C -0.3490(2) 0.98993(19) 0.26057(14) 0.0327(4) Uani 1 1 d . . . . .
H3 H -0.4146 1.0387 0.2471 0.039 Uiso 1 1 calc R U . . .
C4 C -0.2409(2) 0.73597(17) 0.34343(13) 0.0287(4) Uani 1 1 d . . . . .
C5 C -0.3916(2) 0.6850(2) 0.37080(14) 0.0367(5) Uani 1 1 d . . . . .
H5A H -0.4237 0.7439 0.4102 0.055 Uiso 1 1 calc R U . . .
H5B H -0.3835 0.6165 0.3971 0.055 Uiso 1 1 calc R U . . .
H5C H -0.4621 0.6625 0.3223 0.055 Uiso 1 1 calc R U . . .
C6 C -0.1956(3) 0.64381(19) 0.27711(15) 0.0378(5) Uani 1 1 d . . . . .
H6A H -0.2670 0.6264 0.2290 0.057 Uiso 1 1 calc R U . . .
H6B H -0.1905 0.5725 0.3005 0.057 Uiso 1 1 calc R U . . .
H6C H -0.1006 0.6745 0.2601 0.057 Uiso 1 1 calc R U . . .
C7 C -0.1296(2) 0.7712(2) 0.42067(13) 0.0343(5) Uani 1 1 d . . . . .
H7A H -0.0358 0.8053 0.4040 0.051 Uiso 1 1 calc R U . . .
H7B H -0.1197 0.7022 0.4459 0.051 Uiso 1 1 calc R U . . .
H7C H -0.1633 0.8284 0.4608 0.051 Uiso 1 1 calc R U . . .
C8 C -0.1164(2) 1.11336(19) 0.21782(15) 0.0354(5) Uani 1 1 d . . . . .
C9 C -0.2229(3) 1.1966(2) 0.1997(2) 0.0563(8) Uani 1 1 d . . . . .
H9A H -0.2968 1.1567 0.1556 0.085 Uiso 1 1 calc R U . . .
H9B H -0.1694 1.2663 0.1822 0.085 Uiso 1 1 calc R U . . .
H9C H -0.2694 1.2189 0.2498 0.085 Uiso 1 1 calc R U . . .
C10 C -0.0496(3) 1.0727(2) 0.13671(15) 0.0444(6) Uani 1 1 d . . . . .
H10A H 0.0158 1.0190 0.1475 0.067 Uiso 1 1 calc R U . . .
H10B H 0.0045 1.1403 0.1170 0.067 Uiso 1 1 calc R U . . .
H10C H -0.1270 1.0330 0.0945 0.067 Uiso 1 1 calc R U . . .
C11 C 0.0020(2) 1.1779(2) 0.28659(17) 0.0435(6) Uani 1 1 d . . . . .
H11A H -0.0438 1.2060 0.3357 0.065 Uiso 1 1 calc R U . . .
H11B H 0.0591 1.2441 0.2666 0.065 Uiso 1 1 calc R U . . .
H11C H 0.0654 1.1244 0.3008 0.065 Uiso 1 1 calc R U . . .
C12 C 0.1503(2) 0.71380(17) 0.06763(12) 0.0294(4) Uani 1 1 d . . . . .
C13 C 0.0176(2) 0.68939(18) 0.01636(13) 0.0328(4) Uani 1 1 d . . . . .
C14 C 0.0090(3) 0.61259(19) -0.05944(13) 0.0399(5) Uani 1 1 d . . . . .
H14 H -0.0782 0.5956 -0.0947 0.048 Uiso 1 1 calc R U . . .
C15 C 0.1277(3) 0.5612(2) -0.08321(14) 0.0436(6) Uani 1 1 d . . . . .
H15 H 0.1199 0.5094 -0.1338 0.052 Uiso 1 1 calc R U . . .
C16 C 0.2583(3) 0.5867(2) -0.03182(15) 0.0418(5) Uani 1 1 d . . . . .
H16 H 0.3378 0.5519 -0.0485 0.050 Uiso 1 1 calc R U . . .
C17 C 0.2731(2) 0.66360(18) 0.04456(13) 0.0344(5) Uani 1 1 d . . . . .
C18 C 0.4142(3) 0.6923(2) 0.10092(17) 0.0485(6) Uani 1 1 d . . . . .
H18A H 0.4828 0.6448 0.0784 0.073 Uiso 1 1 calc R U . . .
H18B H 0.3946 0.6757 0.1564 0.073 Uiso 1 1 calc R U . . .
H18C H 0.4556 0.7749 0.1040 0.073 Uiso 1 1 calc R U . . .
C19 C -0.1129(3) 0.7428(2) 0.04308(15) 0.0433(5) Uani 1 1 d . . . . .
H19A H -0.1275 0.7332 0.1005 0.065 Uiso 1 1 calc R U . . .
H19B H -0.1993 0.7036 0.0073 0.065 Uiso 1 1 calc R U . . .
H19C H -0.0953 0.8258 0.0386 0.065 Uiso 1 1 calc R U . . .
C20 C 0.35273(19) 1.12566(17) 0.23091(12) 0.0260(4) Uani 1 1 d . . . . .
C21 C 0.3902(2) 1.21909(18) 0.29838(13) 0.0304(4) Uani 1 1 d . . . . .
C22 C 0.4431(2) 1.33237(19) 0.28070(15) 0.0386(5) Uani 1 1 d . . . . .
H22 H 0.4676 1.3955 0.3248 0.046 Uiso 1 1 calc R U . . .
C23 C 0.4600(3) 1.3526(2) 0.19905(16) 0.0426(5) Uani 1 1 d . . . . .
H23 H 0.4946 1.4288 0.1883 0.051 Uiso 1 1 calc R U . . .
C24 C 0.4251(2) 1.2590(2) 0.13344(15) 0.0383(5) Uani 1 1 d . . . . .
H24 H 0.4374 1.2731 0.0785 0.046 Uiso 1 1 calc R U . . .
C25 C 0.3721(2) 1.14404(19) 0.14737(13) 0.0305(4) Uani 1 1 d . . . . .
C26 C 0.3406(3) 1.0418(2) 0.07628(14) 0.0396(5) Uani 1 1 d . . . . .
H26A H 0.3619 1.0700 0.0242 0.059 Uiso 1 1 calc R U . . .
H26B H 0.2385 1.0055 0.0729 0.059 Uiso 1 1 calc R U . . .
H26C H 0.4012 0.9844 0.0862 0.059 Uiso 1 1 calc R U . . .
C27 C 0.3737(3) 1.1965(2) 0.38739(14) 0.0408(5) Uani 1 1 d . . . . .
H27A H 0.2726 1.1641 0.3930 0.061 Uiso 1 1 calc R U . . .
H27B H 0.4027 1.2697 0.4255 0.061 Uiso 1 1 calc R U . . .
H27C H 0.4352 1.1411 0.4006 0.061 Uiso 1 1 calc R U . . .
C28 C 0.2355(2) 0.72309(18) 0.38374(12) 0.0271(4) Uani 1 1 d . . . . .
C29 C 0.2566(2) 0.7789(2) 0.46764(13) 0.0329(4) Uani 1 1 d . . . . .
C30 C 0.2417(3) 0.7077(3) 0.53077(15) 0.0467(6) Uani 1 1 d . . . . .
H30 H 0.2571 0.7430 0.5871 0.056 Uiso 1 1 calc R U . . .
C31 C 0.2047(3) 0.5857(3) 0.51124(18) 0.0560(7) Uani 1 1 d . . . . .
H31 H 0.1944 0.5395 0.5541 0.067 Uiso 1 1 calc R U . . .
C32 C 0.1828(3) 0.5326(2) 0.42817(18) 0.0495(6) Uani 1 1 d . . . . .
H32 H 0.1572 0.4504 0.4156 0.059 Uiso 1 1 calc R U . . .
C33 C 0.1983(2) 0.59944(19) 0.36239(14) 0.0343(5) Uani 1 1 d . . . . .
C34 C 0.1755(3) 0.5413(2) 0.27199(16) 0.0443(6) Uani 1 1 d . . . . .
H34A H 0.1105 0.5799 0.2411 0.067 Uiso 1 1 calc R U . . .
H34B H 0.1327 0.4590 0.2689 0.067 Uiso 1 1 calc R U . . .
H34C H 0.2687 0.5476 0.2480 0.067 Uiso 1 1 calc R U . . .
C35 C 0.2911(3) 0.9119(2) 0.48709(15) 0.0460(6) Uani 1 1 d . . . . .
H35A H 0.3797 0.9405 0.4624 0.069 Uiso 1 1 calc R U . . .
H35B H 0.3049 0.9361 0.5471 0.069 Uiso 1 1 calc R U . . .
H35C H 0.2109 0.9443 0.4642 0.069 Uiso 1 1 calc R U . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N1 1.7738(16) . ?
Ti1 O1 1.8128(14) . ?
Ti1 O2 1.8465(14) . ?
Ti1 O3 1.8505(13) . ?
O1 C12 1.354(2) . ?
O2 C20 1.352(2) . ?
O3 C28 1.357(2) . ?
N1 C1 1.321(2) . ?
N2 C1 1.379(2) . ?
N2 C2 1.386(2) . ?
N2 C4 1.497(2) . ?
N3 C1 1.370(2) . ?
N3 C3 1.386(2) . ?
N3 C8 1.498(3) . ?
C2 C3 1.333(3) . ?
C2 H2 0.9300 . ?
C3 H3 0.9300 . ?
C4 C7 1.523(3) . ?
C4 C6 1.526(3) . ?
C4 C5 1.533(3) . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C7 H7A 0.9600 . ?
C7 H7B 0.9600 . ?
C7 H7C 0.9600 . ?
C8 C11 1.522(3) . ?
C8 C10 1.525(3) . ?
C8 C9 1.528(3) . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 C13 1.397(3) . ?
C12 C17 1.404(3) . ?
C13 C14 1.392(3) . ?
C13 C19 1.502(3) . ?
C14 C15 1.381(3) . ?
C14 H14 0.9300 . ?
C15 C16 1.381(4) . ?
C15 H15 0.9300 . ?
C16 C17 1.395(3) . ?
C16 H16 0.9300 . ?
C17 C18 1.500(3) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 C21 1.400(3) . ?
C20 C25 1.406(3) . ?
C21 C22 1.394(3) . ?
C21 C27 1.502(3) . ?
C22 C23 1.378(3) . ?
C22 H22 0.9300 . ?
C23 C24 1.380(3) . ?
C23 H23 0.9300 . ?
C24 C25 1.392(3) . ?
C24 H24 0.9300 . ?
C25 C26 1.500(3) . ?
C26 H26A 0.9600 . ?
C26 H26B 0.9600 . ?
C26 H26C 0.9600 . ?
C27 H27A 0.9600 . ?
C27 H27B 0.9600 . ?
C27 H27C 0.9600 . ?
C28 C29 1.397(3) . ?
C28 C33 1.401(3) . ?
C29 C30 1.393(3) . ?
C29 C35 1.501(3) . ?
C30 C31 1.380(4) . ?
C30 H30 0.9300 . ?
C31 C32 1.376(4) . ?
C31 H31 0.9300 . ?
C32 C33 1.396(3) . ?
C32 H32 0.9300 . ?
C33 C34 1.498(3) . ?
C34 H34A 0.9600 . ?
C34 H34B 0.9600 . ?
C34 H34C 0.9600 . ?
C35 H35A 0.9600 . ?
C35 H35B 0.9600 . ?
C35 H35C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 O1 110.35(7) . . ?
N1 Ti1 O2 111.73(7) . . ?
O1 Ti1 O2 108.29(7) . . ?
N1 Ti1 O3 111.35(7) . . ?
O1 Ti1 O3 107.26(7) . . ?
O2 Ti1 O3 107.70(6) . . ?
C12 O1 Ti1 175.08(14) . . ?
C20 O2 Ti1 157.80(12) . . ?
C28 O3 Ti1 148.25(12) . . ?
C1 N1 Ti1 168.30(15) . . ?
C1 N2 C2 108.70(16) . . ?
C1 N2 C4 125.43(16) . . ?
C2 N2 C4 125.84(16) . . ?
C1 N3 C3 108.80(16) . . ?
C1 N3 C8 126.04(16) . . ?
C3 N3 C8 125.07(17) . . ?
N1 C1 N3 126.86(17) . . ?
N1 C1 N2 126.99(17) . . ?
N3 C1 N2 106.15(16) . . ?
C3 C2 N2 108.01(17) . . ?
C3 C2 H2 126.0 . . ?
N2 C2 H2 126.0 . . ?
C2 C3 N3 108.33(17) . . ?
C2 C3 H3 125.8 . . ?
N3 C3 H3 125.8 . . ?
N2 C4 C7 108.81(16) . . ?
N2 C4 C6 108.65(16) . . ?
C7 C4 C6 112.43(18) . . ?
N2 C4 C5 108.81(16) . . ?
C7 C4 C5 109.24(17) . . ?
C6 C4 C5 108.84(17) . . ?
C4 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C4 C6 H6A 109.5 . . ?
C4 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C4 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C4 C7 H7A 109.5 . . ?
C4 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
C4 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
N3 C8 C11 108.45(18) . . ?
N3 C8 C10 109.49(18) . . ?
C11 C8 C10 111.51(19) . . ?
N3 C8 C9 108.99(17) . . ?
C11 C8 C9 109.2(2) . . ?
C10 C8 C9 109.2(2) . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C8 C10 H10A 109.5 . . ?
C8 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C8 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C8 C11 H11A 109.5 . . ?
C8 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C8 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
O1 C12 C13 119.27(18) . . ?
O1 C12 C17 118.80(18) . . ?
C13 C12 C17 121.92(19) . . ?
C14 C13 C12 118.2(2) . . ?
C14 C13 C19 121.0(2) . . ?
C12 C13 C19 120.89(19) . . ?
C15 C14 C13 121.1(2) . . ?
C15 C14 H14 119.5 . . ?
C13 C14 H14 119.5 . . ?
C14 C15 C16 120.0(2) . . ?
C14 C15 H15 120.0 . . ?
C16 C15 H15 120.0 . . ?
C15 C16 C17 121.3(2) . . ?
C15 C16 H16 119.4 . . ?
C17 C16 H16 119.4 . . ?
C16 C17 C12 117.6(2) . . ?
C16 C17 C18 121.9(2) . . ?
C12 C17 C18 120.5(2) . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C13 C19 H19A 109.5 . . ?
C13 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C13 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
O2 C20 C21 119.32(18) . . ?
O2 C20 C25 119.40(18) . . ?
C21 C20 C25 121.19(18) . . ?
C22 C21 C20 118.4(2) . . ?
C22 C21 C27 121.4(2) . . ?
C20 C21 C27 120.24(19) . . ?
C23 C22 C21 121.2(2) . . ?
C23 C22 H22 119.4 . . ?
C21 C22 H22 119.4 . . ?
C22 C23 C24 119.6(2) . . ?
C22 C23 H23 120.2 . . ?
C24 C23 H23 120.2 . . ?
C23 C24 C25 121.6(2) . . ?
C23 C24 H24 119.2 . . ?
C25 C24 H24 119.2 . . ?
C24 C25 C20 117.9(2) . . ?
C24 C25 C26 121.4(2) . . ?
C20 C25 C26 120.63(19) . . ?
C25 C26 H26A 109.5 . . ?
C25 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
C25 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
C21 C27 H27A 109.5 . . ?
C21 C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
C21 C27 H27C 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
O3 C28 C29 119.02(18) . . ?
O3 C28 C33 119.16(18) . . ?
C29 C28 C33 121.80(19) . . ?
C30 C29 C28 118.1(2) . . ?
C30 C29 C35 122.2(2) . . ?
C28 C29 C35 119.70(19) . . ?
C31 C30 C29 121.1(2) . . ?
C31 C30 H30 119.4 . . ?
C29 C30 H30 119.4 . . ?
C32 C31 C30 119.9(2) . . ?
C32 C31 H31 120.1 . . ?
C30 C31 H31 120.1 . . ?
C31 C32 C33 121.4(2) . . ?
C31 C32 H32 119.3 . . ?
C33 C32 H32 119.3 . . ?
C32 C33 C28 117.7(2) . . ?
C32 C33 C34 121.3(2) . . ?
C28 C33 C34 121.01(19) . . ?
C33 C34 H34A 109.5 . . ?
C33 C34 H34B 109.5 . . ?
H34A C34 H34B 109.5 . . ?
C33 C34 H34C 109.5 . . ?
H34A C34 H34C 109.5 . . ?
H34B C34 H34C 109.5 . . ?
C29 C35 H35A 109.5 . . ?
C29 C35 H35B 109.5 . . ?
H35A C35 H35B 109.5 . . ?
C29 C35 H35C 109.5 . . ?
H35A C35 H35C 109.5 . . ?
H35B C35 H35C 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
N1 Ti1 O2 C20 -45.2(4) . . . . ?
O1 Ti1 O2 C20 76.5(3) . . . . ?
O3 Ti1 O2 C20 -167.8(3) . . . . ?
N1 Ti1 O3 C28 14.4(3) . . . . ?
O1 Ti1 O3 C28 -106.4(2) . . . . ?
O2 Ti1 O3 C28 137.2(2) . . . . ?
O1 Ti1 N1 C1 -24.3(7) . . . . ?
O2 Ti1 N1 C1 96.2(7) . . . . ?
O3 Ti1 N1 C1 -143.3(7) . . . . ?
Ti1 N1 C1 N3 -66.3(8) . . . . ?
Ti1 N1 C1 N2 112.8(7) . . . . ?
C3 N3 C1 N1 178.20(19) . . . . ?
C8 N3 C1 N1 -5.3(3) . . . . ?
C3 N3 C1 N2 -1.1(2) . . . . ?
C8 N3 C1 N2 175.47(18) . . . . ?
C2 N2 C1 N1 -178.24(19) . . . . ?
C4 N2 C1 N1 3.6(3) . . . . ?
C2 N2 C1 N3 1.0(2) . . . . ?
C4 N2 C1 N3 -177.13(17) . . . . ?
C1 N2 C2 C3 -0.6(2) . . . . ?
C4 N2 C2 C3 177.54(18) . . . . ?
N2 C2 C3 N3 -0.1(2) . . . . ?
C1 N3 C3 C2 0.7(2) . . . . ?
C8 N3 C3 C2 -175.85(19) . . . . ?
C1 N2 C4 C7 58.5(2) . . . . ?
C2 N2 C4 C7 -119.4(2) . . . . ?
C1 N2 C4 C6 -64.2(2) . . . . ?
C2 N2 C4 C6 117.9(2) . . . . ?
C1 N2 C4 C5 177.40(18) . . . . ?
C2 N2 C4 C5 -0.4(3) . . . . ?
C1 N3 C8 C11 -58.1(3) . . . . ?
C3 N3 C8 C11 117.9(2) . . . . ?
C1 N3 C8 C10 63.8(3) . . . . ?
C3 N3 C8 C10 -120.2(2) . . . . ?
C1 N3 C8 C9 -176.8(2) . . . . ?
C3 N3 C8 C9 -0.8(3) . . . . ?
O1 C12 C13 C14 -179.34(18) . . . . ?
C17 C12 C13 C14 0.2(3) . . . . ?
O1 C12 C13 C19 -0.4(3) . . . . ?
C17 C12 C13 C19 179.1(2) . . . . ?
C12 C13 C14 C15 0.4(3) . . . . ?
C19 C13 C14 C15 -178.5(2) . . . . ?
C13 C14 C15 C16 -0.7(3) . . . . ?
C14 C15 C16 C17 0.3(3) . . . . ?
C15 C16 C17 C12 0.3(3) . . . . ?
C15 C16 C17 C18 -179.9(2) . . . . ?
O1 C12 C17 C16 178.97(18) . . . . ?
C13 C12 C17 C16 -0.6(3) . . . . ?
O1 C12 C17 C18 -0.9(3) . . . . ?
C13 C12 C17 C18 179.6(2) . . . . ?
Ti1 O2 C20 C21 115.2(3) . . . . ?
Ti1 O2 C20 C25 -68.2(4) . . . . ?
O2 C20 C21 C22 178.57(17) . . . . ?
C25 C20 C21 C22 2.0(3) . . . . ?
O2 C20 C21 C27 -1.2(3) . . . . ?
C25 C20 C21 C27 -177.80(18) . . . . ?
C20 C21 C22 C23 -0.7(3) . . . . ?
C27 C21 C22 C23 179.2(2) . . . . ?
C21 C22 C23 C24 -0.6(3) . . . . ?
C22 C23 C24 C25 0.5(3) . . . . ?
C23 C24 C25 C20 0.8(3) . . . . ?
C23 C24 C25 C26 -177.3(2) . . . . ?
O2 C20 C25 C24 -178.66(17) . . . . ?
C21 C20 C25 C24 -2.1(3) . . . . ?
O2 C20 C25 C26 -0.5(3) . . . . ?
C21 C20 C25 C26 176.06(18) . . . . ?
Ti1 O3 C28 C29 -91.4(3) . . . . ?
Ti1 O3 C28 C33 90.3(3) . . . . ?
O3 C28 C29 C30 -177.34(18) . . . . ?
C33 C28 C29 C30 1.0(3) . . . . ?
O3 C28 C29 C35 3.8(3) . . . . ?
C33 C28 C29 C35 -177.87(19) . . . . ?
C28 C29 C30 C31 -1.2(3) . . . . ?
C35 C29 C30 C31 177.6(2) . . . . ?
C29 C30 C31 C32 0.5(4) . . . . ?
C30 C31 C32 C33 0.5(4) . . . . ?
C31 C32 C33 C28 -0.7(4) . . . . ?
C31 C32 C33 C34 179.6(2) . . . . ?
O3 C28 C33 C32 178.23(19) . . . . ?
C29 C28 C33 C32 -0.1(3) . . . . ?
O3 C28 C33 C34 -2.0(3) . . . . ?
C29 C28 C33 C34 179.71(19) . . . . ?

