# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

####################################################################### 
# 
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1495489'
_audit_update_record             
;
2016-12-27 deposited with the CCDC.
2017-01-11 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         ?
_chemical_formula_sum            'C34 H68 Cl14 N6 O12 Ti3'
_chemical_formula_weight         1392.94

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 '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                   10.7343(6)
_cell_length_b                   11.1683(6)
_cell_length_c                   14.4997(12)
_cell_angle_alpha                106.064(5)
_cell_angle_beta                 102.815(5)
_cell_angle_gamma                104.401(4)
_cell_volume                     1537.03(18)
_cell_formula_units_Z            1
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4664
_cell_measurement_theta_min      2.1535
_cell_measurement_theta_max      26.9815

_exptl_crystal_description       needle
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_F_000             714
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    1.042
_shelx_estimated_absorpt_T_min   0.851
_shelx_estimated_absorpt_T_max   0.903
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8510
_exptl_absorpt_correction_T_max  0.9030
_exptl_absorpt_process_details   
; 
 Data were corrected for Lorentz polarization and absorption
 effects (empirical absorption correction SADABS).
 R(int) =  0.1045 (selected reflections only, before parameter refinement)
 R(int) =  0.0625 (selected reflections only, after parameter refinement)
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22419
_diffrn_reflns_av_unetI/netI     0.0732
_diffrn_reflns_av_R_equivalents  0.0753
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.538
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             6032
_reflns_number_gt                4044
_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       'APEX2 (Bruker AXS, 2006)'
_computing_cell_refinement       'APEX2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT (Bruker AXS, 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1996)'
_computing_publication_material  'XCIF (Bruker AXS, 2001)'
_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)+(0.0421P)²+0.7047P] 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         6032
_refine_ls_number_parameters     313
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0846
_refine_ls_R_factor_gt           0.0428
_refine_ls_wR_factor_ref         0.1075
_refine_ls_wR_factor_gt          0.0886
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_restrained_S_all      1.020
_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
C1 C 0.2937(4) 0.5440(4) 0.1010(3) 0.0199(8) Uani 1 1 d . . . . .
C2 C 0.4996(4) 0.5159(4) 0.1868(3) 0.0297(9) Uani 1 1 d . . . . .
H2A H 0.5386 0.6134 0.2169 0.036 Uiso 1 1 calc R U . . .
H2B H 0.5698 0.4823 0.1657 0.036 Uiso 1 1 calc R U . . .
C3 C 0.4645(5) 0.4626(5) 0.2659(4) 0.0474(12) Uani 1 1 d . . . . .
H3A H 0.5460 0.4901 0.3236 0.071 Uiso 1 1 calc R U . . .
H3B H 0.3966 0.4971 0.2883 0.071 Uiso 1 1 calc R U . . .
H3C H 0.4278 0.3660 0.2371 0.071 Uiso 1 1 calc R U . . .
C4 C 0.3584(4) 0.3661(4) 0.0049(3) 0.0262(9) Uani 1 1 d . . . . .
H4A H 0.4466 0.3558 0.0021 0.031 Uiso 1 1 calc R U . . .
H4B H 0.3193 0.3859 -0.0554 0.031 Uiso 1 1 calc R U . . .
C5 C 0.2651(4) 0.2370(4) 0.0006(3) 0.0348(10) Uani 1 1 d . . . . .
H5A H 0.2540 0.1666 -0.0617 0.052 Uiso 1 1 calc R U . . .
H5B H 0.3041 0.2153 0.0591 0.052 Uiso 1 1 calc R U . . .
H5C H 0.1766 0.2455 0.0016 0.052 Uiso 1 1 calc R U . . .
C6 C 0.0595(3) 0.6882(4) 0.2081(3) 0.0187(8) Uani 1 1 d . . . . .
C7 C 0.0380(4) 0.8394(4) 0.3556(3) 0.0243(9) Uani 1 1 d . . . . .
H7A H 0.1378 0.8801 0.3792 0.029 Uiso 1 1 calc R U . . .
H7B H 0.0090 0.8306 0.4143 0.029 Uiso 1 1 calc R U . . .
C8 C -0.0255(4) 0.9283(4) 0.3144(3) 0.0338(10) Uani 1 1 d . . . . .
H8A H 0.0023 1.0150 0.3674 0.051 Uiso 1 1 calc R U . . .
H8B H 0.0044 0.9384 0.2570 0.051 Uiso 1 1 calc R U . . .
H8C H -0.1243 0.8890 0.2922 0.051 Uiso 1 1 calc R U . . .
C9 C -0.1120(4) 0.6003(4) 0.2803(3) 0.0271(9) Uani 1 1 d . . . . .
H9A H -0.1517 0.5305 0.2125 0.032 Uiso 1 1 calc R U . . .
H9B H -0.1838 0.6353 0.2963 0.032 Uiso 1 1 calc R U . . .
C10 C -0.0633(5) 0.5409(4) 0.3575(3) 0.0429(12) Uani 1 1 d . . . . .
H10A H -0.1395 0.4702 0.3565 0.064 Uiso 1 1 calc R U . . .
H10B H 0.0066 0.5046 0.3412 0.064 Uiso 1 1 calc R U . . .
H10C H -0.0254 0.6094 0.4249 0.064 Uiso 1 1 calc R U . . .
C11 C -0.1591(3) 0.2511(3) 0.0120(3) 0.0180(8) Uani 1 1 d . . . . .
C12 C -0.0308(4) 0.2394(4) 0.1685(3) 0.0269(9) Uani 1 1 d . . . . .
H12A H -0.0498 0.2509 0.2336 0.032 Uiso 1 1 calc R U . . .
H12B H 0.0340 0.3238 0.1747 0.032 Uiso 1 1 calc R U . . .
C13 C 0.0323(4) 0.1333(5) 0.1480(4) 0.0417(12) Uani 1 1 d . . . . .
H13A H 0.1161 0.1578 0.2032 0.063 Uiso 1 1 calc R U . . .
H13B H -0.0308 0.0499 0.1432 0.063 Uiso 1 1 calc R U . . .
H13C H 0.0530 0.1228 0.0843 0.063 Uiso 1 1 calc R U . . .
C14 C -0.2822(4) 0.1209(4) 0.0921(3) 0.0227(8) Uani 1 1 d . . . . .
H14A H -0.2590 0.0711 0.1365 0.027 Uiso 1 1 calc R U . . .
H14B H -0.3342 0.0563 0.0234 0.027 Uiso 1 1 calc R U . . .
C15 C -0.3693(4) 0.1979(4) 0.1310(3) 0.0295(9) Uani 1 1 d . . . . .
H15A H -0.4517 0.1368 0.1320 0.044 Uiso 1 1 calc R U . . .
H15B H -0.3187 0.2608 0.1995 0.044 Uiso 1 1 calc R U . . .
H15C H -0.3939 0.2460 0.0865 0.044 Uiso 1 1 calc R U . . .
C16 C 0.6783(4) 0.1773(4) 0.4072(3) 0.0292(9) Uani 1 1 d . . . . .
H16A H 0.6032 0.1267 0.3433 0.035 Uiso 1 1 calc R U . . .
H16B H 0.6685 0.1298 0.4549 0.035 Uiso 1 1 calc R U . . .
C17 C 0.6736(5) 0.7970(5) 0.5257(4) 0.0405(11) Uani 1 1 d . . . . .
H17A H 0.6886 0.8722 0.5872 0.049 Uiso 1 1 calc R U . . .
H17B H 0.5747 0.7539 0.4929 0.049 Uiso 1 1 calc R U . . .
Cl1 Cl 0.33783(9) 1.04198(9) 0.21945(7) 0.0235(2) Uani 1 1 d . . . . .
Cl2 Cl 0.41013(9) 0.87641(9) 0.37481(7) 0.0238(2) Uani 1 1 d . . . . .
Cl3 Cl 0.55275(9) 0.86903(9) 0.19062(7) 0.0226(2) Uani 1 1 d . . . . .
Cl4 Cl 0.83442(10) 0.18662(10) 0.38362(8) 0.0308(2) Uani 1 1 d . . . . .
Cl5 Cl 0.66798(11) 0.33617(11) 0.45833(10) 0.0419(3) Uani 1 1 d . . . . .
Cl6 Cl 0.74588(11) 0.85638(11) 0.44232(8) 0.0380(3) Uani 1 1 d . . . . .
Cl7 Cl 0.74384(15) 0.68339(13) 0.56005(11) 0.0619(4) Uani 1 1 d . . . . .
N1 N 0.3817(3) 0.4789(3) 0.0964(2) 0.0212(7) Uani 1 1 d . . . . .
N2 N -0.0009(3) 0.7077(3) 0.2786(2) 0.0198(7) Uani 1 1 d . . . . .
N3 N -0.1560(3) 0.2086(3) 0.0889(2) 0.0193(7) Uani 1 1 d . . . . .
O1 O 0.3172(2) 0.6428(2) 0.18044(18) 0.0192(5) Uani 1 1 d . . . . .
O2 O 0.1866(2) 0.5039(2) 0.02348(18) 0.0190(5) Uani 1 1 d . . . . .
O3 O 0.1505(2) 0.7877(2) 0.20740(18) 0.0182(5) Uani 1 1 d . . . . .
O4 O 0.0257(2) 0.5706(2) 0.14282(18) 0.0183(5) Uani 1 1 d . . . . .
O5 O -0.0465(2) 0.3264(2) 0.00961(18) 0.0181(5) Uani 1 1 d . . . . .
O6 O 0.2714(2) 0.7815(2) 0.05684(18) 0.0200(6) Uani 1 1 d . . . . .
Ti1 Ti 0.0000 0.5000 0.0000 0.0168(2) Uani 1 2 d S . P . .
Ti2 Ti 0.33807(6) 0.83117(6) 0.20479(5) 0.01739(16) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 O1 1.279(4) . ?
C1 O2 1.295(4) . ?
C1 N1 1.329(4) . ?
C2 N1 1.482(5) . ?
C2 C3 1.506(6) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 N1 1.477(5) . ?
C4 C5 1.513(5) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
C6 O3 1.288(4) . ?
C6 O4 1.294(4) . ?
C6 N2 1.325(4) . ?
C7 N2 1.471(4) . ?
C7 C8 1.514(5) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 N2 1.476(4) . ?
C9 C10 1.514(6) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 O6 1.277(4) 2_565 ?
C11 O5 1.303(4) . ?
C11 N3 1.324(4) . ?
C12 N3 1.456(4) . ?
C12 C13 1.499(5) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 N3 1.479(4) . ?
C14 C15 1.517(5) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 Cl5 1.766(4) . ?
C16 Cl4 1.767(4) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 Cl7 1.757(4) . ?
C17 Cl6 1.763(4) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
Cl1 Ti2 2.3054(11) . ?
Cl2 Ti2 2.2805(11) . ?
Cl3 Ti2 2.3033(10) . ?
O1 Ti2 1.980(2) . ?
O2 Ti1 1.943(2) . ?
O3 Ti2 1.962(2) . ?
O4 Ti1 1.929(2) . ?
O5 Ti1 1.930(2) . ?
O6 C11 1.276(4) 2_565 ?
O6 Ti2 1.971(2) . ?
Ti1 O4 1.929(2) 2_565 ?
Ti1 O5 1.930(2) 2_565 ?
Ti1 O2 1.943(2) 2_565 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 O2 122.6(3) . . ?
O1 C1 N1 119.6(3) . . ?
O2 C1 N1 117.8(3) . . ?
N1 C2 C3 113.1(3) . . ?
N1 C2 H2A 109.0 . . ?
C3 C2 H2A 109.0 . . ?
N1 C2 H2B 109.0 . . ?
C3 C2 H2B 109.0 . . ?
H2A C2 H2B 107.8 . . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N1 C4 C5 113.6(3) . . ?
N1 C4 H4A 108.8 . . ?
C5 C4 H4A 108.8 . . ?
N1 C4 H4B 108.8 . . ?
C5 C4 H4B 108.8 . . ?
H4A C4 H4B 107.7 . . ?
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 . . ?
O3 C6 O4 122.4(3) . . ?
O3 C6 N2 118.4(3) . . ?
O4 C6 N2 119.1(3) . . ?
N2 C7 C8 111.5(3) . . ?
N2 C7 H7A 109.3 . . ?
C8 C7 H7A 109.3 . . ?
N2 C7 H7B 109.3 . . ?
C8 C7 H7B 109.3 . . ?
H7A C7 H7B 108.0 . . ?
C7 C8 H8A 109.5 . . ?
C7 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C7 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
N2 C9 C10 111.7(3) . . ?
N2 C9 H9A 109.3 . . ?
C10 C9 H9A 109.3 . . ?
N2 C9 H9B 109.3 . . ?
C10 C9 H9B 109.3 . . ?
H9A C9 H9B 107.9 . . ?
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 . . ?
O6 C11 O5 121.9(3) 2_565 . ?
O6 C11 N3 119.5(3) 2_565 . ?
O5 C11 N3 118.6(3) . . ?
N3 C12 C13 112.1(3) . . ?
N3 C12 H12A 109.2 . . ?
C13 C12 H12A 109.2 . . ?
N3 C12 H12B 109.2 . . ?
C13 C12 H12B 109.2 . . ?
H12A C12 H12B 107.9 . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
N3 C14 C15 111.8(3) . . ?
N3 C14 H14A 109.3 . . ?
C15 C14 H14A 109.3 . . ?
N3 C14 H14B 109.3 . . ?
C15 C14 H14B 109.3 . . ?
H14A C14 H14B 107.9 . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
Cl5 C16 Cl4 111.2(2) . . ?
Cl5 C16 H16A 109.4 . . ?
Cl4 C16 H16A 109.4 . . ?
Cl5 C16 H16B 109.4 . . ?
Cl4 C16 H16B 109.4 . . ?
H16A C16 H16B 108.0 . . ?
Cl7 C17 Cl6 111.5(2) . . ?
Cl7 C17 H17A 109.3 . . ?
Cl6 C17 H17A 109.3 . . ?
Cl7 C17 H17B 109.3 . . ?
Cl6 C17 H17B 109.3 . . ?
H17A C17 H17B 108.0 . . ?
C1 N1 C4 120.7(3) . . ?
C1 N1 C2 119.0(3) . . ?
C4 N1 C2 120.1(3) . . ?
C6 N2 C7 120.5(3) . . ?
C6 N2 C9 121.5(3) . . ?
C7 N2 C9 118.0(3) . . ?
C11 N3 C12 122.2(3) . . ?
C11 N3 C14 119.5(3) . . ?
C12 N3 C14 118.2(3) . . ?
C1 O1 Ti2 133.2(2) . . ?
C1 O2 Ti1 136.6(2) . . ?
C6 O3 Ti2 137.3(2) . . ?
C6 O4 Ti1 134.5(2) . . ?
C11 O5 Ti1 130.8(2) . . ?
C11 O6 Ti2 138.2(2) 2_565 . ?
O4 Ti1 O4 180.0 2_565 . ?
O4 Ti1 O5 87.62(10) 2_565 2_565 ?
O4 Ti1 O5 92.38(10) . 2_565 ?
O4 Ti1 O5 92.38(10) 2_565 . ?
O4 Ti1 O5 87.62(10) . . ?
O5 Ti1 O5 180.0 2_565 . ?
O4 Ti1 O2 87.79(10) 2_565 . ?
O4 Ti1 O2 92.21(10) . . ?
O5 Ti1 O2 91.40(9) 2_565 . ?
O5 Ti1 O2 88.60(9) . . ?
O4 Ti1 O2 92.21(10) 2_565 2_565 ?
O4 Ti1 O2 87.79(10) . 2_565 ?
O5 Ti1 O2 88.60(9) 2_565 2_565 ?
O5 Ti1 O2 91.40(9) . 2_565 ?
O2 Ti1 O2 180.0 . 2_565 ?
O3 Ti2 O6 89.56(10) . . ?
O3 Ti2 O1 87.09(10) . . ?
O6 Ti2 O1 86.87(10) . . ?
O3 Ti2 Cl2 89.27(8) . . ?
O6 Ti2 Cl2 176.78(8) . . ?
O1 Ti2 Cl2 90.08(8) . . ?
O3 Ti2 Cl3 175.74(8) . . ?
O6 Ti2 Cl3 87.04(7) . . ?
O1 Ti2 Cl3 90.16(7) . . ?
Cl2 Ti2 Cl3 94.00(4) . . ?
O3 Ti2 Cl1 88.13(7) . . ?
O6 Ti2 Cl1 88.46(8) . . ?
O1 Ti2 Cl1 173.34(8) . . ?
Cl2 Ti2 Cl1 94.49(4) . . ?