_refine_diff_density_max         0.254
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.061

####################################################################### 
# 
# 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_3a
_database_code_depnum_ccdc_archive 'CCDC 1880615'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H64 N8 Ti, C12 H19 N'
_chemical_formula_sum            'C48 H83 N9 Ti'
_chemical_formula_weight         834.10

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ti Ti 0.2776 0.4457 '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'
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'

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

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

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

_cell_length_a                   32.9866(10)
_cell_length_b                   10.4591(2)
_cell_length_c                   34.4041(10)
_cell_angle_alpha                90
_cell_angle_beta                 122.401(4)
_cell_angle_gamma                90
_cell_volume                     10021.9(6)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    11154
_cell_measurement_theta_min      3.0384
_cell_measurement_theta_max      71.5592

_exptl_crystal_description       needle
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.106
_exptl_crystal_F_000             3648
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    0.211
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.90125
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22209
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         1.402
_diffrn_reflns_theta_max         25.955
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             9540
_reflns_number_gt                8319
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0784P)²+7.7671P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         9540
_refine_ls_number_parameters     563
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0494
_refine_ls_wR_factor_ref         0.1429
_refine_ls_wR_factor_gt          0.1361
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_restrained_S_all      1.036
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.69052(2) 0.12471(3) 0.10220(2) 0.02798(10) Uani 1 1 d . . . . .
N1 N 0.65820(5) 0.25071(15) 0.11135(5) 0.0305(3) Uani 1 1 d . . . . .
N2 N 0.67936(6) 0.12949(14) 0.04397(5) 0.0301(3) Uani 1 1 d . . . . .
N3 N 0.76106(5) 0.15612(15) 0.14909(5) 0.0317(3) Uani 1 1 d . . . . .
H3 H 0.764438 0.196265 0.172470 0.038 Uiso 1 1 calc R U . . .
N4 N 0.66996(6) -0.03347(16) 0.11561(6) 0.0376(4) Uani 1 1 d . . . . .
N5 N 0.57924(6) 0.34083(17) 0.08298(6) 0.0368(4) Uani 1 1 d . . . . .
N6 N 0.64113(6) 0.43031(16) 0.14384(6) 0.0351(4) Uani 1 1 d . . . . .
N7 N 0.64399(5) 0.08515(15) -0.03641(5) 0.0310(3) Uani 1 1 d . . . . .
N8 N 0.67150(5) 0.28047(14) -0.01333(5) 0.0283(3) Uani 1 1 d . . . . .
N9 N 0.58198(7) 0.5440(2) 0.22499(6) 0.0509(5) Uani 1 1 d . . . . .
H9AA H 0.591197 0.622486 0.229837 0.061 Uiso 1 1 calc R U . . .
H9BB H 0.599242 0.486394 0.244944 0.061 Uiso 1 1 calc R U . . .
C1 C 0.62885(7) 0.33213(18) 0.11254(6) 0.0317(4) Uani 1 1 d . . . . .
C2 C 0.56295(8) 0.4436(2) 0.09621(8) 0.0470(5) Uani 1 1 d . . . . .
H2 H 0.531155 0.469961 0.081845 0.056 Uiso 1 1 calc R U . . .
C3 C 0.60023(8) 0.4985(2) 0.13286(8) 0.0459(5) Uani 1 1 d . . . . .
H3AA H 0.599086 0.569875 0.148357 0.055 Uiso 1 1 calc R U . . .
C4 C 0.54840(7) 0.2521(2) 0.04427(7) 0.0412(5) Uani 1 1 d . . . . .
C5 C 0.49595(8) 0.2938(3) 0.02120(9) 0.0554(6) Uani 1 1 d . . . . .
H5A H 0.486668 0.291305 0.043296 0.083 Uiso 1 1 calc R U . . .
H5B H 0.475889 0.236881 -0.003792 0.083 Uiso 1 1 calc R U . . .
H5C H 0.492390 0.379256 0.009630 0.083 Uiso 1 1 calc R U . . .
C6 C 0.55394(9) 0.1172(2) 0.06313(9) 0.0527(6) Uani 1 1 d . . . . .
H6A H 0.586775 0.090562 0.077497 0.079 Uiso 1 1 calc R U . . .
H6B H 0.533649 0.059911 0.038376 0.079 Uiso 1 1 calc R U . . .
H6C H 0.544882 0.116142 0.085395 0.079 Uiso 1 1 calc R U . . .
C7 C 0.56242(8) 0.2586(3) 0.00861(7) 0.0491(5) Uani 1 1 d . . . . .
H7A H 0.558792 0.344719 -0.002456 0.074 Uiso 1 1 calc R U . . .
H7B H 0.542034 0.202811 -0.016642 0.074 Uiso 1 1 calc R U . . .
H7C H 0.595248 0.232382 0.022518 0.074 Uiso 1 1 calc R U . . .
C8 C 0.69078(7) 0.4609(2) 0.18226(7) 0.0382(4) Uani 1 1 d . . . . .
C9 C 0.68908(9) 0.5715(2) 0.21071(8) 0.0521(6) Uani 1 1 d . . . . .
H9A H 0.675952 0.646078 0.191639 0.078 Uiso 1 1 calc R U . . .
H9B H 0.720972 0.589794 0.236106 0.078 Uiso 1 1 calc R U . . .
H9C H 0.669241 0.547857 0.222179 0.078 Uiso 1 1 calc R U . . .
C10 C 0.71956(7) 0.5021(2) 0.16148(8) 0.0423(5) Uani 1 1 d . . . . .
H10A H 0.720033 0.433838 0.143072 0.063 Uiso 1 1 calc R U . . .
H10B H 0.751837 0.522155 0.185729 0.063 Uiso 1 1 calc R U . . .
H10C H 0.704932 0.576253 0.142551 0.063 Uiso 1 1 calc R U . . .
C11 C 0.71283(8) 0.3440(2) 0.21342(7) 0.0452(5) Uani 1 1 d . . . . .
H11A H 0.693821 0.321058 0.225852 0.068 Uiso 1 1 calc R U . . .
H11B H 0.744932 0.363753 0.238117 0.068 Uiso 1 1 calc R U . . .
H11C H 0.713597 0.273809 0.195842 0.068 Uiso 1 1 calc R U . . .
C12 C 0.66670(6) 0.16240(17) 0.00249(6) 0.0283(4) Uani 1 1 d . . . . .
C13 C 0.63325(7) 0.1569(2) -0.07480(6) 0.0352(4) Uani 1 1 d . . . . .
H13 H 0.617190 0.127707 -0.105019 0.042 Uiso 1 1 calc R U . . .
C14 C 0.64999(7) 0.27505(19) -0.06073(6) 0.0333(4) Uani 1 1 d . . . . .
H14 H 0.647651 0.342342 -0.079503 0.040 Uiso 1 1 calc R U . . .
C15 C 0.69567(7) 0.39694(17) 0.01494(6) 0.0307(4) Uani 1 1 d . . . . .
C16 C 0.66575(8) 0.4517(2) 0.03251(7) 0.0410(5) Uani 1 1 d . . . . .
H16A H 0.634155 0.471536 0.006898 0.061 Uiso 1 1 calc R U . . .
H16B H 0.680693 0.528167 0.049796 0.061 Uiso 1 1 calc R U . . .
H16C H 0.663504 0.390096 0.051957 0.061 Uiso 1 1 calc R U . . .
C17 C 0.74635(7) 0.3614(2) 0.05432(7) 0.0427(5) Uani 1 1 d . . . . .
H17A H 0.744498 0.295991 0.072879 0.064 Uiso 1 1 calc R U . . .
H17B H 0.761860 0.435546 0.072921 0.064 Uiso 1 1 calc R U . . .
H17C H 0.764487 0.330426 0.041859 0.064 Uiso 1 1 calc R U . . .
C18 C 0.69980(8) 0.49634(19) -0.01516(7) 0.0398(4) Uani 1 1 d . . . . .
H18A H 0.717025 0.460450 -0.027884 0.060 Uiso 1 1 calc R U . . .
H18B H 0.716726 0.569827 0.003116 0.060 Uiso 1 1 calc R U . . .
H18C H 0.668269 0.521346 -0.039677 0.060 Uiso 1 1 calc R U . . .
C19 C 0.63249(7) -0.05281(19) -0.03717(7) 0.0363(4) Uani 1 1 d . . . . .
C20 C 0.67813(8) -0.12429(19) -0.00336(8) 0.0423(5) Uani 1 1 d . . . . .
H20A H 0.700101 -0.120594 -0.013539 0.063 Uiso 1 1 calc R U . . .
H20B H 0.670546 -0.211908 -0.001645 0.063 Uiso 1 1 calc R U . . .
H20C H 0.692616 -0.085601 0.026506 0.063 Uiso 1 1 calc R U . . .
C21 C 0.59378(8) -0.0656(2) -0.02612(9) 0.0470(5) Uani 1 1 d . . . . .
H21A H 0.604535 -0.025965 0.003023 0.070 Uiso 1 1 calc R U . . .
H21B H 0.587426 -0.154470 -0.024696 0.070 Uiso 1 1 calc R U . . .
H21C H 0.564951 -0.024382 -0.049706 0.070 Uiso 1 1 calc R U . . .
C22 C 0.61372(10) -0.1062(2) -0.08544(8) 0.0556(6) Uani 1 1 d . . . . .
H22A H 0.584554 -0.063016 -0.107387 0.083 Uiso 1 1 calc R U . . .
H22B H 0.607545 -0.196070 -0.085893 0.083 Uiso 1 1 calc R U . . .
H22C H 0.637325 -0.092995 -0.093247 0.083 Uiso 1 1 calc R U . . .
C23 C 0.80579(7) 0.13328(18) 0.15544(6) 0.0309(4) Uani 1 1 d . . . . .
C24 C 0.81701(7) 0.01105(18) 0.14508(6) 0.0334(4) Uani 1 1 d . . . . .
C25 C 0.86189(7) -0.0089(2) 0.15148(7) 0.0378(4) Uani 1 1 d . . . . .
H25 H 0.868762 -0.088586 0.144369 0.045 Uiso 1 1 calc R U . . .
C26 C 0.89668(7) 0.0854(2) 0.16805(7) 0.0390(4) Uani 1 1 d . . . . .
H26 H 0.926451 0.069640 0.172073 0.047 Uiso 1 1 calc R U . . .
C27 C 0.88614(7) 0.2041(2) 0.17852(6) 0.0358(4) Uani 1 1 d . . . . .
H27 H 0.909354 0.268011 0.189768 0.043 Uiso 1 1 calc R U . . .
C28 C 0.84186(7) 0.23028(18) 0.17268(6) 0.0320(4) Uani 1 1 d . . . . .
C29 C 0.83229(7) 0.36046(18) 0.18584(6) 0.0340(4) Uani 1 1 d . . . . .
H29 H 0.798056 0.378651 0.164687 0.041 Uiso 1 1 calc R U . . .
C30 C 0.84173(8) 0.3576(2) 0.23467(7) 0.0437(5) Uani 1 1 d . . . . .
H30A H 0.823682 0.289297 0.236965 0.066 Uiso 1 1 calc R U . . .
H30B H 0.832059 0.437511 0.240979 0.066 Uiso 1 1 calc R U . . .
H30C H 0.875347 0.344233 0.256573 0.066 Uiso 1 1 calc R U . . .
C31 C 0.85990(9) 0.4704(2) 0.18167(9) 0.0502(5) Uani 1 1 d . . . . .
H31A H 0.893597 0.459615 0.203851 0.075 Uiso 1 1 calc R U . . .
H31B H 0.849277 0.549739 0.187278 0.075 Uiso 1 1 calc R U . . .
H31C H 0.854252 0.471161 0.151241 0.075 Uiso 1 1 calc R U . . .
C32 C 0.78169(8) -0.09822(19) 0.13144(7) 0.0376(4) Uani 1 1 d . . . . .
H32 H 0.749405 -0.063377 0.110846 0.045 Uiso 1 1 calc R U . . .
C33 C 0.78421(9) -0.1484(2) 0.17465(8) 0.0469(5) Uani 1 1 d . . . . .
H33A H 0.815091 -0.186338 0.195008 0.070 Uiso 1 1 calc R U . . .
H33B H 0.759595 -0.211319 0.165915 0.070 Uiso 1 1 calc R U . . .
H33C H 0.779504 -0.078757 0.190018 0.070 Uiso 1 1 calc R U . . .
C34 C 0.78849(9) -0.2075(2) 0.10607(8) 0.0480(5) Uani 1 1 d . . . . .
H34A H 0.788493 -0.174035 0.080086 0.072 Uiso 1 1 calc R U . . .
H34B H 0.762720 -0.267729 0.095649 0.072 Uiso 1 1 calc R U . . .
H34C H 0.818519 -0.249388 0.126507 0.072 Uiso 1 1 calc R U . . .
C35 C 0.66799(10) -0.0334(3) 0.15723(8) 0.0539(6) Uani 1 1 d . . . . .
H35A H 0.635418 -0.045651 0.148820 0.081 Uiso 1 1 calc R U . . .
H35B H 0.679642 0.046971 0.172857 0.081 Uiso 1 1 calc R U . . .
H35C H 0.687631 -0.101395 0.177233 0.081 Uiso 1 1 calc R U . . .
C36 C 0.65220(10) -0.1538(2) 0.09232(9) 0.0566(6) Uani 1 1 d . . . . .
H36A H 0.670184 -0.222288 0.113110 0.085 Uiso 1 1 calc R U . . .
H36B H 0.655648 -0.157032 0.066345 0.085 Uiso 1 1 calc R U . . .
H36C H 0.618909 -0.162515 0.081952 0.085 Uiso 1 1 calc R U . . .
C37 C 0.53888(7) 0.5100(2) 0.18460(7) 0.0402(5) Uani 1 1 d . . . . .
C38 C 0.51093(7) 0.6040(2) 0.15225(7) 0.0380(4) Uani 1 1 d . . . . .
C39 C 0.46912(7) 0.5679(2) 0.11152(7) 0.0421(5) Uani 1 1 d . . . . .
H39 H 0.450140 0.630083 0.090075 0.051 Uiso 1 1 calc R U . . .
C40 C 0.45529(8) 0.4406(2) 0.10235(8) 0.0490(5) Uani 1 1 d . . . . .
H40 H 0.427155 0.417352 0.075169 0.059 Uiso 1 1 calc R U . . .
C41 C 0.48404(9) 0.3492(2) 0.13430(9) 0.0557(6) Uani 1 1 d . . . . .
H41 H 0.475174 0.263667 0.128070 0.067 Uiso 1 1 calc R U . . .
C42 C 0.52565(9) 0.3813(2) 0.17533(8) 0.0512(6) Uani 1 1 d . . . . .
C43 C 0.55829(13) 0.2791(3) 0.21023(10) 0.0781(9) Uani 1 1 d . . . . .
H43 H 0.537641 0.208732 0.191028 0.094 Uiso 1 1 calc R U . A 1
C44A C 0.5956(3) 0.2422(10) 0.2056(3) 0.066(3) Uani 0.454(17) 1 d . . P B 1
H44A H 0.590559 0.275698 0.177333 0.099 Uiso 0.454(17) 1 calc R U P B 1
H44B H 0.625311 0.274634 0.231031 0.099 Uiso 0.454(17) 1 calc R U P B 1
H44C H 0.596989 0.150560 0.205172 0.099 Uiso 0.454(17) 1 calc R U P B 1
C44B C 0.5731(5) 0.1742(12) 0.1879(4) 0.101(4) Uani 0.546(17) 1 d . . P B 2
H44D H 0.593376 0.112503 0.210847 0.152 Uiso 0.546(17) 1 calc R U P B 2
H44E H 0.544798 0.132486 0.163688 0.152 Uiso 0.546(17) 1 calc R U P B 2
H44F H 0.590089 0.213081 0.175479 0.152 Uiso 0.546(17) 1 calc R U P B 2
C45 C 0.52649(8) 0.7426(2) 0.16288(8) 0.0464(5) Uani 1 1 d . . . . .
H45 H 0.561654 0.743610 0.181948 0.056 Uiso 1 1 calc R U . . .
C46 C 0.51143(12) 0.8224(3) 0.12050(10) 0.0686(8) Uani 1 1 d . . . . .
H46A H 0.522535 0.782512 0.102736 0.103 Uiso 1 1 calc R U . . .
H46B H 0.525155 0.906293 0.129690 0.103 Uiso 1 1 calc R U . . .
H46C H 0.477060 0.828956 0.102215 0.103 Uiso 1 1 calc R U . . .
C47 C 0.50819(10) 0.8021(3) 0.19135(10) 0.0622(7) Uani 1 1 d . . . . .
H47A H 0.473889 0.810362 0.172604 0.093 Uiso 1 1 calc R U . . .
H47B H 0.522378 0.885021 0.202024 0.093 Uiso 1 1 calc R U . . .
H47C H 0.516832 0.748277 0.217284 0.093 Uiso 1 1 calc R U . . .
C48A C 0.5505(4) 0.2549(9) 0.2436(3) 0.104(4) Uani 0.473(8) 1 d . . P B 1
H48A H 0.521034 0.294776 0.236379 0.156 Uiso 0.473(8) 1 calc R U P B 1
H48B H 0.548236 0.164247 0.246263 0.156 Uiso 0.473(8) 1 calc R U P B 1
H48C H 0.576558 0.288321 0.272122 0.156 Uiso 0.473(8) 1 calc R U P B 1
C48B C 0.5220(3) 0.1526(7) 0.2029(3) 0.117(4) Uani 0.527(8) 1 d . . P B 2
H48D H 0.540934 0.085846 0.224148 0.175 Uiso 0.527(8) 1 calc R U P B 2
H48E H 0.497833 0.179796 0.208572 0.175 Uiso 0.527(8) 1 calc R U P B 2
H48F H 0.506978 0.121206 0.171988 0.175 Uiso 0.527(8) 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 N1 1.8252(16) . ?
Ti1 N2 1.8334(15) . ?
Ti1 N4 1.9353(17) . ?
Ti1 N3 2.0253(16) . ?
N1 C1 1.307(2) . ?
N2 C12 1.300(2) . ?
N3 C23 1.391(2) . ?
N4 C36 1.438(3) . ?
N4 C35 1.468(3) . ?
N5 C2 1.383(3) . ?
N5 C1 1.392(2) . ?
N5 C4 1.489(3) . ?
N6 C1 1.382(2) . ?
N6 C3 1.388(3) . ?
N6 C8 1.487(2) . ?
N7 C12 1.390(2) . ?
N7 C13 1.390(2) . ?
N7 C19 1.489(2) . ?
N8 C14 1.388(2) . ?
N8 C12 1.392(2) . ?
N8 C15 1.495(2) . ?
N9 C37 1.401(3) . ?
C2 C3 1.331(3) . ?
C4 C6 1.522(3) . ?
C4 C7 1.527(3) . ?
C4 C5 1.530(3) . ?
C8 C10 1.525(3) . ?
C8 C11 1.529(3) . ?
C8 C9 1.536(3) . ?
C13 C14 1.334(3) . ?
C15 C16 1.519(3) . ?
C15 C18 1.524(3) . ?
C15 C17 1.530(3) . ?
C19 C20 1.517(3) . ?
C19 C21 1.521(3) . ?
C19 C22 1.533(3) . ?
C23 C28 1.428(3) . ?
C23 C24 1.428(3) . ?
C24 C25 1.391(3) . ?
C24 C32 1.516(3) . ?
C25 C26 1.384(3) . ?
C26 C27 1.388(3) . ?
C27 C28 1.391(3) . ?
C28 C29 1.520(3) . ?
C29 C31 1.520(3) . ?
C29 C30 1.536(3) . ?
C32 C34 1.526(3) . ?
C32 C33 1.536(3) . ?
C37 C38 1.398(3) . ?
C37 C42 1.399(3) . ?
C38 C39 1.392(3) . ?
C38 C45 1.516(3) . ?
C39 C40 1.387(3) . ?
C40 C41 1.380(3) . ?
C41 C42 1.383(3) . ?
C42 C43 1.535(4) . ?
C43 C48A 1.327(8) . ?
C43 C44A 1.379(8) . ?
C43 C44B 1.559(10) . ?
C43 C48B 1.709(7) . ?
C45 C46 1.514(3) . ?
C45 C47 1.531(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 N2 112.01(7) . . ?
N1 Ti1 N4 105.34(7) . . ?
N2 Ti1 N4 113.13(7) . . ?
N1 Ti1 N3 105.87(7) . . ?
N2 Ti1 N3 109.77(7) . . ?
N4 Ti1 N3 110.41(7) . . ?
C1 N1 Ti1 170.80(14) . . ?
C12 N2 Ti1 164.77(14) . . ?
C23 N3 Ti1 140.01(12) . . ?
C36 N4 C35 109.06(18) . . ?
C36 N4 Ti1 134.90(15) . . ?
C35 N4 Ti1 115.87(14) . . ?
C2 N5 C1 108.80(17) . . ?
C2 N5 C4 125.36(17) . . ?
C1 N5 C4 125.81(16) . . ?
C1 N6 C3 109.47(16) . . ?
C1 N6 C8 125.16(15) . . ?
C3 N6 C8 125.33(17) . . ?
C12 N7 C13 109.41(15) . . ?
C12 N7 C19 125.54(15) . . ?
C13 N7 C19 125.04(16) . . ?
C14 N8 C12 109.23(15) . . ?
C14 N8 C15 123.81(15) . . ?
C12 N8 C15 126.96(14) . . ?
N1 C1 N6 126.58(17) . . ?
N1 C1 N5 128.36(17) . . ?
N6 C1 N5 105.06(15) . . ?
C3 C2 N5 108.81(19) . . ?
C2 C3 N6 107.84(19) . . ?
N5 C4 C6 109.14(18) . . ?
N5 C4 C7 109.57(17) . . ?
C6 C4 C7 111.4(2) . . ?
N5 C4 C5 109.10(18) . . ?
C6 C4 C5 109.21(19) . . ?
C7 C4 C5 108.40(19) . . ?
N6 C8 C10 108.03(16) . . ?
N6 C8 C11 109.56(17) . . ?
C10 C8 C11 111.89(17) . . ?
N6 C8 C9 109.25(16) . . ?
C10 C8 C9 109.30(18) . . ?
C11 C8 C9 108.78(18) . . ?
N2 C12 N7 126.41(17) . . ?
N2 C12 N8 128.82(16) . . ?
N7 C12 N8 104.76(15) . . ?
C14 C13 N7 108.09(16) . . ?
C13 C14 N8 108.40(17) . . ?
N8 C15 C16 109.43(15) . . ?
N8 C15 C18 108.94(15) . . ?
C16 C15 C18 109.09(16) . . ?
N8 C15 C17 109.08(15) . . ?
C16 C15 C17 111.95(17) . . ?
C18 C15 C17 108.30(16) . . ?
N7 C19 C20 108.98(16) . . ?
N7 C19 C21 108.72(16) . . ?
C20 C19 C21 112.71(18) . . ?
N7 C19 C22 108.86(17) . . ?
C20 C19 C22 108.05(18) . . ?
C21 C19 C22 109.45(19) . . ?
N3 C23 C28 121.37(17) . . ?
N3 C23 C24 120.62(17) . . ?
C28 C23 C24 118.01(17) . . ?
C25 C24 C23 119.42(18) . . ?
C25 C24 C32 120.80(18) . . ?
C23 C24 C32 119.55(17) . . ?
C26 C25 C24 122.39(19) . . ?
C25 C26 C27 118.49(19) . . ?
C26 C27 C28 121.88(19) . . ?
C27 C28 C23 119.81(18) . . ?
C27 C28 C29 120.17(18) . . ?
C23 C28 C29 120.00(16) . . ?
C28 C29 C31 114.75(17) . . ?
C28 C29 C30 110.82(16) . . ?
C31 C29 C30 109.71(17) . . ?
C24 C32 C34 114.69(18) . . ?
C24 C32 C33 108.89(17) . . ?
C34 C32 C33 110.46(18) . . ?
C38 C37 C42 120.2(2) . . ?
C38 C37 N9 119.8(2) . . ?
C42 C37 N9 119.8(2) . . ?
C39 C38 C37 119.0(2) . . ?
C39 C38 C45 121.8(2) . . ?
C37 C38 C45 119.12(19) . . ?
C40 C39 C38 121.1(2) . . ?
C41 C40 C39 118.8(2) . . ?
C40 C41 C42 121.9(2) . . ?
C41 C42 C37 118.9(2) . . ?
C41 C42 C43 121.8(2) . . ?
C37 C42 C43 119.3(2) . . ?
C48A C43 C44A 130.2(5) . . ?
C48A C43 C42 115.4(4) . . ?
C44A C43 C42 113.6(4) . . ?
C42 C43 C44B 112.2(3) . . ?
C42 C43 C48B 106.3(3) . . ?
C44B C43 C48B 76.2(7) . . ?
C46 C45 C38 113.6(2) . . ?
C46 C45 C47 110.7(2) . . ?
C38 C45 C47 110.2(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
N1 Ti1 N2 C12 13.0(6) . . . . ?
N4 Ti1 N2 C12 131.9(5) . . . . ?
N3 Ti1 N2 C12 -104.3(5) . . . . ?
C3 N6 C1 N1 177.9(2) . . . . ?
C8 N6 C1 N1 0.0(3) . . . . ?
C3 N6 C1 N5 -1.4(2) . . . . ?
C8 N6 C1 N5 -179.31(18) . . . . ?
C2 N5 C1 N1 -178.2(2) . . . . ?
C4 N5 C1 N1 3.4(3) . . . . ?
C2 N5 C1 N6 1.1(2) . . . . ?
C4 N5 C1 N6 -177.26(18) . . . . ?
C1 N5 C2 C3 -0.4(3) . . . . ?
C4 N5 C2 C3 178.0(2) . . . . ?
N5 C2 C3 N6 -0.5(3) . . . . ?
C1 N6 C3 C2 1.2(3) . . . . ?
C8 N6 C3 C2 179.1(2) . . . . ?
C2 N5 C4 C6 -118.6(2) . . . . ?
C1 N5 C4 C6 59.4(3) . . . . ?
C2 N5 C4 C7 119.1(2) . . . . ?
C1 N5 C4 C7 -62.8(3) . . . . ?
C2 N5 C4 C5 0.6(3) . . . . ?
C1 N5 C4 C5 178.71(19) . . . . ?
C1 N6 C8 C10 64.3(2) . . . . ?
C3 N6 C8 C10 -113.3(2) . . . . ?
C1 N6 C8 C11 -57.8(2) . . . . ?
C3 N6 C8 C11 124.6(2) . . . . ?
C1 N6 C8 C9 -176.90(19) . . . . ?
C3 N6 C8 C9 5.5(3) . . . . ?
Ti1 N2 C12 N7 -136.3(5) . . . . ?
Ti1 N2 C12 N8 42.1(6) . . . . ?
C13 N7 C12 N2 175.71(18) . . . . ?
C19 N7 C12 N2 -3.8(3) . . . . ?
C13 N7 C12 N8 -3.05(19) . . . . ?
C19 N7 C12 N8 177.42(16) . . . . ?
C14 N8 C12 N2 -175.76(18) . . . . ?
C15 N8 C12 N2 4.3(3) . . . . ?
C14 N8 C12 N7 2.96(19) . . . . ?
C15 N8 C12 N7 -177.01(15) . . . . ?
C12 N7 C13 C14 2.0(2) . . . . ?
C19 N7 C13 C14 -178.42(17) . . . . ?
N7 C13 C14 N8 -0.1(2) . . . . ?
C12 N8 C14 C13 -1.8(2) . . . . ?
C15 N8 C14 C13 178.16(16) . . . . ?
C14 N8 C15 C16 109.84(19) . . . . ?
C12 N8 C15 C16 -70.2(2) . . . . ?
C14 N8 C15 C18 -9.3(2) . . . . ?
C12 N8 C15 C18 170.62(16) . . . . ?
C14 N8 C15 C17 -127.38(18) . . . . ?
C12 N8 C15 C17 52.6(2) . . . . ?
C12 N7 C19 C20 -54.9(2) . . . . ?
C13 N7 C19 C20 125.63(19) . . . . ?
C12 N7 C19 C21 68.3(2) . . . . ?
C13 N7 C19 C21 -111.2(2) . . . . ?
C12 N7 C19 C22 -172.54(19) . . . . ?
C13 N7 C19 C22 8.0(3) . . . . ?
Ti1 N3 C23 C28 135.74(18) . . . . ?
Ti1 N3 C23 C24 -44.7(3) . . . . ?
N3 C23 C24 C25 179.61(16) . . . . ?
C28 C23 C24 C25 -0.8(3) . . . . ?
N3 C23 C24 C32 -5.9(3) . . . . ?
C28 C23 C24 C32 173.73(16) . . . . ?
C23 C24 C25 C26 0.6(3) . . . . ?
C32 C24 C25 C26 -173.84(18) . . . . ?
C24 C25 C26 C27 -0.1(3) . . . . ?
C25 C26 C27 C28 -0.2(3) . . . . ?
C26 C27 C28 C23 0.0(3) . . . . ?
C26 C27 C28 C29 178.29(17) . . . . ?
N3 C23 C28 C27 -179.90(16) . . . . ?
C24 C23 C28 C27 0.5(3) . . . . ?
N3 C23 C28 C29 1.8(3) . . . . ?
C24 C23 C28 C29 -177.81(16) . . . . ?
C27 C28 C29 C31 29.4(2) . . . . ?
C23 C28 C29 C31 -152.30(18) . . . . ?
C27 C28 C29 C30 -95.5(2) . . . . ?
C23 C28 C29 C30 82.8(2) . . . . ?
C25 C24 C32 C34 -25.2(3) . . . . ?
C23 C24 C32 C34 160.35(17) . . . . ?
C25 C24 C32 C33 99.1(2) . . . . ?
C23 C24 C32 C33 -75.3(2) . . . . ?
C42 C37 C38 C39 2.0(3) . . . . ?
N9 C37 C38 C39 177.59(19) . . . . ?
C42 C37 C38 C45 -179.1(2) . . . . ?
N9 C37 C38 C45 -3.5(3) . . . . ?
C37 C38 C39 C40 -1.0(3) . . . . ?
C45 C38 C39 C40 -179.8(2) . . . . ?
C38 C39 C40 C41 -0.6(3) . . . . ?
C39 C40 C41 C42 1.1(4) . . . . ?
C40 C41 C42 C37 0.0(4) . . . . ?
C40 C41 C42 C43 -178.3(3) . . . . ?
C38 C37 C42 C41 -1.6(4) . . . . ?
N9 C37 C42 C41 -177.1(2) . . . . ?
C38 C37 C42 C43 176.8(2) . . . . ?
N9 C37 C42 C43 1.2(4) . . . . ?
C41 C42 C43 C48A -94.8(6) . . . . ?
C37 C42 C43 C48A 86.9(6) . . . . ?
C41 C42 C43 C44A 94.6(7) . . . . ?
C37 C42 C43 C44A -83.7(6) . . . . ?
C41 C42 C43 C44B 53.3(8) . . . . ?
C37 C42 C43 C44B -125.0(7) . . . . ?
C41 C42 C43 C48B -28.2(5) . . . . ?
C37 C42 C43 C48B 153.5(4) . . . . ?
C39 C38 C45 C46 -30.9(3) . . . . ?
C37 C38 C45 C46 150.3(2) . . . . ?
C39 C38 C45 C47 94.0(3) . . . . ?
C37 C38 C45 C47 -84.9(2) . . . . ?