Cl3 Ti2 Cl1 94.35(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C1 N1 C4 -178.8(3) . . . . ?
O2 C1 N1 C4 1.1(5) . . . . ?
O1 C1 N1 C2 4.8(5) . . . . ?
O2 C1 N1 C2 -175.3(3) . . . . ?
C5 C4 N1 C1 -83.1(4) . . . . ?
C5 C4 N1 C2 93.2(4) . . . . ?
C3 C2 N1 C1 78.0(4) . . . . ?
C3 C2 N1 C4 -98.5(4) . . . . ?
O3 C6 N2 C7 -1.5(5) . . . . ?
O4 C6 N2 C7 178.3(3) . . . . ?
O3 C6 N2 C9 176.1(3) . . . . ?
O4 C6 N2 C9 -4.1(5) . . . . ?
C8 C7 N2 C6 79.1(4) . . . . ?
C8 C7 N2 C9 -98.6(4) . . . . ?
C10 C9 N2 C6 101.0(4) . . . . ?
C10 C9 N2 C7 -81.4(4) . . . . ?
O6 C11 N3 C12 178.4(3) 2_565 . . . ?
O5 C11 N3 C12 -2.1(5) . . . . ?
O6 C11 N3 C14 1.7(5) 2_565 . . . ?
O5 C11 N3 C14 -178.8(3) . . . . ?
C13 C12 N3 C11 -94.0(4) . . . . ?
C13 C12 N3 C14 82.7(4) . . . . ?
C15 C14 N3 C11 -80.8(4) . . . . ?
C15 C14 N3 C12 102.4(4) . . . . ?
O2 C1 O1 Ti2 -58.6(4) . . . . ?
N1 C1 O1 Ti2 121.3(3) . . . . ?
O1 C1 O2 Ti1 -31.5(5) . . . . ?
N1 C1 O2 Ti1 148.6(3) . . . . ?
O4 C6 O3 Ti2 -51.6(5) . . . . ?
N2 C6 O3 Ti2 128.1(3) . . . . ?
O3 C6 O4 Ti1 -39.2(5) . . . . ?
N2 C6 O4 Ti1 141.1(3) . . . . ?
O6 C11 O5 Ti1 55.2(4) 2_565 . . . ?
N3 C11 O5 Ti1 -124.3(3) . . . . ?

_refine_diff_density_max         0.461
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.094

####################################################################### 
# 
# 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_3
_database_code_depnum_ccdc_archive 'CCDC 1495490'
_audit_update_record             
;
2016-12-27 deposited with the CCDC.
2017-01-11 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         ?
_chemical_formula_sum            'C34 H90 Cl10 N20 Ti'
_chemical_formula_weight         1181.65

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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                   8.6586(9)
_cell_length_b                   13.0597(14)
_cell_length_c                   14.2197(15)
_cell_angle_alpha                82.059(8)
_cell_angle_beta                 76.615(7)
_cell_angle_gamma                78.133(7)
_cell_volume                     1523.9(3)
_cell_formula_units_Z            1
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3079
_cell_measurement_theta_min      2.2505
_cell_measurement_theta_max      26.3255

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_F_000             626
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.622
_shelx_estimated_absorpt_T_min   0.912
_shelx_estimated_absorpt_T_max   0.940
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.9125
_exptl_absorpt_correction_T_max  0.9404
_exptl_absorpt_process_details   
; 
 Data were corrected for Lorentz polarization and absorption
 effects (empirical absorption correction SADABS).
 R(int) =  0.1230 (selected reflections only, before parameter refinement)
 R(int) =  0.0795 (selected reflections only, after parameter refinement)
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5269
_diffrn_reflns_av_unetI/netI     0.0887
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.479
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_full        25.027
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             5269
_reflns_number_gt                3802
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 _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       'APEX2 (Bruker AXS, 2006)'
_computing_cell_refinement       'APEX2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT (Bruker AXS, 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1996)'
_computing_publication_material  'XCIF (Bruker AXS, 2001)'
_refine_special_details          
;
 Refined as a 2-component twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1187P)²+3.5854P] 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         5269
_refine_ls_number_parameters     309
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.0869
_refine_ls_wR_factor_ref         0.2456
_refine_ls_wR_factor_gt          0.2260
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_restrained_S_all      1.106
_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 0.5000 0.0000 0.5000 0.0175(4) Uani 1 2 d S . P . .
Cl1 Cl 0.3308(2) 0.00393(14) 0.39231(13) 0.0228(4) Uani 1 1 d . . . . .
Cl2 Cl 0.4225(2) -0.15611(13) 0.58363(13) 0.0224(4) Uani 1 1 d . . . . .
Cl3 Cl 0.2898(2) 0.09883(14) 0.60318(13) 0.0233(4) Uani 1 1 d . . . . .
Cl4 Cl 0.8845(2) 0.73216(15) 0.96226(13) 0.0246(4) Uani 1 1 d . . . . .
Cl5 Cl 0.3280(2) 0.70694(15) 0.13635(14) 0.0274(5) Uani 1 1 d . . . . .
N1 N 0.3126(7) 0.3381(5) 0.8253(4) 0.0226(13) Uani 1 1 d . . . . .
H1A H 0.4150 0.3152 0.8270 0.027 Uiso 1 1 calc R U . . .
H1B H 0.2413 0.3506 0.8795 0.027 Uiso 1 1 calc R U . . .
N2 N 0.1086(8) 0.3900(5) 0.7399(4) 0.0231(14) Uani 1 1 d . . . . .
N3 N 0.3742(7) 0.3351(5) 0.6597(4) 0.0220(13) Uani 1 1 d . . . . .
C1 C 0.2661(9) 0.3540(5) 0.7417(5) 0.0196(15) Uani 1 1 d . . . . .
C2 C -0.0005(10) 0.4473(6) 0.8184(6) 0.0278(17) Uani 1 1 d . . . . .
H2A H -0.0648 0.5098 0.7906 0.042 Uiso 1 1 calc R U . . .
H2B H 0.0629 0.4686 0.8588 0.042 Uiso 1 1 calc R U . . .
H2C H -0.0724 0.4017 0.8584 0.042 Uiso 1 1 calc R U . . .
C3 C 0.0304(10) 0.3604(7) 0.6687(6) 0.0298(18) Uani 1 1 d . . . . .
H3A H -0.0761 0.3449 0.7013 0.045 Uiso 1 1 calc R U . . .
H3B H 0.0971 0.2980 0.6393 0.045 Uiso 1 1 calc R U . . .
H3C H 0.0183 0.4187 0.6180 0.045 Uiso 1 1 calc R U . . .
C4 C 0.5303(9) 0.2659(6) 0.6596(6) 0.0254(17) Uani 1 1 d . . . . .
H4A H 0.5610 0.2267 0.6021 0.038 Uiso 1 1 calc R U . . .
H4B H 0.5222 0.2166 0.7183 0.038 Uiso 1 1 calc R U . . .
H4C H 0.6122 0.3082 0.6583 0.038 Uiso 1 1 calc R U . . .
C5 C 0.3563(11) 0.3893(7) 0.5649(6) 0.034(2) Uani 1 1 d . . . . .
H5A H 0.4533 0.4188 0.5344 0.051 Uiso 1 1 calc R U . . .
H5B H 0.2621 0.4462 0.5731 0.051 Uiso 1 1 calc R U . . .
H5C H 0.3414 0.3395 0.5237 0.051 Uiso 1 1 calc R U . . .
N4 N 0.5519(7) 0.6778(5) 0.9264(4) 0.0239(14) Uani 1 1 d . . . . .
H4D H 0.4862 0.6723 0.9834 0.029 Uiso 1 1 calc R U . . .
H4E H 0.6402 0.7038 0.9202 0.029 Uiso 1 1 calc R U . . .
N5 N 0.3844(7) 0.6072(5) 0.8565(4) 0.0199(13) Uani 1 1 d . . . . .
N6 N 0.6175(7) 0.6581(5) 0.7616(4) 0.0235(14) Uani 1 1 d . . . . .
C6 C 0.5179(9) 0.6470(5) 0.8495(5) 0.0218(16) Uani 1 1 d . . . . .
C7 C 0.2973(9) 0.5658(6) 0.9498(5) 0.0235(16) Uani 1 1 d . . . . .
H7A H 0.2611 0.5019 0.9415 0.035 Uiso 1 1 calc R U . . .