_refine_diff_density_max         0.365
_refine_diff_density_min         -0.537
_refine_diff_density_rms         0.053

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

data_7
_database_code_depnum_ccdc_archive 'CCDC 1880613'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C60 H70 N10 S2 Ti'
_chemical_formula_sum            'C60 H70 N10 S2 Ti'
_chemical_formula_weight         1043.25

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   11.9485(5)
_cell_length_b                   12.6031(6)
_cell_length_c                   21.2454(8)
_cell_angle_alpha                92.364(4)
_cell_angle_beta                 97.250(3)
_cell_angle_gamma                118.055(5)
_cell_volume                     2782.2(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9522
_cell_measurement_theta_min      3.9983
_cell_measurement_theta_max      71.4745

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.245
_exptl_crystal_F_000             1108
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_exptl_absorpt_coefficient_mu    2.373
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.77592
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11). Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18429
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         4.001
_diffrn_reflns_theta_max         71.631
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             10617
_reflns_number_gt                9146
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0717P)²+0.5039P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         10617
_refine_ls_number_parameters     674
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0460
_refine_ls_wR_factor_ref         0.1294
_refine_ls_wR_factor_gt          0.1228
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.033
_refine_ls_shift/su_max          0.013
_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 0.32820(3) 0.75383(3) 0.24420(2) 0.02188(9) Uani 1 1 d . . . . .
S1 S 0.43664(5) 0.83118(5) 0.35686(2) 0.03387(13) Uani 1 1 d . . . . .
S2 S 0.15731(4) 0.70645(4) 0.14909(2) 0.02751(11) Uani 1 1 d . . . . .
N1 N 0.47957(15) 0.85518(14) 0.21541(8) 0.0264(3) Uani 1 1 d . . . . .
N2 N 0.59551(17) 1.01672(16) 0.15401(9) 0.0341(4) Uani 1 1 d . . . . .
N3 N 0.71018(16) 0.97658(17) 0.22848(9) 0.0370(4) Uani 1 1 d . . . . .
N4 N 0.31195(15) 0.60161(14) 0.23268(7) 0.0254(3) Uani 1 1 d . . . . .
N5 N 0.25626(19) 0.41957(15) 0.16608(8) 0.0336(4) Uani 1 1 d . . . . .
N6 N 0.28414(18) 0.41427(15) 0.26956(8) 0.0311(4) Uani 1 1 d . . . . .
N7 N 0.19425(16) 0.70250(15) 0.31929(8) 0.0294(3) Uani 1 1 d . . . . .
N8 N 0.2540(2) 0.78273(19) 0.42967(9) 0.0429(5) Uani 1 1 d . . . . .
N9 N 0.25235(15) 0.88728(14) 0.23527(8) 0.0265(3) Uani 1 1 d . . . . .
N10 N 0.08785(17) 0.88110(15) 0.15558(8) 0.0324(4) Uani 1 1 d . . . . .
C1 C 0.58283(19) 0.93989(18) 0.20157(9) 0.0279(4) Uani 1 1 d . . . . .
C2 C 0.7247(2) 1.0949(2) 0.15296(12) 0.0450(6) Uani 1 1 d . . . . .
H2 H 0.756574 1.153794 0.125407 0.054 Uiso 1 1 calc R U . . .
C3 C 0.7948(2) 1.0711(2) 0.19804(12) 0.0476(6) Uani 1 1 d . . . . .
H3 H 0.884054 1.110341 0.207618 0.057 Uiso 1 1 calc R U . . .
C4 C 0.28627(19) 0.49132(17) 0.22360(9) 0.0262(4) Uani 1 1 d . . . . .
C5 C 0.2393(3) 0.3052(2) 0.17718(11) 0.0474(6) Uani 1 1 d . . . . .
H5 H 0.218966 0.241940 0.146121 0.057 Uiso 1 1 calc R U . . .
C6 C 0.2574(3) 0.3025(2) 0.24040(11) 0.0457(6) Uani 1 1 d . . . . .
H6 H 0.252773 0.237304 0.261103 0.055 Uiso 1 1 calc R U . . .
C7 C 0.2795(2) 0.76436(19) 0.37052(10) 0.0323(4) Uani 1 1 d . . . . .
C8 C 0.1397(3) 0.7913(3) 0.43828(13) 0.0508(6) Uani 1 1 d . . . . .
H8A H 0.088199 0.778807 0.397382 0.076 Uiso 1 1 calc R U . . .
H8B H 0.164573 0.870047 0.459033 0.076 Uiso 1 1 calc R U . . .
H8C H 0.090933 0.730660 0.464121 0.076 Uiso 1 1 calc R U . . .
C9 C 0.3571(3) 0.8372(3) 0.48423(13) 0.0629(8) Uani 1 1 d . . . . .
H9A H 0.424449 0.818781 0.477717 0.094 Uiso 1 1 calc R U . . .
H9B H 0.324429 0.805421 0.522178 0.094 Uiso 1 1 calc R U . . .
H9C H 0.390547 0.923350 0.488861 0.094 Uiso 1 1 calc R U . . .
C10 C 0.16557(19) 0.83824(17) 0.18303(9) 0.0271(4) Uani 1 1 d . . . . .
C11 C -0.0092(2) 0.8119(2) 0.10005(11) 0.0414(5) Uani 1 1 d . . . . .
H11A H 0.030445 0.825005 0.062481 0.062 Uiso 1 1 calc R U . . .
H11B H -0.073428 0.837673 0.095575 0.062 Uiso 1 1 calc R U . . .
H11C H -0.048731 0.727376 0.105441 0.062 Uiso 1 1 calc R U . . .
C12 C 0.1236(2) 1.0091(2) 0.16436(11) 0.0400(5) Uani 1 1 d . . . . .
H12A H 0.071865 1.020853 0.192037 0.060 Uiso 1 1 calc R U . . .
H12B H 0.109908 1.035376 0.123710 0.060 Uiso 1 1 calc R U . . .
H12C H 0.212729 1.055272 0.183109 0.060 Uiso 1 1 calc R U . . .
C13 C 0.4937(2) 1.02812(19) 0.11693(10) 0.0321(4) Uani 1 1 d . . . . .
C14 C 0.4103(2) 0.9378(2) 0.06798(10) 0.0348(5) Uani 1 1 d . . . . .
C15 C 0.3197(2) 0.9583(3) 0.03036(12) 0.0480(6) Uani 1 1 d . . . . .
H15 H 0.260806 0.898179 -0.001575 0.058 Uiso 1 1 calc R U . . .
C16 C 0.3145(3) 1.0657(3) 0.03899(14) 0.0554(7) Uani 1 1 d . . . . .
C17 C 0.3980(3) 1.1518(3) 0.08849(13) 0.0509(7) Uani 1 1 d . . . . .
H17 H 0.394837 1.223760 0.094679 0.061 Uiso 1 1 calc R U . . .
C18 C 0.4863(2) 1.1343(2) 0.12925(11) 0.0410(5) Uani 1 1 d . . . . .
C19 C 0.5697(3) 1.2271(2) 0.18534(13) 0.0591(8) Uani 1 1 d . . . . .
H19A H 0.575395 1.186808 0.222013 0.089 Uiso 1 1 calc R U . . .
H19B H 0.532595 1.277930 0.194369 0.089 Uiso 1 1 calc R U . . .
H19C H 0.654120 1.275699 0.175368 0.089 Uiso 1 1 calc R U . . .
C20 C 0.2211(4) 1.0886(4) -0.00574(17) 0.0856(12) Uani 1 1 d . . . . .
H20A H 0.174960 1.115395 0.018753 0.128 Uiso 1 1 calc R U . . .
H20B H 0.161398 1.015133 -0.032491 0.128 Uiso 1 1 calc R U . . .
H20C H 0.267597 1.149748 -0.031873 0.128 Uiso 1 1 calc R U . . .
C21 C 0.4192(2) 0.8246(2) 0.05501(11) 0.0440(5) Uani 1 1 d . . . . .
H21A H 0.506359 0.845356 0.051788 0.066 Uiso 1 1 calc R U . . .
H21B H 0.364138 0.780188 0.015648 0.066 Uiso 1 1 calc R U . . .
H21C H 0.392741 0.775733 0.089282 0.066 Uiso 1 1 calc R U . . .
C22 C 0.75067(18) 0.9402(2) 0.28640(10) 0.0342(5) Uani 1 1 d . . . . .
C23 C 0.78704(19) 0.8508(2) 0.28320(11) 0.0364(5) Uani 1 1 d . . . . .
C24 C 0.8279(2) 0.8195(2) 0.34039(11) 0.0394(5) Uani 1 1 d . . . . .
H24 H 0.853469 0.760356 0.339101 0.047 Uiso 1 1 calc R U . . .
C25 C 0.8314(2) 0.8740(2) 0.39917(11) 0.0410(5) Uani 1 1 d . . . . .
C26 C 0.7977(2) 0.9651(2) 0.40031(11) 0.0401(5) Uani 1 1 d . . . . .
H26 H 0.802257 1.003809 0.439507 0.048 Uiso 1 1 calc R U . . .
C27 C 0.75723(19) 1.0005(2) 0.34458(11) 0.0363(5) Uani 1 1 d . . . . .
C28 C 0.7215(2) 1.0995(2) 0.34736(13) 0.0475(6) Uani 1 1 d . . . . .
H28A H 0.629630 1.064619 0.342387 0.071 Uiso 1 1 calc R U . . .
H28B H 0.752100 1.148708 0.313643 0.071 Uiso 1 1 calc R U . . .
H28C H 0.759727 1.148492 0.387841 0.071 Uiso 1 1 calc R U . . .
C29 C 0.7832(3) 0.7886(3) 0.22039(12) 0.0507(6) Uani 1 1 d . . . . .
H29A H 0.714868 0.784779 0.189617 0.076 Uiso 1 1 calc R U . . .
H29B H 0.768498 0.708063 0.225847 0.076 Uiso 1 1 calc R U . . .
H29C H 0.863637 0.833217 0.205616 0.076 Uiso 1 1 calc R U . . .
C30 C 0.8684(3) 0.8338(3) 0.46071(13) 0.0585(7) Uani 1 1 d . . . . .
H30A H 0.888801 0.770380 0.451208 0.088 Uiso 1 1 calc R U . . .
H30B H 0.797856 0.804378 0.484099 0.088 Uiso 1 1 calc R U . . .
H30C H 0.941992 0.901067 0.485926 0.088 Uiso 1 1 calc R U . . .
C31 C 0.2508(2) 0.45590(17) 0.10325(9) 0.0298(4) Uani 1 1 d . . . . .
C32 C 0.3657(2) 0.5172(2) 0.07940(10) 0.0354(5) Uani 1 1 d . . . . .
C33 C 0.3579(2) 0.5415(2) 0.01620(11) 0.0388(5) Uani 1 1 d . . . . .
H33 H 0.433223 0.581269 -0.000866 0.047 Uiso 1 1 calc R U . . .
C34 C 0.2415(2) 0.5083(2) -0.02188(10) 0.0364(5) Uani 1 1 d . . . . .
C35 C 0.1293(2) 0.4501(2) 0.00410(11) 0.0372(5) Uani 1 1 d . . . . .
H35 H 0.050720 0.429308 -0.020940 0.045 Uiso 1 1 calc R U . . .
C36 C 0.1323(2) 0.42234(19) 0.06666(10) 0.0339(4) Uani 1 1 d . . . . .
C37 C 0.0098(3) 0.3566(3) 0.09399(14) 0.0528(6) Uani 1 1 d . . . . .
H37A H -0.000457 0.279718 0.104844 0.079 Uiso 1 1 calc R U . . .
H37B H -0.062142 0.344268 0.062888 0.079 Uiso 1 1 calc R U . . .
H37C H 0.014015 0.404099 0.131626 0.079 Uiso 1 1 calc R U . . .
C38 C 0.4921(3) 0.5586(3) 0.12186(13) 0.0574(7) Uani 1 1 d . . . . .
H38A H 0.560736 0.598845 0.097988 0.086 Uiso 1 1 calc R U . . .
H38B H 0.495879 0.489838 0.137667 0.086 Uiso 1 1 calc R U . . .
H38C H 0.500804 0.613496 0.157122 0.086 Uiso 1 1 calc R U . . .
C39 C 0.2367(3) 0.5373(3) -0.09042(12) 0.0528(6) Uani 1 1 d . . . . .
H39A H 0.276174 0.623486 -0.090894 0.079 Uiso 1 1 calc R U . . .
H39B H 0.148773 0.500881 -0.111184 0.079 Uiso 1 1 calc R U . . .
H39C H 0.282121 0.506073 -0.112557 0.079 Uiso 1 1 calc R U . . .
C40 C 0.29909(19) 0.44418(17) 0.33671(9) 0.0275(4) Uani 1 1 d . . . . .
C41 C 0.1932(2) 0.38240(19) 0.36756(10) 0.0320(4) Uani 1 1 d . . . . .
C42 C 0.2096(2) 0.4123(2) 0.43280(11) 0.0377(5) Uani 1 1 d . . . . .
H42 H 0.141028 0.370451 0.454277 0.045 Uiso 1 1 calc R U . . .
C43 C 0.3241(3) 0.5022(2) 0.46704(11) 0.0422(5) Uani 1 1 d . . . . .
C44 C 0.4269(2) 0.5600(2) 0.43486(11) 0.0421(5) Uani 1 1 d . . . . .
H44 H 0.504871 0.619829 0.457540 0.051 Uiso 1 1 calc R U . . .
C45 C 0.4174(2) 0.5317(2) 0.36967(11) 0.0341(4) Uani 1 1 d . . . . .
C46 C 0.5312(2) 0.5924(3) 0.33660(13) 0.0513(7) Uani 1 1 d . . . . .
H46A H 0.540145 0.532380 0.311664 0.077 Uiso 1 1 calc R U . . .
H46B H 0.607386 0.637830 0.367810 0.077 Uiso 1 1 calc R U . . .
H46C H 0.519291 0.646086 0.309086 0.077 Uiso 1 1 calc R U . . .
C47 C 0.0650(2) 0.2890(2) 0.33152(13) 0.0474(6) Uani 1 1 d . . . . .
H47A H 0.002905 0.262401 0.359900 0.071 Uiso 1 1 calc R U . . .
H47B H 0.072097 0.221242 0.314248 0.071 Uiso 1 1 calc R U . . .
H47C H 0.037886 0.323604 0.297343 0.071 Uiso 1 1 calc R U . . .
C48 C 0.3360(3) 0.5383(3) 0.53741(12) 0.0630(8) Uani 1 1 d . . . . .
H48A H 0.423630 0.569603 0.557703 0.095 Uiso 1 1 calc R U . . .
H48B H 0.281568 0.468746 0.556802 0.095 Uiso 1 1 calc R U . . .
H48C H 0.310255 0.599320 0.542346 0.095 Uiso 1 1 calc R U . . .
C49 C 0.0653(2) 0.61692(18) 0.32163(10) 0.0304(4) Uani 1 1 d . . . . .
C50 C 0.0324(2) 0.5416(2) 0.37032(13) 0.0419(5) Uani 1 1 d . . . . .
H50 H 0.095977 0.549339 0.403190 0.050 Uiso 1 1 calc R U . . .
C51 C -0.0947(3) 0.4554(2) 0.36983(14) 0.0500(6) Uani 1 1 d . . . . .
H51 H -0.115260 0.405811 0.402437 0.060 Uiso 1 1 calc R U . . .
C52 C -0.1905(2) 0.4422(2) 0.32196(13) 0.0464(6) Uani 1 1 d . . . . .
H52 H -0.275607 0.385289 0.322362 0.056 Uiso 1 1 calc R U . . .
C53 C -0.1585(2) 0.5147(2) 0.27339(12) 0.0469(6) Uani 1 1 d . . . . .
H53 H -0.222604 0.505935 0.240571 0.056 Uiso 1 1 calc R U . . .
C54 C -0.0318(2) 0.6006(2) 0.27265(11) 0.0415(5) Uani 1 1 d . . . . .
H54 H -0.011959 0.647662 0.238996 0.050 Uiso 1 1 calc R U . . .
C55 C 0.25931(19) 0.97405(17) 0.28202(9) 0.0278(4) Uani 1 1 d . . . . .
C56 C 0.3810(2) 1.06714(19) 0.30950(11) 0.0361(5) Uani 1 1 d . . . . .
H56 H 0.453533 1.073190 0.294673 0.043 Uiso 1 1 calc R U . . .
C57 C 0.3947(2) 1.1500(2) 0.35831(12) 0.0448(6) Uani 1 1 d . . . . .
H57 H 0.476326 1.211478 0.375918 0.054 Uiso 1 1 calc R U . . .
C58 C 0.2881(3) 1.1429(2) 0.38149(11) 0.0443(6) Uani 1 1 d . . . . .
H58 H 0.297538 1.199814 0.413888 0.053 Uiso 1 1 calc R U . . .
C59 C 0.1676(2) 1.0496(2) 0.35557(11) 0.0407(5) Uani 1 1 d . . . . .
H59 H 0.095598 1.042941 0.371258 0.049 Uiso 1 1 calc R U . . .
C60 C 0.1528(2) 0.96531(18) 0.30617(10) 0.0326(4) Uani 1 1 d . . . . .
H60 H 0.071165 0.902929 0.289282 0.039 Uiso 1 1 calc R U . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N4 1.8377(16) . ?
Ti1 N1 1.8568(16) . ?
Ti1 N9 2.2590(16) . ?
Ti1 N7 2.2980(17) . ?
Ti1 S1 2.4889(6) . ?
Ti1 S2 2.5141(6) . ?
S1 C7 1.729(2) . ?
S2 C10 1.7371(19) . ?
N1 C1 1.275(2) . ?
N2 C2 1.390(3) . ?
N2 C1 1.401(2) . ?
N2 C13 1.433(3) . ?
N3 C1 1.398(3) . ?
N3 C3 1.398(3) . ?
N3 C22 1.436(3) . ?
N4 C4 1.275(2) . ?
N5 C4 1.390(3) . ?
N5 C5 1.392(3) . ?
N5 C31 1.433(2) . ?
N6 C6 1.387(3) . ?
N6 C4 1.399(2) . ?
N6 C40 1.427(2) . ?
N7 C7 1.317(3) . ?
N7 C49 1.414(3) . ?
N8 C7 1.365(3) . ?
N8 C8 1.452(3) . ?
N8 C9 1.453(3) . ?
N9 C10 1.319(3) . ?
N9 C55 1.412(2) . ?
N10 C10 1.362(2) . ?
N10 C11 1.455(3) . ?
N10 C12 1.458(3) . ?
C2 C3 1.329(3) . ?
C2 H2 0.9300 . ?
C3 H3 0.9300 . ?
C5 C6 1.338(3) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
C13 C14 1.394(3) . ?
C13 C18 1.398(3) . ?
C14 C15 1.392(3) . ?
C14 C21 1.497(3) . ?
C15 C16 1.389(4) . ?
C15 H15 0.9300 . ?
C16 C17 1.379(4) . ?
C16 C20 1.513(4) . ?
C17 C18 1.384(4) . ?
C17 H17 0.9300 . ?
C18 C19 1.506(4) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 C23 1.388(3) . ?
C22 C27 1.398(3) . ?
C23 C24 1.393(3) . ?
C23 C29 1.504(3) . ?
C24 C25 1.386(3) . ?
C24 H24 0.9300 . ?
C25 C26 1.384(4) . ?
C25 C30 1.510(3) . ?
C26 C27 1.392(3) . ?
C26 H26 0.9300 . ?
C27 C28 1.498(3) . ?
C28 H28A 0.9600 . ?
C28 H28B 0.9600 . ?
C28 H28C 0.9600 . ?
C29 H29A 0.9600 . ?
C29 H29B 0.9600 . ?
C29 H29C 0.9600 . ?
C30 H30A 0.9600 . ?
C30 H30B 0.9600 . ?
C30 H30C 0.9600 . ?
C31 C36 1.386(3) . ?
C31 C32 1.396(3) . ?
C32 C33 1.391(3) . ?
C32 C38 1.498(3) . ?
C33 C34 1.381(3) . ?
C33 H33 0.9300 . ?
C34 C35 1.390(3) . ?
C34 C39 1.517(3) . ?
C35 C36 1.389(3) . ?
C35 H35 0.9300 . ?
C36 C37 1.510(3) . ?
C37 H37A 0.9600 . ?
C37 H37B 0.9600 . ?
C37 H37C 0.9600 . ?
C38 H38A 0.9600 . ?
C38 H38B 0.9600 . ?
C38 H38C 0.9600 . ?
C39 H39A 0.9600 . ?
C39 H39B 0.9600 . ?
C39 H39C 0.9600 . ?
C40 C45 1.387(3) . ?
C40 C41 1.401(3) . ?
C41 C42 1.386(3) . ?
C41 C47 1.501(3) . ?
C42 C43 1.381(3) . ?
C42 H42 0.9300 . ?
C43 C44 1.385(3) . ?
C43 C48 1.514(3) . ?
C44 C45 1.393(3) . ?
C44 H44 0.9300 . ?
C45 C46 1.496(3) . ?
C46 H46A 0.9600 . ?
C46 H46B 0.9600 . ?
C46 H46C 0.9600 . ?
C47 H47A 0.9600 . ?
C47 H47B 0.9600 . ?
C47 H47C 0.9600 . ?
C48 H48A 0.9600 . ?
C48 H48B 0.9600 . ?
C48 H48C 0.9600 . ?
C49 C54 1.388(3) . ?
C49 C50 1.399(3) . ?
C50 C51 1.390(3) . ?
C50 H50 0.9300 . ?
C51 C52 1.373(4) . ?
C51 H51 0.9300 . ?
C52 C53 1.376(4) . ?
C52 H52 0.9300 . ?
C53 C54 1.389(3) . ?
C53 H53 0.9300 . ?
C54 H54 0.9300 . ?
C55 C60 1.391(3) . ?
C55 C56 1.399(3) . ?
C56 C57 1.378(3) . ?
C56 H56 0.9300 . ?
C57 C58 1.388(4) . ?
C57 H57 0.9300 . ?
C58 C59 1.383(4) . ?
C58 H58 0.9300 . ?
C59 C60 1.394(3) . ?
C59 H59 0.9300 . ?
C60 H60 0.9300 . ?