H7B H 0.2035 0.6185 0.9743 0.035 Uiso 1 1 calc R U . . .
H7C H 0.3688 0.5492 0.9962 0.035 Uiso 1 1 calc R U . . .
C8 C 0.2953(9) 0.6260(6) 0.7775(5) 0.0251(17) Uani 1 1 d . . . . .
H8A H 0.1799 0.6478 0.8041 0.038 Uiso 1 1 calc R U . . .
H8B H 0.3124 0.5613 0.7460 0.038 Uiso 1 1 calc R U . . .
H8C H 0.3343 0.6816 0.7297 0.038 Uiso 1 1 calc R U . . .
C9 C 0.6426(10) 0.5829(6) 0.6896(6) 0.0299(18) Uani 1 1 d . . . . .
H9A H 0.7576 0.5670 0.6594 0.045 Uiso 1 1 calc R U . . .
H9B H 0.5808 0.6133 0.6396 0.045 Uiso 1 1 calc R U . . .
H9C H 0.6063 0.5180 0.7216 0.045 Uiso 1 1 calc R U . . .
C10 C 0.7226(9) 0.7363(6) 0.7407(6) 0.0294(18) Uani 1 1 d . . . . .
H10A H 0.7267 0.7686 0.6739 0.044 Uiso 1 1 calc R U . . .
H10B H 0.8315 0.7021 0.7483 0.044 Uiso 1 1 calc R U . . .
H10C H 0.6802 0.7906 0.7859 0.044 Uiso 1 1 calc R U . . .
N7 N 1.0036(7) -0.1319(5) 0.1018(5) 0.0263(15) Uani 1 1 d . . . . .
H7D H 0.9391 -0.1638 0.0814 0.032 Uiso 1 1 calc R U . . .
H7E H 1.1057 -0.1609 0.0981 0.032 Uiso 1 1 calc R U . . .
N8 N 0.7916(7) 0.0033(5) 0.1433(4) 0.0226(13) Uani 1 1 d . . . . .
N9 N 1.0453(7) 0.0094(5) 0.1693(4) 0.0233(14) Uani 1 1 d . . . . .
C11 C 0.9466(9) -0.0394(6) 0.1383(5) 0.0226(16) Uani 1 1 d . . . . .
C12 C 0.7335(10) 0.1157(6) 0.1366(6) 0.0284(17) Uani 1 1 d . . . . .
H12A H 0.6631 0.1346 0.0896 0.043 Uiso 1 1 calc R U . . .
H12B H 0.8255 0.1524 0.1153 0.043 Uiso 1 1 calc R U . . .
H12C H 0.6727 0.1363 0.2004 0.043 Uiso 1 1 calc R U . . .
C13 C 0.6670(9) -0.0596(6) 0.1494(6) 0.0265(17) Uani 1 1 d . . . . .
H13A H 0.5710 -0.0334 0.1975 0.040 Uiso 1 1 calc R U . . .
H13B H 0.7081 -0.1333 0.1689 0.040 Uiso 1 1 calc R U . . .
H13C H 0.6386 -0.0542 0.0858 0.040 Uiso 1 1 calc R U . . .
C14 C 0.9878(10) 0.0745(6) 0.2508(6) 0.0272(17) Uani 1 1 d . . . . .
H14A H 1.0468 0.0454 0.3024 0.041 Uiso 1 1 calc R U . . .
H14B H 0.8722 0.0753 0.2758 0.041 Uiso 1 1 calc R U . . .
H14C H 1.0059 0.1464 0.2286 0.041 Uiso 1 1 calc R U . . .
C15 C 1.2187(9) -0.0126(7) 0.1354(6) 0.0292(18) Uani 1 1 d . . . . .
H15A H 1.2601 0.0536 0.1213 0.044 Uiso 1 1 calc R U . . .
H15B H 1.2452 -0.0488 0.0762 0.044 Uiso 1 1 calc R U . . .
H15C H 1.2683 -0.0574 0.1856 0.044 Uiso 1 1 calc R U . . .
N21 N 0.0899(12) 0.6308(7) 0.5731(8) 0.066(3) Uani 1 1 d . . . . .
C21 C 0.0772(10) 0.7164(7) 0.5397(7) 0.035(2) Uani 1 1 d . . . . .
C22 C 0.0615(11) 0.8235(7) 0.4992(7) 0.039(2) Uani 1 1 d . . . . .
H22A H -0.0500 0.8595 0.5200 0.059 Uiso 1 1 calc R U . . .
H22B H 0.0891 0.8261 0.4281 0.059 Uiso 1 1 calc R U . . .
H22C H 0.1347 0.8583 0.5215 0.059 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 Cl3 2.3348(18) 2_656 ?
Ti1 Cl3 2.3348(18) . ?
Ti1 Cl1 2.3409(17) . ?
Ti1 Cl1 2.3410(17) 2_656 ?
Ti1 Cl2 2.3546(17) . ?
Ti1 Cl2 2.3547(17) 2_656 ?
N1 C1 1.318(9) . ?
N1 H1A 0.8800 . ?
N1 H1B 0.8800 . ?
N2 C1 1.353(10) . ?
N2 C2 1.466(10) . ?
N2 C3 1.472(10) . ?
N3 C1 1.333(9) . ?
N3 C5 1.459(10) . ?
N3 C4 1.463(9) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 H4A 0.9800 . ?
C4 H4B 0.9800 . ?
C4 H4C 0.9800 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
N4 C6 1.329(10) . ?
N4 H4D 0.8800 . ?
N4 H4E 0.8800 . ?
N5 C6 1.340(9) . ?
N5 C7 1.458(9) . ?
N5 C8 1.471(9) . ?
N6 C6 1.352(9) . ?
N6 C10 1.461(9) . ?
N6 C9 1.465(10) . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C9 H9C 0.9800 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
N7 C11 1.334(10) . ?
N7 H7D 0.8800 . ?
N7 H7E 0.8800 . ?
N8 C11 1.333(9) . ?
N8 C12 1.449(10) . ?
N8 C13 1.465(9) . ?
N9 C11 1.345(9) . ?
N9 C15 1.448(9) . ?
N9 C14 1.464(10) . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
N21 C21 1.147(12) . ?
C21 C22 1.429(13) . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl3 Ti1 Cl3 180.00(8) 2_656 . ?
Cl3 Ti1 Cl1 89.61(6) 2_656 . ?
Cl3 Ti1 Cl1 90.39(6) . . ?
Cl3 Ti1 Cl1 90.39(6) 2_656 2_656 ?
Cl3 Ti1 Cl1 89.61(6) . 2_656 ?
Cl1 Ti1 Cl1 180.0 . 2_656 ?
Cl3 Ti1 Cl2 89.89(6) 2_656 . ?
Cl3 Ti1 Cl2 90.11(6) . . ?
Cl1 Ti1 Cl2 90.64(6) . . ?
Cl1 Ti1 Cl2 89.36(6) 2_656 . ?
Cl3 Ti1 Cl2 90.11(6) 2_656 2_656 ?
Cl3 Ti1 Cl2 89.89(6) . 2_656 ?
Cl1 Ti1 Cl2 89.36(6) . 2_656 ?
Cl1 Ti1 Cl2 90.64(6) 2_656 2_656 ?
Cl2 Ti1 Cl2 180.00(8) . 2_656 ?
C1 N1 H1A 120.0 . . ?
C1 N1 H1B 120.0 . . ?
H1A N1 H1B 120.0 . . ?
C1 N2 C2 121.4(6) . . ?
C1 N2 C3 122.5(6) . . ?
C2 N2 C3 115.4(6) . . ?
C1 N3 C5 123.7(6) . . ?
C1 N3 C4 121.8(6) . . ?
C5 N3 C4 114.2(6) . . ?
N1 C1 N3 120.0(7) . . ?
N1 C1 N2 119.5(7) . . ?
N3 C1 N2 120.5(6) . . ?
N2 C2 H2A 109.5 . . ?
N2 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N2 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
N2 C3 H3A 109.5 . . ?
N2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
N2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N3 C4 H4A 109.5 . . ?
N3 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
N3 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
N3 C5 H5A 109.5 . . ?
N3 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N3 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C6 N4 H4D 120.0 . . ?
C6 N4 H4E 120.0 . . ?
H4D N4 H4E 120.0 . . ?
C6 N5 C7 121.4(6) . . ?
C6 N5 C8 121.9(6) . . ?
C7 N5 C8 115.0(6) . . ?