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
N4 Ti1 N1 105.26(7) . . ?
N4 Ti1 N9 153.01(7) . . ?
N1 Ti1 N9 93.21(7) . . ?
N4 Ti1 N7 93.16(6) . . ?
N1 Ti1 N7 152.16(7) . . ?
N9 Ti1 N7 78.01(6) . . ?
N4 Ti1 S1 104.59(5) . . ?
N1 Ti1 S1 90.38(5) . . ?
N9 Ti1 S1 94.61(4) . . ?
N7 Ti1 S1 64.48(5) . . ?
N4 Ti1 S2 91.72(5) . . ?
N1 Ti1 S2 103.50(5) . . ?
N9 Ti1 S2 64.49(4) . . ?
N7 Ti1 S2 96.48(5) . . ?
S1 Ti1 S2 155.12(2) . . ?
C7 S1 Ti1 82.07(7) . . ?
C10 S2 Ti1 81.30(7) . . ?
C1 N1 Ti1 169.74(15) . . ?
C2 N2 C1 110.32(18) . . ?
C2 N2 C13 122.71(18) . . ?
C1 N2 C13 126.43(17) . . ?
C1 N3 C3 110.42(18) . . ?
C1 N3 C22 125.54(17) . . ?
C3 N3 C22 123.09(18) . . ?
C4 N4 Ti1 173.18(15) . . ?
C4 N5 C5 110.36(17) . . ?
C4 N5 C31 126.79(16) . . ?
C5 N5 C31 122.72(17) . . ?
C6 N6 C4 110.43(17) . . ?
C6 N6 C40 124.89(17) . . ?
C4 N6 C40 124.56(16) . . ?
C7 N7 C49 123.31(18) . . ?
C7 N7 Ti1 99.34(13) . . ?
C49 N7 Ti1 136.42(13) . . ?
C7 N8 C8 122.0(2) . . ?
C7 N8 C9 120.5(2) . . ?
C8 N8 C9 113.9(2) . . ?
C10 N9 C55 125.84(17) . . ?
C10 N9 Ti1 101.38(12) . . ?
C55 N9 Ti1 129.56(13) . . ?
C10 N10 C11 119.96(17) . . ?
C10 N10 C12 121.89(18) . . ?
C11 N10 C12 114.85(18) . . ?
N1 C1 N3 128.87(18) . . ?
N1 C1 N2 127.95(18) . . ?
N3 C1 N2 103.16(16) . . ?
C3 C2 N2 108.36(19) . . ?
C3 C2 H2 125.8 . . ?
N2 C2 H2 125.8 . . ?
C2 C3 N3 107.7(2) . . ?
C2 C3 H3 126.1 . . ?
N3 C3 H3 126.1 . . ?
N4 C4 N5 128.53(17) . . ?
N4 C4 N6 127.99(18) . . ?
N5 C4 N6 103.46(16) . . ?
C6 C5 N5 107.96(19) . . ?
C6 C5 H5 126.0 . . ?
N5 C5 H5 126.0 . . ?
C5 C6 N6 107.76(19) . . ?
C5 C6 H6 126.1 . . ?
N6 C6 H6 126.1 . . ?
N7 C7 N8 126.5(2) . . ?
N7 C7 S1 113.63(15) . . ?
N8 C7 S1 119.86(17) . . ?
N8 C8 H8A 109.5 . . ?
N8 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N8 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
N8 C9 H9A 109.5 . . ?
N8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N9 C10 N10 126.69(18) . . ?
N9 C10 S2 112.81(14) . . ?
N10 C10 S2 120.50(15) . . ?
N10 C11 H11A 109.5 . . ?
N10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
N10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N10 C12 H12A 109.5 . . ?
N10 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
N10 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C14 C13 C18 122.1(2) . . ?
C14 C13 N2 119.9(2) . . ?
C18 C13 N2 117.9(2) . . ?
C15 C14 C13 117.3(2) . . ?
C15 C14 C21 121.0(2) . . ?
C13 C14 C21 121.7(2) . . ?
C16 C15 C14 122.1(3) . . ?
C16 C15 H15 119.0 . . ?
C14 C15 H15 119.0 . . ?
C17 C16 C15 118.5(2) . . ?
C17 C16 C20 120.8(3) . . ?
C15 C16 C20 120.7(3) . . ?
C16 C17 C18 122.0(2) . . ?
C16 C17 H17 119.0 . . ?
C18 C17 H17 119.0 . . ?
C17 C18 C13 117.9(2) . . ?
C17 C18 C19 120.2(2) . . ?
C13 C18 C19 121.9(2) . . ?
C18 C19 H19A 109.5 . . ?
C18 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C18 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C16 C20 H20A 109.5 . . ?
C16 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C16 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C14 C21 H21A 109.5 . . ?
C14 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C14 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C23 C22 C27 122.0(2) . . ?
C23 C22 N3 119.6(2) . . ?
C27 C22 N3 118.3(2) . . ?
C22 C23 C24 117.9(2) . . ?
C22 C23 C29 121.7(2) . . ?
C24 C23 C29 120.3(2) . . ?
C25 C24 C23 121.9(2) . . ?
C25 C24 H24 119.1 . . ?
C23 C24 H24 119.1 . . ?
C26 C25 C24 118.4(2) . . ?
C26 C25 C30 120.4(2) . . ?
C24 C25 C30 121.1(2) . . ?
C25 C26 C27 122.0(2) . . ?
C25 C26 H26 119.0 . . ?
C27 C26 H26 119.0 . . ?
C26 C27 C22 117.7(2) . . ?
C26 C27 C28 120.8(2) . . ?
C22 C27 C28 121.5(2) . . ?
C27 C28 H28A 109.5 . . ?
C27 C28 H28B 109.5 . . ?
H28A C28 H28B 109.5 . . ?
C27 C28 H28C 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
C23 C29 H29A 109.5 . . ?
C23 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C23 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
C25 C30 H30A 109.5 . . ?
C25 C30 H30B 109.5 . . ?
H30A C30 H30B 109.5 . . ?
C25 C30 H30C 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
C36 C31 C32 122.14(19) . . ?
C36 C31 N5 119.42(19) . . ?
C32 C31 N5 118.29(19) . . ?
C33 C32 C31 117.7(2) . . ?
C33 C32 C38 121.9(2) . . ?
C31 C32 C38 120.4(2) . . ?
C34 C33 C32 121.8(2) . . ?
C34 C33 H33 119.1 . . ?
C32 C33 H33 119.1 . . ?
C33 C34 C35 118.9(2) . . ?
C33 C34 C39 120.3(2) . . ?
C35 C34 C39 120.8(2) . . ?
C36 C35 C34 121.4(2) . . ?
C36 C35 H35 119.3 . . ?
C34 C35 H35 119.3 . . ?
C31 C36 C35 118.2(2) . . ?
C31 C36 C37 120.8(2) . . ?
C35 C36 C37 121.0(2) . . ?
C36 C37 H37A 109.5 . . ?
C36 C37 H37B 109.5 . . ?
H37A C37 H37B 109.5 . . ?
C36 C37 H37C 109.5 . . ?
H37A C37 H37C 109.5 . . ?
H37B C37 H37C 109.5 . . ?
C32 C38 H38A 109.5 . . ?
C32 C38 H38B 109.5 . . ?
H38A C38 H38B 109.5 . . ?
C32 C38 H38C 109.5 . . ?
H38A C38 H38C 109.5 . . ?
H38B C38 H38C 109.5 . . ?
C34 C39 H39A 109.5 . . ?
C34 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
C34 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?
C45 C40 C41 121.90(19) . . ?
C45 C40 N6 119.60(18) . . ?
C41 C40 N6 118.50(18) . . ?
C42 C41 C40 117.7(2) . . ?
C42 C41 C47 120.6(2) . . ?
C40 C41 C47 121.7(2) . . ?
C43 C42 C41 122.3(2) . . ?
C43 C42 H42 118.9 . . ?
C41 C42 H42 118.9 . . ?
C42 C43 C44 118.1(2) . . ?
C42 C43 C48 120.9(2) . . ?
C44 C43 C48 121.0(2) . . ?
C43 C44 C45 122.2(2) . . ?
C43 C44 H44 118.9 . . ?
C45 C44 H44 118.9 . . ?
C40 C45 C44 117.7(2) . . ?
C40 C45 C46 121.2(2) . . ?
C44 C45 C46 121.1(2) . . ?
C45 C46 H46A 109.5 . . ?
C45 C46 H46B 109.5 . . ?
H46A C46 H46B 109.5 . . ?
C45 C46 H46C 109.5 . . ?
H46A C46 H46C 109.5 . . ?
H46B C46 H46C 109.5 . . ?
C41 C47 H47A 109.5 . . ?
C41 C47 H47B 109.5 . . ?
H47A C47 H47B 109.5 . . ?
C41 C47 H47C 109.5 . . ?
H47A C47 H47C 109.5 . . ?
H47B C47 H47C 109.5 . . ?
C43 C48 H48A 109.5 . . ?
C43 C48 H48B 109.5 . . ?
H48A C48 H48B 109.5 . . ?
C43 C48 H48C 109.5 . . ?
H48A C48 H48C 109.5 . . ?
H48B C48 H48C 109.5 . . ?
C54 C49 C50 118.0(2) . . ?
C54 C49 N7 119.96(19) . . ?
C50 C49 N7 121.9(2) . . ?
C51 C50 C49 120.4(2) . . ?
C51 C50 H50 119.8 . . ?
C49 C50 H50 119.8 . . ?
C52 C51 C50 121.0(2) . . ?
C52 C51 H51 119.5 . . ?
C50 C51 H51 119.5 . . ?
C51 C52 C53 118.9(2) . . ?
C51 C52 H52 120.6 . . ?
C53 C52 H52 120.6 . . ?
C52 C53 C54 121.0(2) . . ?
C52 C53 H53 119.5 . . ?
C54 C53 H53 119.5 . . ?
C49 C54 C53 120.7(2) . . ?
C49 C54 H54 119.7 . . ?
C53 C54 H54 119.7 . . ?
C60 C55 C56 118.42(19) . . ?
C60 C55 N9 123.30(18) . . ?
C56 C55 N9 118.01(18) . . ?
C57 C56 C55 120.8(2) . . ?
C57 C56 H56 119.6 . . ?
C55 C56 H56 119.6 . . ?
C56 C57 C58 120.8(2) . . ?
C56 C57 H57 119.6 . . ?
C58 C57 H57 119.6 . . ?
C59 C58 C57 118.8(2) . . ?
C59 C58 H58 120.6 . . ?
C57 C58 H58 120.6 . . ?
C58 C59 C60 120.8(2) . . ?
C58 C59 H59 119.6 . . ?
C60 C59 H59 119.6 . . ?
C55 C60 C59 120.4(2) . . ?
C55 C60 H60 119.8 . . ?
C59 C60 H60 119.8 . . ?

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
N4 Ti1 N1 C1 -160.5(8) . . . . ?
N9 Ti1 N1 C1 39.4(8) . . . . ?
N7 Ti1 N1 C1 -30.8(9) . . . . ?
S1 Ti1 N1 C1 -55.3(8) . . . . ?
S2 Ti1 N1 C1 103.9(8) . . . . ?
Ti1 N1 C1 N3 98.3(8) . . . . ?
Ti1 N1 C1 N2 -83.7(9) . . . . ?
C3 N3 C1 N1 178.3(2) . . . . ?
C22 N3 C1 N1 -12.6(4) . . . . ?
C3 N3 C1 N2 -0.1(2) . . . . ?
C22 N3 C1 N2 169.0(2) . . . . ?
C2 N2 C1 N1 -178.3(2) . . . . ?
C13 N2 C1 N1 10.0(4) . . . . ?
C2 N2 C1 N3 0.1(2) . . . . ?
C13 N2 C1 N3 -171.6(2) . . . . ?
C1 N2 C2 C3 -0.1(3) . . . . ?
C13 N2 C2 C3 171.9(2) . . . . ?
N2 C2 C3 N3 0.1(3) . . . . ?
C1 N3 C3 C2 0.0(3) . . . . ?
C22 N3 C3 C2 -169.4(2) . . . . ?
C5 N5 C4 N4 177.8(2) . . . . ?
C31 N5 C4 N4 1.7(4) . . . . ?
C5 N5 C4 N6 -1.1(2) . . . . ?
C31 N5 C4 N6 -177.1(2) . . . . ?
C6 N6 C4 N4 -177.3(2) . . . . ?
C40 N6 C4 N4 6.4(3) . . . . ?
C6 N6 C4 N5 1.5(2) . . . . ?
C40 N6 C4 N5 -174.66(18) . . . . ?
C4 N5 C5 C6 0.2(3) . . . . ?
C31 N5 C5 C6 176.5(2) . . . . ?
N5 C5 C6 N6 0.8(3) . . . . ?
C4 N6 C6 C5 -1.5(3) . . . . ?
C40 N6 C6 C5 174.7(2) . . . . ?
C49 N7 C7 N8 -19.0(3) . . . . ?
Ti1 N7 C7 N8 170.3(2) . . . . ?
C49 N7 C7 S1 163.76(15) . . . . ?
Ti1 N7 C7 S1 -6.87(16) . . . . ?
C8 N8 C7 N7 -31.9(4) . . . . ?
C9 N8 C7 N7 170.6(2) . . . . ?
C8 N8 C7 S1 145.2(2) . . . . ?
C9 N8 C7 S1 -12.3(3) . . . . ?
Ti1 S1 C7 N7 6.32(15) . . . . ?
Ti1 S1 C7 N8 -171.08(18) . . . . ?
C55 N9 C10 N10 17.8(3) . . . . ?
Ti1 N9 C10 N10 179.04(18) . . . . ?
C55 N9 C10 S2 -162.50(15) . . . . ?
Ti1 N9 C10 S2 -1.29(15) . . . . ?
C11 N10 C10 N9 -176.0(2) . . . . ?
C12 N10 C10 N9 25.6(3) . . . . ?
C11 N10 C10 S2 4.4(3) . . . . ?
C12 N10 C10 S2 -154.04(16) . . . . ?
Ti1 S2 C10 N9 1.15(13) . . . . ?
Ti1 S2 C10 N10 -179.16(17) . . . . ?
C2 N2 C13 C14 114.5(2) . . . . ?
C1 N2 C13 C14 -74.8(3) . . . . ?
C2 N2 C13 C18 -62.1(3) . . . . ?
C1 N2 C13 C18 108.7(2) . . . . ?
C18 C13 C14 C15 1.3(3) . . . . ?
N2 C13 C14 C15 -175.05(19) . . . . ?
C18 C13 C14 C21 179.8(2) . . . . ?
N2 C13 C14 C21 3.4(3) . . . . ?
C13 C14 C15 C16 2.4(3) . . . . ?
C21 C14 C15 C16 -176.1(2) . . . . ?
C14 C15 C16 C17 -3.2(4) . . . . ?
C14 C15 C16 C20 175.6(2) . . . . ?
C15 C16 C17 C18 0.2(4) . . . . ?
C20 C16 C17 C18 -178.5(2) . . . . ?
C16 C17 C18 C13 3.3(4) . . . . ?
C16 C17 C18 C19 -175.9(2) . . . . ?
C14 C13 C18 C17 -4.1(3) . . . . ?
N2 C13 C18 C17 172.35(19) . . . . ?
C14 C13 C18 C19 175.1(2) . . . . ?
N2 C13 C18 C19 -8.5(3) . . . . ?
C1 N3 C22 C23 101.2(3) . . . . ?
C3 N3 C22 C23 -91.1(3) . . . . ?
C1 N3 C22 C27 -81.5(3) . . . . ?
C3 N3 C22 C27 86.3(3) . . . . ?
C27 C22 C23 C24 1.7(3) . . . . ?
N3 C22 C23 C24 178.89(18) . . . . ?
C27 C22 C23 C29 -178.3(2) . . . . ?
N3 C22 C23 C29 -1.1(3) . . . . ?
C22 C23 C24 C25 0.7(3) . . . . ?
C29 C23 C24 C25 -179.3(2) . . . . ?
C23 C24 C25 C26 -2.4(3) . . . . ?
C23 C24 C25 C30 176.3(2) . . . . ?
C24 C25 C26 C27 1.9(3) . . . . ?
C30 C25 C26 C27 -176.9(2) . . . . ?
C25 C26 C27 C22 0.3(3) . . . . ?
C25 C26 C27 C28 -180.0(2) . . . . ?
C23 C22 C27 C26 -2.2(3) . . . . ?
N3 C22 C27 C26 -179.43(18) . . . . ?
C23 C22 C27 C28 178.1(2) . . . . ?
N3 C22 C27 C28 0.9(3) . . . . ?
C4 N5 C31 C36 -102.7(3) . . . . ?
C5 N5 C31 C36 81.6(3) . . . . ?
C4 N5 C31 C32 81.6(3) . . . . ?
C5 N5 C31 C32 -94.0(3) . . . . ?
C36 C31 C32 C33 -1.6(3) . . . . ?
N5 C31 C32 C33 173.89(19) . . . . ?
C36 C31 C32 C38 176.2(2) . . . . ?
N5 C31 C32 C38 -8.3(3) . . . . ?
C31 C32 C33 C34 0.9(3) . . . . ?
C38 C32 C33 C34 -176.9(2) . . . . ?
C32 C33 C34 C35 0.7(3) . . . . ?
C32 C33 C34 C39 179.4(2) . . . . ?
C33 C34 C35 C36 -1.7(3) . . . . ?
C39 C34 C35 C36 179.6(2) . . . . ?
C32 C31 C36 C35 0.7(3) . . . . ?
N5 C31 C36 C35 -174.75(18) . . . . ?
C32 C31 C36 C37 -179.7(2) . . . . ?
N5 C31 C36 C37 4.8(3) . . . . ?
C34 C35 C36 C31 1.0(3) . . . . ?
C34 C35 C36 C37 -178.6(2) . . . . ?
C6 N6 C40 C45 115.3(3) . . . . ?
C4 N6 C40 C45 -69.1(3) . . . . ?
C6 N6 C40 C41 -63.9(3) . . . . ?
C4 N6 C40 C41 111.8(2) . . . . ?
C45 C40 C41 C42 0.6(3) . . . . ?
N6 C40 C41 C42 179.78(18) . . . . ?
C45 C40 C41 C47 179.2(2) . . . . ?
N6 C40 C41 C47 -1.7(3) . . . . ?
C40 C41 C42 C43 2.0(3) . . . . ?
C47 C41 C42 C43 -176.6(2) . . . . ?
C41 C42 C43 C44 -2.8(3) . . . . ?
C41 C42 C43 C48 175.9(2) . . . . ?
C42 C43 C44 C45 0.9(3) . . . . ?
C48 C43 C44 C45 -177.7(2) . . . . ?
C41 C40 C45 C44 -2.3(3) . . . . ?
N6 C40 C45 C44 178.55(19) . . . . ?
C41 C40 C45 C46 176.9(2) . . . . ?
N6 C40 C45 C46 -2.2(3) . . . . ?
C43 C44 C45 C40 1.5(3) . . . . ?
C43 C44 C45 C46 -177.7(2) . . . . ?
C7 N7 C49 C54 147.4(2) . . . . ?
Ti1 N7 C49 C54 -46.1(3) . . . . ?
C7 N7 C49 C50 -36.6(3) . . . . ?
Ti1 N7 C49 C50 129.9(2) . . . . ?
C54 C49 C50 C51 -1.5(3) . . . . ?
N7 C49 C50 C51 -177.6(2) . . . . ?
C49 C50 C51 C52 -0.1(4) . . . . ?
C50 C51 C52 C53 1.2(4) . . . . ?
C51 C52 C53 C54 -0.5(4) . . . . ?
C50 C49 C54 C53 2.2(3) . . . . ?
N7 C49 C54 C53 178.3(2) . . . . ?
C52 C53 C54 C49 -1.2(4) . . . . ?
C10 N9 C55 C60 44.8(3) . . . . ?
Ti1 N9 C55 C60 -111.0(2) . . . . ?
C10 N9 C55 C56 -141.3(2) . . . . ?
Ti1 N9 C55 C56 62.9(2) . . . . ?
C60 C55 C56 C57 -1.6(3) . . . . ?
N9 C55 C56 C57 -175.8(2) . . . . ?
C55 C56 C57 C58 0.2(4) . . . . ?
C56 C57 C58 C59 1.2(4) . . . . ?
C57 C58 C59 C60 -1.2(4) . . . . ?
C56 C55 C60 C59 1.5(3) . . . . ?
N9 C55 C60 C59 175.40(19) . . . . ?
C58 C59 C60 C55 -0.2(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C54 H54 S2 0.93 2.82 3.568(2) 137.9 .
C54 H54 S2 0.93 2.82 3.568(2) 137.9 .

_refine_diff_density_max         0.275
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.060

####################################################################### 
# 
# 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_5a
_database_code_depnum_ccdc_archive 'CCDC 1880617'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H19 N3 O'
_chemical_formula_sum            'C14 H19 N3 O'
_chemical_formula_weight         245.32

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_H-M_alt        'P 42/n'
_space_group_name_Hall           '-P 4bc'

_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+1/2, z+1/2'
'-x+1/2, -y+1/2, z'
'y+1/2, -x, z+1/2'
'-x, -y, -z'
'y, -x-1/2, -z-1/2'
'x-1/2, y-1/2, -z'
'-y-1/2, x, -z-1/2'

_cell_length_a                   16.6882(4)
_cell_length_b                   16.6882(4)
_cell_length_c                   10.0005(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2785.10(17)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    1877
_cell_measurement_theta_min      5.1570
_cell_measurement_theta_max      69.0880

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_F_000             1056
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_exptl_absorpt_coefficient_mu    0.601
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.34873
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5200
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_theta_min         3.746
_diffrn_reflns_theta_max         69.937
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2594
_reflns_number_gt                1827
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0787P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0044(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2594
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0487
_refine_ls_wR_factor_ref         0.1427
_refine_ls_wR_factor_gt          0.1246
_refine_ls_goodness_of_fit_ref   0.946
_refine_ls_restrained_S_all      0.946
_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
O1 O 0.24820(8) 0.48183(8) 0.11100(12) 0.0598(4) Uani 1 1 d . . . . .
N3 N 0.40653(9) 0.41472(9) 0.47357(15) 0.0529(4) Uani 1 1 d . . . . .
N2 N 0.33326(8) 0.45453(8) 0.28280(13) 0.0458(4) Uani 1 1 d . . . . .
C1 C 0.35017(9) 0.46329(10) 0.41948(17) 0.0462(4) Uani 1 1 d . . . . .
N1 N 0.31497(9) 0.51557(9) 0.49681(15) 0.0552(4) Uani 1 1 d . . . . .
C2 C 0.26874(10) 0.49588(10) 0.22629(17) 0.0476(4) Uani 1 1 d . . . . .
C3 C 0.22937(10) 0.55385(10) 0.31135(19) 0.0496(4) Uani 1 1 d . . . . .
C4 C 0.25579(10) 0.56334(10) 0.4421(2) 0.0526(4) Uani 1 1 d . . . . .
C13 C 0.38494(10) 0.40575(11) 0.19198(18) 0.0530(4) Uani 1 1 d . . . . .
H13 H 0.4274 0.3830 0.2479 0.064 Uiso 1 1 calc R U . . .
C5 C 0.21864(12) 0.62144(12) 0.5226(2) 0.0692(6) Uani 1 1 d . . . . .
H5 H 0.2359 0.6292 0.6101 0.083 Uiso 1 1 calc R U . . .
C8 C 0.16538(11) 0.60009(11) 0.2625(2) 0.0625(5) Uani 1 1 d . . . . .
H8 H 0.1476 0.5928 0.1752 0.075 Uiso 1 1 calc R U . . .
C9 C 0.42187(12) 0.41502(12) 0.61765(19) 0.0628(5) Uani 1 1 d . . . . .
H9 H 0.4256 0.4708 0.6475 0.075 Uiso 1 1 calc R U . . .
C14 C 0.34220(13) 0.33596(12) 0.1290(2) 0.0736(6) Uani 1 1 d . . . . .
H14A H 0.3204 0.3022 0.1977 0.110 Uiso 1 1 calc R U . . .
H14B H 0.3793 0.3057 0.0757 0.110 Uiso 1 1 calc R U . . .
H14C H 0.2996 0.3554 0.0732 0.110 Uiso 1 1 calc R U . . .
C10 C 0.50188(14) 0.37474(14) 0.6428(2) 0.0814(7) Uani 1 1 d . . . . .
H10A H 0.4997 0.3202 0.6123 0.122 Uiso 1 1 calc R U . . .
H10B H 0.5135 0.3756 0.7368 0.122 Uiso 1 1 calc R U . . .
H10C H 0.5432 0.4029 0.5952 0.122 Uiso 1 1 calc R U . . .
C7 C 0.12929(13) 0.65537(13) 0.3422(2) 0.0742(6) Uani 1 1 d . . . . .
H7 H 0.0864 0.6854 0.3102 0.089 Uiso 1 1 calc R U . . .
C12 C 0.42609(14) 0.45759(14) 0.0894(2) 0.0807(7) Uani 1 1 d . . . . .
H12A H 0.3871 0.4783 0.0279 0.121 Uiso 1 1 calc R U . . .
H12B H 0.4648 0.4262 0.0414 0.121 Uiso 1 1 calc R U . . .
H12C H 0.4526 0.5013 0.1334 0.121 Uiso 1 1 calc R U . . .
C6 C 0.15709(13) 0.66668(13) 0.4724(2) 0.0771(7) Uani 1 1 d . . . . .
H6 H 0.1334 0.7056 0.5260 0.092 Uiso 1 1 calc R U . . .
C11 C 0.35472(16) 0.37518(19) 0.6929(2) 0.1056(10) Uani 1 1 d . . . . .
H11A H 0.3054 0.4029 0.6752 0.158 Uiso 1 1 calc R U . . .
H11B H 0.3659 0.3768 0.7870 0.158 Uiso 1 1 calc R U . . .
H11C H 0.3500 0.3204 0.6645 0.158 Uiso 1 1 calc R U . . .
H3A H 0.4235(13) 0.3739(12) 0.430(2) 0.071(7) Uiso 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C2 1.226(2) . ?
N3 C1 1.354(2) . ?
N3 C9 1.463(2) . ?
N3 H3A 0.86(2) . ?
N2 C2 1.398(2) . ?
N2 C1 1.403(2) . ?
N2 C13 1.494(2) . ?
C1 N1 1.305(2) . ?
N1 C4 1.382(2) . ?
C2 C3 1.446(2) . ?
C3 C4 1.388(3) . ?
C3 C8 1.405(2) . ?
C4 C5 1.405(3) . ?
C13 C14 1.504(3) . ?
C13 C12 1.508(3) . ?
C13 H13 0.9800 . ?
C5 C6 1.370(3) . ?
C5 H5 0.9300 . ?
C8 C7 1.360(3) . ?
C8 H8 0.9300 . ?
C9 C11 1.505(3) . ?
C9 C10 1.516(3) . ?
C9 H9 0.9800 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C7 C6 1.395(3) . ?
C7 H7 0.9300 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
C6 H6 0.9300 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N3 C9 120.84(16) . . ?
C1 N3 H3A 119.9(14) . . ?
C9 N3 H3A 116.7(14) . . ?
C2 N2 C1 119.81(14) . . ?
C2 N2 C13 117.89(13) . . ?
C1 N2 C13 122.20(13) . . ?
N1 C1 N3 118.42(16) . . ?
N1 C1 N2 123.79(15) . . ?
N3 C1 N2 117.79(15) . . ?
C1 N1 C4 118.18(15) . . ?
O1 C2 N2 120.09(16) . . ?
O1 C2 C3 123.67(15) . . ?
N2 C2 C3 116.25(15) . . ?
C4 C3 C8 120.39(17) . . ?
C4 C3 C2 119.07(15) . . ?
C8 C3 C2 120.55(17) . . ?
N1 C4 C3 122.28(16) . . ?
N1 C4 C5 119.09(17) . . ?
C3 C4 C5 118.59(17) . . ?
N2 C13 C14 113.77(15) . . ?
N2 C13 C12 111.36(15) . . ?
C14 C13 C12 112.03(17) . . ?
N2 C13 H13 106.4 . . ?
C14 C13 H13 106.4 . . ?
C12 C13 H13 106.4 . . ?
C6 C5 C4 120.1(2) . . ?
C6 C5 H5 120.0 . . ?
C4 C5 H5 120.0 . . ?
C7 C8 C3 120.37(19) . . ?
C7 C8 H8 119.8 . . ?
C3 C8 H8 119.8 . . ?
N3 C9 C11 111.13(18) . . ?
N3 C9 C10 108.42(17) . . ?
C11 C9 C10 112.16(19) . . ?
N3 C9 H9 108.3 . . ?
C11 C9 H9 108.3 . . ?
C10 C9 H9 108.3 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C8 C7 C6 119.43(19) . . ?
C8 C7 H7 120.3 . . ?
C6 C7 H7 120.3 . . ?
C13 C12 H12A 109.5 . . ?
C13 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C13 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C5 C6 C7 121.1(2) . . ?
C5 C6 H6 119.4 . . ?
C7 C6 H6 119.4 . . ?
C9 C11 H11A 109.5 . . ?
C9 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C9 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?