C6 N6 C10 120.7(6) . . ?
C6 N6 C9 121.6(6) . . ?
C10 N6 C9 117.1(6) . . ?
N4 C6 N5 121.4(7) . . ?
N4 C6 N6 119.6(6) . . ?
N5 C6 N6 119.0(7) . . ?
N5 C7 H7A 109.5 . . ?
N5 C7 H7B 109.5 . . ?
H7A C7 H7B 109.5 . . ?
N5 C7 H7C 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
N5 C8 H8A 109.5 . . ?
N5 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
N5 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
N6 C9 H9A 109.5 . . ?
N6 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N6 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N6 C10 H10A 109.5 . . ?
N6 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
N6 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C11 N7 H7D 120.0 . . ?
C11 N7 H7E 120.0 . . ?
H7D N7 H7E 120.0 . . ?
C11 N8 C12 123.0(6) . . ?
C11 N8 C13 122.6(6) . . ?
C12 N8 C13 114.2(6) . . ?
C11 N9 C15 122.0(6) . . ?
C11 N9 C14 122.0(6) . . ?
C15 N9 C14 115.2(6) . . ?
N8 C11 N7 119.1(7) . . ?
N8 C11 N9 120.9(7) . . ?
N7 C11 N9 120.0(7) . . ?
N8 C12 H12A 109.5 . . ?
N8 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
N8 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N8 C13 H13A 109.5 . . ?
N8 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
N8 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
N9 C14 H14A 109.5 . . ?
N9 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N9 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
N9 C15 H15A 109.5 . . ?
N9 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
N9 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N21 C21 C22 179.3(11) . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 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
C5 N3 C1 N1 -152.2(7) . . . . ?
C4 N3 C1 N1 20.8(10) . . . . ?
C5 N3 C1 N2 27.4(10) . . . . ?
C4 N3 C1 N2 -159.6(7) . . . . ?
C2 N2 C1 N1 22.6(10) . . . . ?
C3 N2 C1 N1 -147.6(7) . . . . ?
C2 N2 C1 N3 -157.0(7) . . . . ?
C3 N2 C1 N3 32.9(10) . . . . ?
C7 N5 C6 N4 -19.1(10) . . . . ?
C8 N5 C6 N4 145.3(7) . . . . ?
C7 N5 C6 N6 162.5(6) . . . . ?
C8 N5 C6 N6 -33.1(10) . . . . ?
C10 N6 C6 N4 -23.5(10) . . . . ?
C9 N6 C6 N4 147.0(7) . . . . ?
C10 N6 C6 N5 154.9(7) . . . . ?
C9 N6 C6 N5 -34.6(10) . . . . ?
C12 N8 C11 N7 -149.9(7) . . . . ?
C13 N8 C11 N7 25.8(11) . . . . ?
C12 N8 C11 N9 30.0(11) . . . . ?
C13 N8 C11 N9 -154.3(7) . . . . ?
C15 N9 C11 N8 -157.7(7) . . . . ?
C14 N9 C11 N8 32.7(11) . . . . ?
C15 N9 C11 N7 22.2(11) . . . . ?
C14 N9 C11 N7 -147.4(7) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1A Cl5 0.88 2.35 3.205(6) 162.7 2_666
N1 H1B Cl4 0.88 2.47 3.220(6) 143.7 2_667
N4 H4E Cl4 0.88 2.44 3.267(6) 157.6 .
N4 H4D Cl5 0.88 2.33 3.186(7) 163.0 1_556
N7 H7D Cl4 0.88 2.49 3.290(6) 151.2 1_544
N7 H7E Cl5 0.88 2.42 3.238(6) 155.5 1_645

_refine_diff_density_max         1.076
_refine_diff_density_min         -0.970
_refine_diff_density_rms         0.184

####################################################################### 
# 
# 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_8
_database_code_depnum_ccdc_archive 'CCDC 1511415'
_audit_update_record             
;
2016-12-27 deposited with the CCDC.
2017-01-11 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         ?
_chemical_formula_sum            'C38 H74 Cl4 Hf4 N6 O18'
_chemical_formula_weight         1758.79

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Hf Hf -0.5830 6.1852 '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                   11.5959(12)
_cell_length_b                   18.794(2)
_cell_length_c                   14.5380(16)
_cell_angle_alpha                90
_cell_angle_beta                 102.888(3)
_cell_angle_gamma                90
_cell_volume                     3088.5(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8312
_cell_measurement_theta_min      2.309
_cell_measurement_theta_max      27.859

_exptl_crystal_description       cube
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.891
_exptl_crystal_F_000             1688
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    6.935
_shelx_estimated_absorpt_T_min   0.368
_shelx_estimated_absorpt_T_max   0.443
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.3939
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_process_details   
; 
 Data were corrected for Lorentz polarization and absorption
 effects (empirical absorption correction SADABS).
 R(int) =  0.1339 (selected reflections only, before parameter refinement)
 R(int) =  0.0844(selected reflections only, after parameter refinement)
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'CMOS area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            28411
_diffrn_reflns_av_unetI/netI     0.0790
_diffrn_reflns_av_R_equivalents  0.1059
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.800
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             6078
_reflns_number_gt                4346
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker AXS, 2006)'
_computing_cell_refinement       'APEX2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT (Bruker AXS, 2004)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1996)'
_computing_publication_material  'XCIF (Bruker AXS, 2001)'
_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)+(0.0919P)²+20.1428P] 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         6078
_refine_ls_number_parameters     322
_refine_ls_number_restraints     65
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0635
_refine_ls_wR_factor_ref         0.1701
_refine_ls_wR_factor_gt          0.1510
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_restrained_S_all      1.021
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.1771(12) 0.5469(7) 0.5302(9) 0.036(3) Uani 1 1 d . . . . .
C2 C 0.0841(19) 0.5536(13) 0.6656(17) 0.096(8) Uani 1 1 d . U . . .
H2A H 0.0021 0.5594 0.6738 0.115 Uiso 1 1 calc R U . . .
H2B H 0.1091 0.5038 0.6808 0.115 Uiso 1 1 calc R U . . .
C3 C 0.159(2) 0.6003(12) 0.7240(17) 0.097(7) Uani 1 1 d . U . . .
H3A H 0.1577 0.5906 0.7899 0.146 Uiso 1 1 calc R U . . .
H3B H 0.2401 0.5940 0.7152 0.146 Uiso 1 1 calc R U . . .
H3C H 0.1336 0.6493 0.7082 0.146 Uiso 1 1 calc R U . . .
C4 C -0.0108(12) 0.6067(8) 0.5056(11) 0.044(4) Uani 1 1 d . . . . .
H4A H -0.0844 0.5874 0.5197 0.053 Uiso 1 1 calc R U . . .
H4B H -0.0116 0.5957 0.4388 0.053 Uiso 1 1 calc R U . . .
C5 C -0.0090(15) 0.6853(9) 0.5183(14) 0.064(5) Uani 1 1 d . . . . .
H5A H -0.0787 0.7062 0.4763 0.096 Uiso 1 1 calc R U . . .
H5B H -0.0100 0.6966 0.5840 0.096 Uiso 1 1 calc R U . . .
H5C H 0.0628 0.7049 0.5031 0.096 Uiso 1 1 calc R U . . .
C6 C 0.1461(11) 0.6313(7) 0.2096(11) 0.041(3) Uani 1 1 d . . . . .
C7 C -0.0503(16) 0.6364(13) 0.1132(15) 0.093(8) Uani 1 1 d . . . . .
H7A H -0.0952 0.6679 0.0633 0.112 Uiso 1 1 calc R U . . .
H7B H -0.0772 0.6467 0.1718 0.112 Uiso 1 1 calc R U . . .
C8 C -0.082(2) 0.5606(16) 0.0854(18) 0.128(11) Uani 1 1 d . . . . .
H8A H -0.1671 0.5539 0.0767 0.192 Uiso 1 1 calc R U . . .
H8B H -0.0580 0.5499 0.0262 0.192 Uiso 1 1 calc R U . . .
H8C H -0.0400 0.5286 0.1350 0.192 Uiso 1 1 calc R U . . .
C9 C 0.1189(15) 0.6943(10) 0.0570(13) 0.068(5) Uani 1 1 d . . . . .
H9A H 0.1840 0.7258 0.0890 0.082 Uiso 1 1 calc R U . . .
H9B H 0.0550 0.7248 0.0208 0.082 Uiso 1 1 calc R U . . .
C10 C 0.163(3) 0.6469(15) -0.0098(16) 0.125(10) Uani 1 1 d . . . . .
H10A H 0.1923 0.6759 -0.0559 0.188 Uiso 1 1 calc R U . . .
H10B H 0.2278 0.6173 0.0254 0.188 Uiso 1 1 calc R U . . .
H10C H 0.0988 0.6163 -0.0428 0.188 Uiso 1 1 calc R U . . .
C11 C 0.3755(12) 0.4490(7) 0.2811(10) 0.037(3) Uani 1 1 d . . . . .
C12 C 0.2252(14) 0.3807(9) 0.1748(12) 0.058(3) Uani 1 1 d . U . . .
H12A H 0.2279 0.3523 0.1180 0.069 Uiso 1 1 calc R U . . .
H12B H 0.1905 0.4277 0.1540 0.069 Uiso 1 1 calc R U . . .
C13 C 0.1491(14) 0.3432(9) 0.2315(12) 0.062(4) Uani 1 1 d . U . . .
H13A H 0.0690 0.3372 0.1926 0.093 Uiso 1 1 calc R U . . .
H13B H 0.1831 0.2965 0.2513 0.093 Uiso 1 1 calc R U . . .
H13C H 0.1458 0.3717 0.2873 0.093 Uiso 1 1 calc R U . . .
C14 C 0.4253(16) 0.3259(10) 0.2429(14) 0.072(3) Uani 1 1 d . U . . .
H14A H 0.4757 0.3242 0.3075 0.086 Uiso 1 1 calc R U . . .
H14B H 0.3772 0.2819 0.2323 0.086 Uiso 1 1 calc R U . . .
C15 C 0.496(3) 0.3304(15) 0.177(2) 0.130(10) Uani 1 1 d . U . . .
H15A H 0.5481 0.2889 0.1833 0.196 Uiso 1 1 calc R U . . .
H15B H 0.4454 0.3316 0.1132 0.196 Uiso 1 1 calc R U . . .
H15C H 0.5437 0.3738 0.1882 0.196 Uiso 1 1 calc R U . . .
C16 C 0.5156(12) 0.6198(8) 0.2651(12) 0.053(4) Uani 1 1 d D U . . .
H16 H 0.4623 0.5960 0.2101 0.064 Uiso 0.5 1 calc R U P A 1
H16' H 0.4625 0.6070 0.2032 0.064 Uiso 0.5 1 calc R U P B 2
C17A C 0.542(3) 0.6914(14) 0.231(3) 0.055(7) Uani 0.5 1 d D U P C 1
H17C H 0.4998 0.7292 0.2579 0.066 Uiso 0.5 1 calc R U P C 1
H17D H 0.5195 0.6941 0.1612 0.066 Uiso 0.5 1 calc R U P C 1
C18A C 0.675(3) 0.6968(13) 0.267(3) 0.072(8) Uani 0.5 1 d D U P C 1
H18C H 0.7118 0.7235 0.2224 0.086 Uiso 0.5 1 calc R U P C 1
H18D H 0.6947 0.7213 0.3293 0.086 Uiso 0.5 1 calc R U P C 1
C17B C 0.567(3) 0.6956(13) 0.266(3) 0.055(7) Uani 0.5 1 d D U P C 2
H17A H 0.5933 0.7133 0.3319 0.066 Uiso 0.5 1 calc R U P C 2
H17B H 0.5075 0.7290 0.2304 0.066 Uiso 0.5 1 calc R U P C 2
C18B C 0.673(3) 0.6866(17) 0.219(3) 0.072(8) Uani 0.5 1 d D U P C 2
H18A H 0.6480 0.6769 0.1504 0.086 Uiso 0.5 1 calc R U P C 2
H18B H 0.7284 0.7272 0.2308 0.086 Uiso 0.5 1 calc R U P C 2
C19 C 0.7196(12) 0.6206(8) 0.2769(13) 0.061(4) Uani 1 1 d D U . . .
H19A H 0.7472 0.6062 0.2199 0.074 Uiso 0.5 1 calc R U P C 1
H19B H 0.7862 0.6157 0.3325 0.074 Uiso 0.5 1 calc R U P C 1
H19C H 0.7719 0.5933 0.2445 0.074 Uiso 0.5 1 calc R U P C 2
H19D H 0.7664 0.6351 0.3397 0.074 Uiso 0.5 1 calc R U P C 2
N1 N 0.0908(11) 0.5713(7) 0.5661(9) 0.047(3) Uani 1 1 d . . . . .
N2 N 0.0736(10) 0.6547(7) 0.1286(9) 0.054(4) Uani 1 1 d . . . . .
N3 N 0.3455(12) 0.3900(7) 0.2325(10) 0.059(3) Uani 1 1 d . U . . .
O1 O 0.4130(7) 0.5384(4) 0.4647(5) 0.0251(17) Uani 1 1 d . . . . .
O2 O 0.2655(8) 0.5184(5) 0.5883(6) 0.041(2) Uani 1 1 d . . . . .
O3 O 0.1775(7) 0.5537(4) 0.4438(6) 0.031(2) Uani 1 1 d . . . . .
O4 O 0.2601(8) 0.6472(5) 0.2258(6) 0.040(2) Uani 1 1 d . . . . .
O5 O 0.1110(8) 0.5994(5) 0.2727(7) 0.043(2) Uani 1 1 d . . . . .
O6 O 0.2945(8) 0.4966(5) 0.2815(6) 0.038(2) Uani 1 1 d . . . . .
O7 O 0.4843(8) 0.4563(5) 0.3232(6) 0.036(2) Uani 1 1 d . . . . .
O8 O 0.4634(7) 0.6095(5) 0.3405(6) 0.032(2) Uani 1 1 d . . . . .
O9 O 0.6209(8) 0.5764(5) 0.2880(7) 0.045(2) Uani 1 1 d D U . . .
Cl1 Cl 0.3192(3) 0.37453(18) 0.4831(2) 0.0379(7) Uani 1 1 d . . . . .
Cl2 Cl 0.2955(3) 0.70409(17) 0.4431(3) 0.0398(8) Uani 1 1 d . . . . .
Hf1 Hf 0.42668(4) 0.47063(3) 0.57651(4) 0.02985(18) Uani 1 1 d . . . . .
Hf2 Hf 0.29019(4) 0.59002(3) 0.36122(4) 0.03061(18) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 O3 1.263(15) . ?
C1 O2 1.290(15) . ?
C1 N1 1.310(16) . ?
C2 C3 1.39(3) . ?
C2 N1 1.50(3) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 N1 1.463(17) . ?
C4 C5 1.49(2) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
C6 O5 1.238(17) . ?
C6 O4 1.324(15) . ?
C6 N2 1.358(18) . ?
C6 Hf2 2.571(14) . ?
C7 N2 1.45(2) . ?
C7 C8 1.50(3) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 H8A 0.9800 . ?
C8 H8B 0.9800 . ?
C8 H8C 0.9800 . ?
C9 N2 1.47(2) . ?
C9 C10 1.49(3) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 O7 1.280(16) . ?
C11 O6 1.298(15) . ?
C11 N3 1.320(18) . ?
C12 N3 1.469(19) . ?
C12 C13 1.51(2) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 C15 1.40(3) . ?
C14 N3 1.51(2) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 O8 1.377(16) . ?
C16 O9 1.445(13) . ?
C16 C17A 1.489(18) . ?
C16 C17B 1.543(19) . ?
C16 Hf1 2.819(14) 3_666 ?
C16 H16 1.0000 . ?
C16 H16' 1.0000 . ?
C17A C18A 1.527(19) . ?
C17A H17C 0.9900 . ?
C17A H17D 0.9900 . ?
C18A C19 1.518(18) . ?
C18A H18C 0.9900 . ?
C18A H18D 0.9900 . ?
C17B C18B 1.546(19) . ?
C17B H17A 0.9900 . ?
C17B H17B 0.9900 . ?
C18B C19 1.531(18) . ?
C18B H18A 0.9900 . ?
C18B H18B 0.9900 . ?
C19 O9 1.452(13) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C19 H19C 0.9900 . ?
C19 H19D 0.9900 . ?
O1 Hf1 2.044(8) . ?
O1 Hf2 2.067(7) . ?
O1 Hf1 2.084(8) 3_666 ?
O2 Hf1 2.114(8) . ?
O3 Hf2 2.077(8) . ?