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
N3 H3A O1 0.86(2) 2.30(2) 3.112(2) 159.2(19) 6_566
C13 H13 N3 0.98 2.34 2.843(2) 110.8 .
C14 H14C O1 0.96 2.31 2.902(2) 119.2 .
C10 H10A O1 0.96 2.53 3.281(2) 135.6 6_566
C12 H12A O1 0.96 2.46 3.004(3) 115.5 .
C11 H11A N1 0.96 2.60 3.126(3) 115.0 .

_refine_diff_density_max         0.178
_refine_diff_density_min         -0.151
_refine_diff_density_rms         0.039

####################################################################### 
# 
# 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_2b
_database_code_depnum_ccdc_archive 'CCDC 1880616'
_audit_update_record             
;
2018-12-31 deposited with the CCDC.
2019-01-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C46 H60 N8 Ti'
_chemical_formula_sum            'C46 H60 N8 Ti'
_chemical_formula_weight         772.89

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_H-M_alt        'P c c n'
_space_group_name_Hall           '-P 2ab 2ac'

_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'
'x+1/2, -y, -z+1/2'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'-x-1/2, y, z-1/2'
'x, -y-1/2, z-1/2'

_cell_length_a                   20.4747(4)
_cell_length_b                   20.9986(3)
_cell_length_c                   20.8892(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     8981.1(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    5729
_cell_measurement_theta_min      3.0120
_cell_measurement_theta_max      71.4490
_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.143
_exptl_crystal_F_000             3312
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_exptl_absorpt_coefficient_mu    1.911
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.84474
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
'CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)(compiled Oct 27 2011,15:02:11). Empirical absorption correction using spherical harmonics,implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19723
_diffrn_reflns_av_unetI/netI     0.0620
_diffrn_reflns_av_R_equivalents  0.0408
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         3.014
_diffrn_reflns_theta_max         71.592
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             8561
_reflns_number_gt                6131
_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       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_cell_refinement       
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_data_reduction        
'CrysAlisPro, Agilent Technologies,Version 1.171.35.19 (release 27-10-2011CrysAlis171 .NET)(compiled Oct 27'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP III & Olex 2.1'
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0727P)²+2.0724P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.00038(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         8561
_refine_ls_number_parameters     513
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0560
_refine_ls_wR_factor_ref         0.1679
_refine_ls_wR_factor_gt          0.1519
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_restrained_S_all      1.094
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.44652(2) 0.53084(2) 0.22367(2) 0.02513(14) Uani 1 1 d . . . . .
N1 N 0.35780(12) 0.51492(11) 0.22270(11) 0.0325(5) Uani 1 1 d . . . . .
N2 N 0.46775(12) 0.61683(11) 0.22221(11) 0.0305(5) Uani 1 1 d . . . . .
N3 N 0.48169(12) 0.48363(12) 0.29507(12) 0.0343(6) Uani 1 1 d . . . . .
N4 N 0.49304(13) 0.49499(11) 0.15205(12) 0.0350(6) Uani 1 1 d . . . . .
N5 N 0.26253(11) 0.44955(12) 0.23141(11) 0.0302(5) Uani 1 1 d . . . . .
N6 N 0.27076(11) 0.50806(12) 0.14526(11) 0.0310(5) Uani 1 1 d . . . . .
N7 N 0.45867(12) 0.70244(11) 0.29719(12) 0.0338(6) Uani 1 1 d . . . . .
N8 N 0.49824(12) 0.72567(10) 0.20240(11) 0.0303(5) Uani 1 1 d . . . . .
C1 C 0.30341(13) 0.49343(13) 0.20183(13) 0.0275(6) Uani 1 1 d . . . . .
C2 C 0.47416(13) 0.67486(13) 0.23864(14) 0.0286(6) Uani 1 1 d . . . . .
C3 C 0.20823(14) 0.43744(17) 0.19367(15) 0.0416(8) Uani 1 1 d . . . . .
H3 H 0.1744 0.4094 0.2033 0.050 Uiso 1 1 calc R U . . .
C4 C 0.21309(14) 0.47304(16) 0.14115(15) 0.0426(8) Uani 1 1 d . . . . .
H4 H 0.1832 0.4743 0.1076 0.051 Uiso 1 1 calc R U . . .
C5 C 0.29346(13) 0.55285(14) 0.09874(13) 0.0298(6) Uani 1 1 d . . . . .
C6 C 0.33457(15) 0.53149(14) 0.05006(14) 0.0341(7) Uani 1 1 d . . . . .
C7 C 0.35378(16) 0.57509(16) 0.00353(15) 0.0414(7) Uani 1 1 d . . . . .
H7 H 0.3813 0.5618 -0.0293 0.050 Uiso 1 1 calc R U . . .
C8 C 0.33291(17) 0.63776(15) 0.00505(15) 0.0428(8) Uani 1 1 d . . . . .
C9 C 0.29373(17) 0.65712(15) 0.05457(17) 0.0468(8) Uani 1 1 d . . . . .
H9 H 0.2804 0.6994 0.0561 0.056 Uiso 1 1 calc R U . . .
C10 C 0.27311(15) 0.61579(14) 0.10287(14) 0.0367(7) Uani 1 1 d . . . . .
C11 C 0.23039(19) 0.63776(18) 0.15733(18) 0.0571(10) Uani 1 1 d . . . . .
H11A H 0.1883 0.6178 0.1541 0.086 Uiso 1 1 calc R U . . .
H11B H 0.2253 0.6832 0.1553 0.086 Uiso 1 1 calc R U . . .
H11C H 0.2503 0.6263 0.1973 0.086 Uiso 1 1 calc R U . . .
C12 C 0.35727(17) 0.46355(14) 0.04899(15) 0.0431(8) Uani 1 1 d . . . . .
H12A H 0.3858 0.4560 0.0847 0.065 Uiso 1 1 calc R U . . .
H12B H 0.3803 0.4554 0.0098 0.065 Uiso 1 1 calc R U . . .
H12C H 0.3202 0.4357 0.0518 0.065 Uiso 1 1 calc R U . . .
C13 C 0.3538(2) 0.68357(18) -0.04732(18) 0.0657(12) Uani 1 1 d . . . . .
H13A H 0.4002 0.6896 -0.0455 0.099 Uiso 1 1 calc R U . . .
H13B H 0.3323 0.7238 -0.0413 0.099 Uiso 1 1 calc R U . . .
H13C H 0.3421 0.6663 -0.0883 0.099 Uiso 1 1 calc R U . . .
C14 C 0.27393(13) 0.42417(14) 0.29373(13) 0.0310(6) Uani 1 1 d . . . . .
C15 C 0.30246(15) 0.36446(15) 0.29972(15) 0.0376(7) Uani 1 1 d . . . . .
C16 C 0.31209(16) 0.34052(16) 0.36135(16) 0.0464(8) Uani 1 1 d . . . . .
H16 H 0.3311 0.3006 0.3663 0.056 Uiso 1 1 calc R U . . .
C17 C 0.29410(16) 0.37450(17) 0.41507(16) 0.0440(8) Uani 1 1 d . . . . .
C18 C 0.26626(15) 0.43417(16) 0.40748(15) 0.0403(7) Uani 1 1 d . . . . .
H18 H 0.2546 0.4575 0.4436 0.048 Uiso 1 1 calc R U . . .
C19 C 0.25534(14) 0.46006(14) 0.34688(15) 0.0354(7) Uani 1 1 d . . . . .
C20 C 0.22531(18) 0.52464(16) 0.33847(17) 0.0494(9) Uani 1 1 d . . . . .
H20A H 0.2130 0.5414 0.3795 0.074 Uiso 1 1 calc R U . . .
H20B H 0.1873 0.5212 0.3118 0.074 Uiso 1 1 calc R U . . .
H20C H 0.2564 0.5527 0.3187 0.074 Uiso 1 1 calc R U . . .
C21 C 0.3234(2) 0.32754(19) 0.24123(18) 0.0606(10) Uani 1 1 d . . . . .
H21A H 0.3461 0.2897 0.2543 0.091 Uiso 1 1 calc R U . . .
H21B H 0.3518 0.3534 0.2156 0.091 Uiso 1 1 calc R U . . .
H21C H 0.2856 0.3160 0.2167 0.091 Uiso 1 1 calc R U . . .
C22 C 0.3060(2) 0.3475(2) 0.48103(18) 0.0676(12) Uani 1 1 d . . . . .
H22A H 0.2875 0.3056 0.4837 0.101 Uiso 1 1 calc R U . . .
H22B H 0.2859 0.3745 0.5125 0.101 Uiso 1 1 calc R U . . .
H22C H 0.3521 0.3452 0.4889 0.101 Uiso 1 1 calc R U . . .
C23 C 0.47281(16) 0.76721(14) 0.29607(16) 0.0405(7) Uani 1 1 d . . . . .
H23 H 0.4665 0.7957 0.3296 0.049 Uiso 1 1 calc R U . . .
C24 C 0.49686(16) 0.78142(13) 0.23868(15) 0.0382(7) Uani 1 1 d . . . . .
H24 H 0.5104 0.8215 0.2251 0.046 Uiso 1 1 calc R U . . .
C25 C 0.52389(14) 0.71995(13) 0.13904(13) 0.0295(6) Uani 1 1 d . . . . .
C26 C 0.58210(14) 0.68720(13) 0.12938(14) 0.0311(6) Uani 1 1 d . . . . .
C27 C 0.60661(15) 0.68285(14) 0.06732(15) 0.0364(7) Uani 1 1 d . . . . .
H27 H 0.6453 0.6608 0.0603 0.044 Uiso 1 1 calc R U . . .
C28 C 0.57472(17) 0.71065(14) 0.01567(15) 0.0397(7) Uani 1 1 d . . . . .
C29 C 0.51703(17) 0.74320(15) 0.02697(15) 0.0430(8) Uani 1 1 d . . . . .
H29 H 0.4956 0.7624 -0.0072 0.052 Uiso 1 1 calc R U . . .
C30 C 0.49013(15) 0.74809(14) 0.08817(15) 0.0373(7) Uani 1 1 d . . . . .
C31 C 0.42616(17) 0.78192(18) 0.09878(17) 0.0524(9) Uani 1 1 d . . . . .
H31A H 0.4338 0.8209 0.1215 0.079 Uiso 1 1 calc R U . . .
H31B H 0.3976 0.7552 0.1234 0.079 Uiso 1 1 calc R U . . .
H31C H 0.4063 0.7912 0.0582 0.079 Uiso 1 1 calc R U . . .
C32 C 0.6028(2) 0.70581(17) -0.05119(16) 0.0548(10) Uani 1 1 d . . . . .
H32A H 0.5682 0.7088 -0.0820 0.082 Uiso 1 1 calc R U . . .
H32B H 0.6248 0.6657 -0.0560 0.082 Uiso 1 1 calc R U . . .
H32C H 0.6334 0.7398 -0.0579 0.082 Uiso 1 1 calc R U . . .
C33 C 0.61822(14) 0.65602(14) 0.18366(15) 0.0374(7) Uani 1 1 d . . . . .
H33A H 0.6166 0.6830 0.2207 0.056 Uiso 1 1 calc R U . . .
H33B H 0.6629 0.6493 0.1715 0.056 Uiso 1 1 calc R U . . .
H33C H 0.5982 0.6158 0.1934 0.056 Uiso 1 1 calc R U . . .
C34 C 0.43830(15) 0.66656(13) 0.35178(14) 0.0320(6) Uani 1 1 d . . . . .
C35 C 0.48523(15) 0.63538(14) 0.38889(14) 0.0354(7) Uani 1 1 d . . . . .
C36 C 0.46401(17) 0.60071(15) 0.44156(15) 0.0425(8) Uani 1 1 d . . . . .
H36 H 0.4947 0.5801 0.4670 0.051 Uiso 1 1 calc R U . . .
C37 C 0.39872(18) 0.59597(15) 0.45731(15) 0.0437(8) Uani 1 1 d . . . . .
C38 C 0.35350(17) 0.62692(16) 0.41916(16) 0.0446(8) Uani 1 1 d . . . . .
H38 H 0.3094 0.6241 0.4295 0.054 Uiso 1 1 calc R U . . .
C39 C 0.37207(15) 0.66220(14) 0.36571(15) 0.0377(7) Uani 1 1 d . . . . .
C40 C 0.32254(17) 0.69283(18) 0.32196(18) 0.0546(9) Uani 1 1 d . . . . .
H40A H 0.3302 0.7379 0.3203 0.082 Uiso 1 1 calc R U . . .
H40B H 0.2794 0.6849 0.3380 0.082 Uiso 1 1 calc R U . . .
H40C H 0.3266 0.6752 0.2798 0.082 Uiso 1 1 calc R U . . .
C41 C 0.55582(16) 0.63750(19) 0.36976(17) 0.0503(9) Uani 1 1 d . . . . .
H41A H 0.5822 0.6207 0.4038 0.075 Uiso 1 1 calc R U . . .
H41B H 0.5683 0.6808 0.3614 0.075 Uiso 1 1 calc R U . . .
H41C H 0.5621 0.6124 0.3318 0.075 Uiso 1 1 calc R U . . .
C42 C 0.3771(2) 0.55595(19) 0.51330(17) 0.0617(11) Uani 1 1 d . . . . .
H42A H 0.3776 0.5118 0.5014 0.093 Uiso 1 1 calc R U . . .
H42B H 0.3335 0.5679 0.5255 0.093 Uiso 1 1 calc R U . . .
H42C H 0.4062 0.5626 0.5487 0.093 Uiso 1 1 calc R U . . .
C43 C 0.55192(15) 0.47439(17) 0.30161(18) 0.0485(9) Uani 1 1 d . . . . .
H43A H 0.5671 0.4961 0.3392 0.073 Uiso 1 1 calc R U . . .
H43B H 0.5737 0.4912 0.2646 0.073 Uiso 1 1 calc R U . . .
H43C H 0.5612 0.4297 0.3054 0.073 Uiso 1 1 calc R U . . .
C44 C 0.44752(15) 0.45586(15) 0.34875(15) 0.0387(7) Uani 1 1 d . . . . .
H44A H 0.4554 0.4108 0.3498 0.058 Uiso 1 1 calc R U . . .
H44B H 0.4015 0.4636 0.3444 0.058 Uiso 1 1 calc R U . . .
H44C H 0.4629 0.4748 0.3878 0.058 Uiso 1 1 calc R U . . .
C45 C 0.51081(18) 0.42830(15) 0.14762(17) 0.0466(8) Uani 1 1 d . . . . .
H45A H 0.4972 0.4117 0.1069 0.070 Uiso 1 1 calc R U . . .
H45B H 0.4897 0.4050 0.1813 0.070 Uiso 1 1 calc R U . . .
H45C H 0.5573 0.4240 0.1517 0.070 Uiso 1 1 calc R U . . .
C46 C 0.51952(18) 0.53035(15) 0.09831(15) 0.0444(8) Uani 1 1 d . . . . .
H46A H 0.5664 0.5289 0.0997 0.067 Uiso 1 1 calc R U . . .
H46B H 0.5053 0.5738 0.1007 0.067 Uiso 1 1 calc R U . . .
H46C H 0.5045 0.5118 0.0590 0.067 Uiso 1 1 calc R U . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N1 1.847(2) . ?
Ti1 N2 1.858(2) . ?
Ti1 N4 1.927(2) . ?
Ti1 N3 1.930(2) . ?
N1 C1 1.278(3) . ?
N2 C2 1.273(3) . ?
N3 C44 1.445(4) . ?
N3 C43 1.457(4) . ?
N4 C45 1.450(4) . ?
N4 C46 1.451(4) . ?
N5 C3 1.387(4) . ?
N5 C1 1.390(3) . ?
N5 C14 1.426(3) . ?
N6 C1 1.392(3) . ?