O4 Hf2 2.202(8) . ?
O5 Hf2 2.194(9) . ?
O6 Hf2 2.110(9) . ?
O7 Hf1 2.099(9) 3_666 ?
O8 Hf2 2.129(8) . ?
O8 Hf1 2.160(8) 3_666 ?
O9 Hf1 2.334(9) 3_666 ?
Cl1 Hf1 2.430(3) . ?
Cl2 Hf2 2.446(3) . ?
Hf1 O1 2.084(8) 3_666 ?
Hf1 O7 2.099(9) 3_666 ?
Hf1 O8 2.160(8) 3_666 ?
Hf1 O9 2.334(9) 3_666 ?
Hf1 C16 2.819(14) 3_666 ?
Hf1 Hf1 3.2782(10) 3_666 ?
Hf1 Hf2 3.4018(8) 3_666 ?
Hf2 Hf1 3.4019(8) 3_666 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 C1 O2 120.9(11) . . ?
O3 C1 N1 122.2(11) . . ?
O2 C1 N1 116.8(12) . . ?
C3 C2 N1 107(2) . . ?
C3 C2 H2A 110.4 . . ?
N1 C2 H2A 110.4 . . ?
C3 C2 H2B 110.4 . . ?
N1 C2 H2B 110.4 . . ?
H2A C2 H2B 108.6 . . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N1 C4 C5 112.9(13) . . ?
N1 C4 H4A 109.0 . . ?
C5 C4 H4A 109.0 . . ?
N1 C4 H4B 109.0 . . ?
C5 C4 H4B 109.0 . . ?
H4A C4 H4B 107.8 . . ?
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 . . ?
O5 C6 O4 117.2(12) . . ?
O5 C6 N2 123.8(12) . . ?
O4 C6 N2 118.8(13) . . ?
O5 C6 Hf2 58.5(7) . . ?
O4 C6 Hf2 58.9(7) . . ?
N2 C6 Hf2 177.7(11) . . ?
N2 C7 C8 116(2) . . ?
N2 C7 H7A 108.3 . . ?
C8 C7 H7A 108.3 . . ?
N2 C7 H7B 108.3 . . ?
C8 C7 H7B 108.3 . . ?
H7A C7 H7B 107.4 . . ?
C7 C8 H8A 109.5 . . ?
C7 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C7 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
N2 C9 C10 112.9(16) . . ?
N2 C9 H9A 109.0 . . ?
C10 C9 H9A 109.0 . . ?
N2 C9 H9B 109.0 . . ?
C10 C9 H9B 109.0 . . ?
H9A C9 H9B 107.8 . . ?
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 . . ?
O7 C11 O6 124.1(13) . . ?
O7 C11 N3 117.4(12) . . ?
O6 C11 N3 118.5(13) . . ?
N3 C12 C13 109.9(14) . . ?
N3 C12 H12A 109.7 . . ?
C13 C12 H12A 109.7 . . ?
N3 C12 H12B 109.7 . . ?
C13 C12 H12B 109.7 . . ?
H12A C12 H12B 108.2 . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C15 C14 N3 108.9(18) . . ?
C15 C14 H14A 109.9 . . ?
N3 C14 H14A 109.9 . . ?
C15 C14 H14B 109.9 . . ?
N3 C14 H14B 109.9 . . ?
H14A C14 H14B 108.3 . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
O8 C16 O9 103.7(10) . . ?
O8 C16 C17A 123(2) . . ?
O9 C16 C17A 111.3(17) . . ?
O8 C16 C17B 110.8(18) . . ?
O9 C16 C17B 102.4(17) . . ?
O8 C16 Hf1 48.2(5) . 3_666 ?
O9 C16 Hf1 55.7(6) . 3_666 ?
C17A C16 Hf1 142.0(17) . 3_666 ?
C17B C16 Hf1 121.7(16) . 3_666 ?
O8 C16 H16 105.8 . . ?
O9 C16 H16 105.8 . . ?
C17A C16 H16 105.8 . . ?
Hf1 C16 H16 112.1 3_666 . ?
O8 C16 H16' 113.0 . . ?
O9 C16 H16' 113.0 . . ?
C17B C16 H16' 113.0 . . ?
Hf1 C16 H16' 125.3 3_666 . ?
C16 C17A C18A 102(2) . . ?
C16 C17A H17C 111.3 . . ?
C18A C17A H17C 111.3 . . ?
C16 C17A H17D 111.3 . . ?
C18A C17A H17D 111.3 . . ?
H17C C17A H17D 109.2 . . ?
C19 C18A C17A 105(2) . . ?
C19 C18A H18C 110.7 . . ?
C17A C18A H18C 110.7 . . ?
C19 C18A H18D 110.7 . . ?
C17A C18A H18D 110.7 . . ?
H18C C18A H18D 108.8 . . ?
C16 C17B C18B 104(2) . . ?
C16 C17B H17A 111.0 . . ?
C18B C17B H17A 111.0 . . ?
C16 C17B H17B 111.0 . . ?
C18B C17B H17B 111.0 . . ?
H17A C17B H17B 109.0 . . ?
C19 C18B C17B 94(2) . . ?
C19 C18B H18A 113.0 . . ?
C17B C18B H18A 113.0 . . ?
C19 C18B H18B 113.0 . . ?
C17B C18B H18B 113.0 . . ?
H18A C18B H18B 110.4 . . ?
O9 C19 C18A 107.0(17) . . ?
O9 C19 C18B 109.4(18) . . ?
O9 C19 H19A 110.3 . . ?
C18A C19 H19A 110.3 . . ?
O9 C19 H19B 110.3 . . ?
C18A C19 H19B 110.3 . . ?
H19A C19 H19B 108.6 . . ?
O9 C19 H19C 109.8 . . ?
C18B C19 H19C 109.8 . . ?
O9 C19 H19D 109.8 . . ?
C18B C19 H19D 109.8 . . ?
H19C C19 H19D 108.2 . . ?
C1 N1 C4 120.3(12) . . ?
C1 N1 C2 120.9(13) . . ?
C4 N1 C2 118.1(13) . . ?
C6 N2 C7 117.3(13) . . ?
C6 N2 C9 121.9(12) . . ?
C7 N2 C9 120.7(13) . . ?
C11 N3 C12 120.6(13) . . ?
C11 N3 C14 122.4(13) . . ?
C12 N3 C14 116.5(13) . . ?
Hf1 O1 Hf2 142.2(4) . . ?
Hf1 O1 Hf1 105.2(3) . 3_666 ?
Hf2 O1 Hf1 110.1(4) . 3_666 ?
C1 O2 Hf1 135.3(8) . . ?
C1 O3 Hf2 138.6(9) . . ?
C6 O4 Hf2 90.1(8) . . ?
C6 O5 Hf2 92.8(8) . . ?
C11 O6 Hf2 133.0(9) . . ?
C11 O7 Hf1 133.0(9) . 3_666 ?
C16 O8 Hf2 137.1(8) . . ?
C16 O8 Hf1 103.5(7) . 3_666 ?
Hf2 O8 Hf1 105.0(3) . 3_666 ?
C16 O9 C19 107.4(10) . . ?
C16 O9 Hf1 93.5(7) . 3_666 ?
C19 O9 Hf1 130.6(10) . 3_666 ?
O1 Hf1 O1 74.8(3) . 3_666 ?
O1 Hf1 O7 94.8(3) . 3_666 ?
O1 Hf1 O7 85.4(3) 3_666 3_666 ?
O1 Hf1 O2 83.5(3) . . ?
O1 Hf1 O2 156.9(3) 3_666 . ?
O7 Hf1 O2 88.5(4) 3_666 . ?
O1 Hf1 O8 144.2(3) . 3_666 ?
O1 Hf1 O8 69.6(3) 3_666 3_666 ?
O7 Hf1 O8 86.0(3) 3_666 3_666 ?
O2 Hf1 O8 132.3(3) . 3_666 ?
O1 Hf1 O9 156.4(3) . 3_666 ?
O1 Hf1 O9 127.3(3) 3_666 3_666 ?
O7 Hf1 O9 80.4(3) 3_666 3_666 ?
O2 Hf1 O9 73.3(3) . 3_666 ?
O8 Hf1 O9 59.0(3) 3_666 3_666 ?
O1 Hf1 Cl1 94.6(2) . . ?
O1 Hf1 Cl1 99.1(2) 3_666 . ?
O7 Hf1 Cl1 170.4(3) 3_666 . ?
O2 Hf1 Cl1 90.5(3) . . ?
O8 Hf1 Cl1 87.6(3) 3_666 . ?
O9 Hf1 Cl1 90.1(3) 3_666 . ?
O1 Hf1 C16 171.0(3) . 3_666 ?
O1 Hf1 C16 96.9(3) 3_666 3_666 ?
O7 Hf1 C16 80.6(4) 3_666 3_666 ?
O2 Hf1 C16 104.1(4) . 3_666 ?
O8 Hf1 C16 28.4(3) 3_666 3_666 ?
O9 Hf1 C16 30.8(3) 3_666 3_666 ?
Cl1 Hf1 C16 90.4(4) . 3_666 ?
O1 Hf1 Hf1 37.8(2) . 3_666 ?
O1 Hf1 Hf1 37.0(2) 3_666 3_666 ?
O7 Hf1 Hf1 90.1(2) 3_666 3_666 ?
O2 Hf1 Hf1 120.9(2) . 3_666 ?
O8 Hf1 Hf1 106.5(2) 3_666 3_666 ?
O9 Hf1 Hf1 162.9(2) 3_666 3_666 ?
Cl1 Hf1 Hf1 98.64(8) . 3_666 ?
C16 Hf1 Hf1 133.8(3) 3_666 3_666 ?
O1 Hf1 Hf2 108.7(2) . 3_666 ?
O1 Hf1 Hf2 34.8(2) 3_666 3_666 ?
O7 Hf1 Hf2 74.8(2) 3_666 3_666 ?
O2 Hf1 Hf2 159.9(3) . 3_666 ?
O8 Hf1 Hf2 37.2(2) 3_666 3_666 ?
O9 Hf1 Hf2 92.5(2) 3_666 3_666 ?
Cl1 Hf1 Hf2 104.11(8) . 3_666 ?
C16 Hf1 Hf2 62.7(3) 3_666 3_666 ?
Hf1 Hf1 Hf2 71.184(19) 3_666 3_666 ?
O1 Hf2 O3 81.1(3) . . ?
O1 Hf2 O6 85.0(3) . . ?
O3 Hf2 O6 98.0(4) . . ?
O1 Hf2 O8 70.5(3) . . ?
O3 Hf2 O8 150.9(3) . . ?
O6 Hf2 O8 85.8(4) . . ?
O1 Hf2 O5 150.8(3) . . ?
O3 Hf2 O5 74.3(3) . . ?
O6 Hf2 O5 83.1(4) . . ?
O8 Hf2 O5 134.7(3) . . ?
O1 Hf2 O4 145.7(3) . . ?
O3 Hf2 O4 133.1(3) . . ?
O6 Hf2 O4 86.2(3) . . ?
O8 Hf2 O4 75.9(3) . . ?
O5 Hf2 O4 59.7(3) . . ?
O1 Hf2 Cl2 96.8(2) . . ?
O3 Hf2 Cl2 87.6(3) . . ?
O6 Hf2 Cl2 174.4(3) . . ?
O8 Hf2 Cl2 89.8(3) . . ?
O5 Hf2 Cl2 97.6(3) . . ?
O4 Hf2 Cl2 89.4(3) . . ?
O1 Hf2 C6 167.3(4) . . ?
O3 Hf2 C6 102.9(4) . . ?
O6 Hf2 C6 82.6(4) . . ?
O8 Hf2 C6 106.2(4) . . ?
O5 Hf2 C6 28.7(4) . . ?
O4 Hf2 C6 31.0(4) . . ?
Cl2 Hf2 C6 95.4(3) . . ?
O1 Hf2 Hf1 35.1(2) . 3_666 ?
O3 Hf2 Hf1 115.5(2) . 3_666 ?
O6 Hf2 Hf1 74.2(2) . 3_666 ?
O8 Hf2 Hf1 37.8(2) . 3_666 ?
O5 Hf2 Hf1 156.2(3) . 3_666 ?
O4 Hf2 Hf1 110.7(2) . 3_666 ?
Cl2 Hf2 Hf1 104.26(8) . 3_666 ?
C6 Hf2 Hf1 137.2(3) . 3_666 ?

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
O8 C16 C17A C18A 105(3) . . . . ?
O9 C16 C17A C18A -19(3) . . . . ?
Hf1 C16 C17A C18A 42(5) 3_666 . . . ?
C16 C17A C18A C19 26(4) . . . . ?
O8 C16 C17B C18B 150(2) . . . . ?
O9 C16 C17B C18B 40(3) . . . . ?
Hf1 C16 C17B C18B 98(2) 3_666 . . . ?
C16 C17B C18B C19 -46(3) . . . . ?
C17A C18A C19 O9 -24(3) . . . . ?
C17B C18B C19 O9 39(3) . . . . ?
O3 C1 N1 C4 1(2) . . . . ?
O2 C1 N1 C4 177.9(13) . . . . ?
O3 C1 N1 C2 171.3(16) . . . . ?
O2 C1 N1 C2 -12(2) . . . . ?
C5 C4 N1 C1 -105.3(17) . . . . ?
C5 C4 N1 C2 84(2) . . . . ?
C3 C2 N1 C1 82(2) . . . . ?
C3 C2 N1 C4 -107.7(18) . . . . ?
O5 C6 N2 C7 -5(2) . . . . ?
O4 C6 N2 C7 -180.0(16) . . . . ?
O5 C6 N2 C9 178.0(15) . . . . ?
O4 C6 N2 C9 3(2) . . . . ?
C8 C7 N2 C6 -75(2) . . . . ?
C8 C7 N2 C9 103(2) . . . . ?
C10 C9 N2 C6 85(2) . . . . ?
C10 C9 N2 C7 -92(2) . . . . ?
O7 C11 N3 C12 -174.1(13) . . . . ?
O6 C11 N3 C12 4(2) . . . . ?
O7 C11 N3 C14 14(2) . . . . ?
O6 C11 N3 C14 -167.4(15) . . . . ?
C13 C12 N3 C11 -93.1(18) . . . . ?
C13 C12 N3 C14 79.2(18) . . . . ?
C15 C14 N3 C11 -91(2) . . . . ?
C15 C14 N3 C12 97(2) . . . . ?
O3 C1 O2 Hf1 -3(2) . . . . ?
N1 C1 O2 Hf1 180.0(10) . . . . ?
O2 C1 O3 Hf2 -48(2) . . . . ?
N1 C1 O3 Hf2 128.7(13) . . . . ?
O5 C6 O4 Hf2 4.0(12) . . . . ?
N2 C6 O4 Hf2 179.7(12) . . . . ?
O4 C6 O5 Hf2 -4.1(12) . . . . ?
N2 C6 O5 Hf2 -179.5(13) . . . . ?
O7 C11 O6 Hf2 -12(2) . . . . ?
N3 C11 O6 Hf2 169.5(10) . . . . ?
O6 C11 O7 Hf1 12(2) . . . 3_666 ?
N3 C11 O7 Hf1 -169.3(10) . . . 3_666 ?
O9 C16 O8 Hf2 -135.7(9) . . . . ?
C17A C16 O8 Hf2 97(2) . . . . ?
C17B C16 O8 Hf2 115.1(19) . . . . ?
Hf1 C16 O8 Hf2 -130.4(13) 3_666 . . . ?
O9 C16 O8 Hf1 -5.3(12) . . . 3_666 ?
C17A C16 O8 Hf1 -132.7(18) . . . 3_666 ?
C17B C16 O8 Hf1 -114.5(17) . . . 3_666 ?
O8 C16 O9 C19 -129.9(13) . . . . ?
C17A C16 O9 C19 5(2) . . . . ?
C17B C16 O9 C19 -15(2) . . . . ?
Hf1 C16 O9 C19 -134.6(12) 3_666 . . . ?
O8 C16 O9 Hf1 4.8(11) . . . 3_666 ?
C17A C16 O9 Hf1 139(2) . . . 3_666 ?
C17B C16 O9 Hf1 120.1(16) . . . 3_666 ?
C18A C19 O9 C16 12(2) . . . . ?
C18B C19 O9 C16 -17(2) . . . . ?
C18A C19 O9 Hf1 -98(2) . . . 3_666 ?
C18B C19 O9 Hf1 -127.2(19) . . . 3_666 ?

_refine_diff_density_max         3.759
_refine_diff_density_min         -1.917
_refine_diff_density_rms         0.280