N6 C4 1.394(4) . ?
N6 C5 1.430(3) . ?
N7 C2 1.390(4) . ?
N7 C23 1.391(3) . ?
N7 C34 1.429(4) . ?
N8 C24 1.395(3) . ?
N8 C2 1.398(3) . ?
N8 C25 1.429(3) . ?
C3 C4 1.331(4) . ?
C3 H3 0.9300 . ?
C4 H4 0.9300 . ?
C5 C10 1.388(4) . ?
C5 C6 1.394(4) . ?
C6 C7 1.392(4) . ?
C6 C12 1.501(4) . ?
C7 C8 1.384(4) . ?
C7 H7 0.9300 . ?
C8 C9 1.371(5) . ?
C8 C13 1.518(4) . ?
C9 C10 1.396(4) . ?
C9 H9 0.9300 . ?
C10 C11 1.507(4) . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 C15 1.389(4) . ?
C14 C19 1.395(4) . ?
C15 C16 1.396(4) . ?
C15 C21 1.509(5) . ?
C16 C17 1.380(5) . ?
C16 H16 0.9300 . ?
C17 C18 1.386(4) . ?
C17 C22 1.510(4) . ?
C18 C19 1.396(4) . ?
C18 H18 0.9300 . ?
C19 C20 1.499(4) . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
C23 C24 1.330(4) . ?
C23 H23 0.9300 . ?
C24 H24 0.9300 . ?
C25 C26 1.391(4) . ?
C25 C30 1.399(4) . ?
C26 C27 1.393(4) . ?
C26 C33 1.504(4) . ?
C27 C28 1.390(4) . ?
C27 H27 0.9300 . ?
C28 C29 1.385(5) . ?
C28 C32 1.514(4) . ?
C29 C30 1.396(4) . ?
C29 H29 0.9300 . ?
C30 C31 1.506(4) . ?
C31 H31A 0.9600 . ?
C31 H31B 0.9600 . ?
C31 H31C 0.9600 . ?
C32 H32A 0.9600 . ?
C32 H32B 0.9600 . ?
C32 H32C 0.9600 . ?
C33 H33A 0.9600 . ?
C33 H33B 0.9600 . ?
C33 H33C 0.9600 . ?
C34 C39 1.390(4) . ?
C34 C35 1.397(4) . ?
C35 C36 1.389(4) . ?
C35 C41 1.500(4) . ?
C36 C37 1.380(5) . ?
C36 H36 0.9300 . ?
C37 C38 1.384(5) . ?
C37 C42 1.507(4) . ?
C38 C39 1.393(4) . ?
C38 H38 0.9300 . ?
C39 C40 1.509(4) . ?
C40 H40A 0.9600 . ?
C40 H40B 0.9600 . ?
C40 H40C 0.9600 . ?
C41 H41A 0.9600 . ?
C41 H41B 0.9600 . ?
C41 H41C 0.9600 . ?
C42 H42A 0.9600 . ?
C42 H42B 0.9600 . ?
C42 H42C 0.9600 . ?
C43 H43A 0.9600 . ?
C43 H43B 0.9600 . ?
C43 H43C 0.9600 . ?
C44 H44A 0.9600 . ?
C44 H44B 0.9600 . ?
C44 H44C 0.9600 . ?
C45 H45A 0.9600 . ?
C45 H45B 0.9600 . ?
C45 H45C 0.9600 . ?
C46 H46A 0.9600 . ?
C46 H46B 0.9600 . ?
C46 H46C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 N2 113.94(11) . . ?
N1 Ti1 N4 114.02(11) . . ?
N2 Ti1 N4 104.56(10) . . ?
N1 Ti1 N3 106.40(10) . . ?
N2 Ti1 N3 115.12(11) . . ?
N4 Ti1 N3 102.42(11) . . ?
C1 N1 Ti1 157.6(2) . . ?
C2 N2 Ti1 161.9(2) . . ?
C44 N3 C43 110.6(2) . . ?
C44 N3 Ti1 128.8(2) . . ?
C43 N3 Ti1 120.6(2) . . ?
C45 N4 C46 110.6(2) . . ?
C45 N4 Ti1 123.4(2) . . ?
C46 N4 Ti1 125.84(19) . . ?
C3 N5 C1 110.6(2) . . ?
C3 N5 C14 125.6(2) . . ?
C1 N5 C14 123.7(2) . . ?
C1 N6 C4 110.0(2) . . ?
C1 N6 C5 124.5(2) . . ?
C4 N6 C5 125.5(2) . . ?
C2 N7 C23 110.2(2) . . ?
C2 N7 C34 123.3(2) . . ?
C23 N7 C34 126.1(2) . . ?
C24 N8 C2 109.8(2) . . ?
C24 N8 C25 125.5(2) . . ?
C2 N8 C25 124.5(2) . . ?
N1 C1 N5 127.4(3) . . ?
N1 C1 N6 129.0(3) . . ?
N5 C1 N6 103.6(2) . . ?
N2 C2 N7 127.8(3) . . ?
N2 C2 N8 128.4(3) . . ?
N7 C2 N8 103.8(2) . . ?
C4 C3 N5 107.8(3) . . ?
C4 C3 H3 126.1 . . ?
N5 C3 H3 126.1 . . ?
C3 C4 N6 108.0(3) . . ?
C3 C4 H4 126.0 . . ?
N6 C4 H4 126.0 . . ?
C10 C5 C6 122.2(3) . . ?
C10 C5 N6 119.1(3) . . ?
C6 C5 N6 118.7(3) . . ?
C7 C6 C5 117.9(3) . . ?
C7 C6 C12 121.8(3) . . ?
C5 C6 C12 120.2(3) . . ?
C8 C7 C6 121.5(3) . . ?
C8 C7 H7 119.3 . . ?
C6 C7 H7 119.3 . . ?
C9 C8 C7 118.7(3) . . ?
C9 C8 C13 121.4(3) . . ?
C7 C8 C13 119.9(3) . . ?
C8 C9 C10 122.6(3) . . ?
C8 C9 H9 118.7 . . ?
C10 C9 H9 118.7 . . ?
C5 C10 C9 117.1(3) . . ?
C5 C10 C11 120.8(3) . . ?
C9 C10 C11 122.1(3) . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C6 C12 H12A 109.5 . . ?
C6 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C6 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C8 C13 H13A 109.5 . . ?
C8 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C8 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C15 C14 C19 122.1(3) . . ?
C15 C14 N5 119.2(3) . . ?
C19 C14 N5 118.7(3) . . ?
C14 C15 C16 117.9(3) . . ?
C14 C15 C21 120.7(3) . . ?
C16 C15 C21 121.4(3) . . ?
C17 C16 C15 121.7(3) . . ?
C17 C16 H16 119.1 . . ?
C15 C16 H16 119.1 . . ?
C16 C17 C18 119.0(3) . . ?
C16 C17 C22 120.3(3) . . ?
C18 C17 C22 120.7(3) . . ?
C17 C18 C19 121.5(3) . . ?
C17 C18 H18 119.3 . . ?
C19 C18 H18 119.3 . . ?
C14 C19 C18 117.9(3) . . ?
C14 C19 C20 120.5(3) . . ?
C18 C19 C20 121.6(3) . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C19 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C15 C21 H21A 109.5 . . ?
C15 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C15 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C17 C22 H22A 109.5 . . ?
C17 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C17 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C24 C23 N7 108.2(3) . . ?
C24 C23 H23 125.9 . . ?
N7 C23 H23 125.9 . . ?
C23 C24 N8 108.0(3) . . ?
C23 C24 H24 126.0 . . ?
N8 C24 H24 126.0 . . ?
C26 C25 C30 121.5(3) . . ?
C26 C25 N8 119.4(2) . . ?
C30 C25 N8 119.1(3) . . ?
C25 C26 C27 118.4(3) . . ?
C25 C26 C33 121.8(3) . . ?
C27 C26 C33 119.7(3) . . ?
C28 C27 C26 121.7(3) . . ?
C28 C27 H27 119.1 . . ?
C26 C27 H27 119.1 . . ?
C29 C28 C27 118.4(3) . . ?
C29 C28 C32 121.0(3) . . ?
C27 C28 C32 120.6(3) . . ?
C28 C29 C30 121.9(3) . . ?
C28 C29 H29 119.0 . . ?
C30 C29 H29 119.0 . . ?
C29 C30 C25 118.0(3) . . ?
C29 C30 C31 120.8(3) . . ?
C25 C30 C31 121.1(3) . . ?
C30 C31 H31A 109.5 . . ?
C30 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
C30 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
C28 C32 H32A 109.5 . . ?
C28 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
C28 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
C26 C33 H33A 109.5 . . ?
C26 C33 H33B 109.5 . . ?
H33A C33 H33B 109.5 . . ?
C26 C33 H33C 109.5 . . ?
H33A C33 H33C 109.5 . . ?
H33B C33 H33C 109.5 . . ?
C39 C34 C35 121.6(3) . . ?
C39 C34 N7 119.1(3) . . ?
C35 C34 N7 119.3(3) . . ?
C36 C35 C34 118.0(3) . . ?
C36 C35 C41 121.9(3) . . ?
C34 C35 C41 120.1(3) . . ?
C37 C36 C35 122.0(3) . . ?
C37 C36 H36 119.0 . . ?
C35 C36 H36 119.0 . . ?
C36 C37 C38 118.5(3) . . ?
C36 C37 C42 120.7(3) . . ?
C38 C37 C42 120.8(3) . . ?
C37 C38 C39 121.9(3) . . ?
C37 C38 H38 119.0 . . ?
C39 C38 H38 119.0 . . ?
C34 C39 C38 118.0(3) . . ?
C34 C39 C40 120.1(3) . . ?
C38 C39 C40 121.9(3) . . ?
C39 C40 H40A 109.5 . . ?
C39 C40 H40B 109.5 . . ?
H40A C40 H40B 109.5 . . ?
C39 C40 H40C 109.5 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
C35 C41 H41A 109.5 . . ?
C35 C41 H41B 109.5 . . ?
H41A C41 H41B 109.5 . . ?
C35 C41 H41C 109.5 . . ?
H41A C41 H41C 109.5 . . ?
H41B C41 H41C 109.5 . . ?
C37 C42 H42A 109.5 . . ?
C37 C42 H42B 109.5 . . ?
H42A C42 H42B 109.5 . . ?
C37 C42 H42C 109.5 . . ?
H42A C42 H42C 109.5 . . ?
H42B C42 H42C 109.5 . . ?
N3 C43 H43A 109.5 . . ?
N3 C43 H43B 109.5 . . ?
H43A C43 H43B 109.5 . . ?
N3 C43 H43C 109.5 . . ?
H43A C43 H43C 109.5 . . ?
H43B C43 H43C 109.5 . . ?
N3 C44 H44A 109.5 . . ?
N3 C44 H44B 109.5 . . ?
H44A C44 H44B 109.5 . . ?
N3 C44 H44C 109.5 . . ?
H44A C44 H44C 109.5 . . ?
H44B C44 H44C 109.5 . . ?
N4 C45 H45A 109.5 . . ?
N4 C45 H45B 109.5 . . ?
H45A C45 H45B 109.5 . . ?
N4 C45 H45C 109.5 . . ?
H45A C45 H45C 109.5 . . ?
H45B C45 H45C 109.5 . . ?
N4 C46 H46A 109.5 . . ?
N4 C46 H46B 109.5 . . ?
H46A C46 H46B 109.5 . . ?
N4 C46 H46C 109.5 . . ?
H46A C46 H46C 109.5 . . ?
H46B C46 H46C 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
N2 Ti1 N1 C1 118.5(6) . . . . ?
N4 Ti1 N1 C1 -1.4(6) . . . . ?
N3 Ti1 N1 C1 -113.5(6) . . . . ?
N1 Ti1 N2 C2 67.6(7) . . . . ?
N4 Ti1 N2 C2 -167.2(7) . . . . ?
N3 Ti1 N2 C2 -55.7(8) . . . . ?
Ti1 N1 C1 N5 118.8(5) . . . . ?
Ti1 N1 C1 N6 -61.6(7) . . . . ?
C3 N5 C1 N1 -179.3(3) . . . . ?
C14 N5 C1 N1 4.3(5) . . . . ?
C3 N5 C1 N6 1.1(3) . . . . ?
C14 N5 C1 N6 -175.4(2) . . . . ?
C4 N6 C1 N1 179.3(3) . . . . ?
C5 N6 C1 N1 -1.0(5) . . . . ?
C4 N6 C1 N5 -1.0(3) . . . . ?
C5 N6 C1 N5 178.6(3) . . . . ?
Ti1 N2 C2 N7 4.3(10) . . . . ?
Ti1 N2 C2 N8 -175.6(5) . . . . ?
C23 N7 C2 N2 -179.9(3) . . . . ?
C34 N7 C2 N2 6.6(5) . . . . ?
C23 N7 C2 N8 0.1(3) . . . . ?
C34 N7 C2 N8 -173.4(3) . . . . ?
C24 N8 C2 N2 180.0(3) . . . . ?
C25 N8 C2 N2 -3.5(5) . . . . ?
C24 N8 C2 N7 0.0(3) . . . . ?
C25 N8 C2 N7 176.6(2) . . . . ?
C1 N5 C3 C4 -0.7(4) . . . . ?
C14 N5 C3 C4 175.6(3) . . . . ?
N5 C3 C4 N6 0.0(4) . . . . ?
C1 N6 C4 C3 0.6(4) . . . . ?
C5 N6 C4 C3 -179.0(3) . . . . ?
C1 N6 C5 C10 -92.1(3) . . . . ?
C4 N6 C5 C10 87.5(4) . . . . ?
C1 N6 C5 C6 88.9(4) . . . . ?
C4 N6 C5 C6 -91.5(4) . . . . ?
C10 C5 C6 C7 -1.8(4) . . . . ?
N6 C5 C6 C7 177.1(3) . . . . ?
C10 C5 C6 C12 177.7(3) . . . . ?
N6 C5 C6 C12 -3.3(4) . . . . ?
C5 C6 C7 C8 -0.1(5) . . . . ?
C12 C6 C7 C8 -179.6(3) . . . . ?
C6 C7 C8 C9 1.6(5) . . . . ?
C6 C7 C8 C13 -178.8(3) . . . . ?
C7 C8 C9 C10 -1.2(5) . . . . ?
C13 C8 C9 C10 179.1(3) . . . . ?
C6 C5 C10 C9 2.2(4) . . . . ?
N6 C5 C10 C9 -176.8(3) . . . . ?
C6 C5 C10 C11 -178.0(3) . . . . ?
N6 C5 C10 C11 3.0(4) . . . . ?
C8 C9 C10 C5 -0.6(5) . . . . ?
C8 C9 C10 C11 179.6(3) . . . . ?
C3 N5 C14 C15 85.0(4) . . . . ?
C1 N5 C14 C15 -99.0(3) . . . . ?
C3 N5 C14 C19 -94.3(4) . . . . ?
C1 N5 C14 C19 81.6(4) . . . . ?
C19 C14 C15 C16 0.3(5) . . . . ?
N5 C14 C15 C16 -179.1(3) . . . . ?
C19 C14 C15 C21 -178.6(3) . . . . ?
N5 C14 C15 C21 2.1(4) . . . . ?
C14 C15 C16 C17 0.0(5) . . . . ?
C21 C15 C16 C17 178.9(3) . . . . ?
C15 C16 C17 C18 -0.6(5) . . . . ?
C15 C16 C17 C22 -179.3(3) . . . . ?
C16 C17 C18 C19 0.9(5) . . . . ?
C22 C17 C18 C19 179.6(3) . . . . ?
C15 C14 C19 C18 0.0(4) . . . . ?
N5 C14 C19 C18 179.4(3) . . . . ?
C15 C14 C19 C20 179.4(3) . . . . ?
N5 C14 C19 C20 -1.3(4) . . . . ?
C17 C18 C19 C14 -0.6(5) . . . . ?
C17 C18 C19 C20 -179.9(3) . . . . ?
C2 N7 C23 C24 -0.1(4) . . . . ?
C34 N7 C23 C24 173.2(3) . . . . ?
N7 C23 C24 N8 0.1(4) . . . . ?
C2 N8 C24 C23 0.0(4) . . . . ?
C25 N8 C24 C23 -176.6(3) . . . . ?
C24 N8 C25 C26 108.6(3) . . . . ?
C2 N8 C25 C26 -67.5(4) . . . . ?
C24 N8 C25 C30 -70.7(4) . . . . ?
C2 N8 C25 C30 113.2(3) . . . . ?
C30 C25 C26 C27 0.0(4) . . . . ?
N8 C25 C26 C27 -179.3(2) . . . . ?
C30 C25 C26 C33 -179.1(3) . . . . ?
N8 C25 C26 C33 1.6(4) . . . . ?
C25 C26 C27 C28 0.5(4) . . . . ?
C33 C26 C27 C28 179.7(3) . . . . ?
C26 C27 C28 C29 -0.2(5) . . . . ?
C26 C27 C28 C32 179.3(3) . . . . ?
C27 C28 C29 C30 -0.7(5) . . . . ?
C32 C28 C29 C30 179.8(3) . . . . ?
C28 C29 C30 C25 1.2(5) . . . . ?
C28 C29 C30 C31 -177.9(3) . . . . ?
C26 C25 C30 C29 -0.9(4) . . . . ?
N8 C25 C30 C29 178.4(3) . . . . ?
C26 C25 C30 C31 178.3(3) . . . . ?
N8 C25 C30 C31 -2.4(4) . . . . ?
C2 N7 C34 C39 -98.8(3) . . . . ?
C23 N7 C34 C39 88.7(4) . . . . ?
C2 N7 C34 C35 79.5(4) . . . . ?
C23 N7 C34 C35 -92.9(4) . . . . ?
C39 C34 C35 C36 -1.5(4) . . . . ?
N7 C34 C35 C36 -179.8(3) . . . . ?
C39 C34 C35 C41 175.8(3) . . . . ?
N7 C34 C35 C41 -2.5(4) . . . . ?
C34 C35 C36 C37 0.7(5) . . . . ?
C41 C35 C36 C37 -176.6(3) . . . . ?
C35 C36 C37 C38 0.0(5) . . . . ?
C35 C36 C37 C42 177.7(3) . . . . ?
C36 C37 C38 C39 0.2(5) . . . . ?
C42 C37 C38 C39 -177.5(3) . . . . ?
C35 C34 C39 C38 1.6(4) . . . . ?
N7 C34 C39 C38 180.0(3) . . . . ?
C35 C34 C39 C40 -175.8(3) . . . . ?
N7 C34 C39 C40 2.5(4) . . . . ?
C37 C38 C39 C34 -1.0(5) . . . . ?
C37 C38 C39 C40 176.4(3) . . . . ?

_refine_diff_density_max         0.326
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.057

