# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_H4L_ibxx81_OR2
_database_code_depnum_ccdc_archive 'CCDC 1962565'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2019-10-30 deposited with the CCDC.	2020-02-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C18 H14 N4 O2, 0.5(N2 H4)'
_chemical_formula_sum            'C18 H16 N5 O2'
_chemical_formula_weight         334.36

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0040 0.0020
'XDISP Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
H H 0.0000 0.0000
'XDISP Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
N N 0.0076 0.0040
'XDISP Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
O O 0.0132 0.0074
'XDISP Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'

_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                   28.460(7)
_cell_length_b                   4.9320(11)
_cell_length_c                   24.318(6)
_cell_angle_alpha                90
_cell_angle_beta                 112.810(9)
_cell_angle_gamma                90
_cell_volume                     3146.4(13)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8541
_cell_measurement_theta_min      3.19
_cell_measurement_theta_max      33.60

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_F_000             1400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.030
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    0.116
_shelx_estimated_absorpt_T_min   0.979
_shelx_estimated_absorpt_T_max   0.998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.634
_exptl_absorpt_correction_T_max  0.745
_exptl_absorpt_process_details   'SADABS-2012/1 - Bruker AXS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.7749
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Advanced Light Source station 11.3.1'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'Bruker APEX II CCD diffractometer'
_diffrn_measurement_method       'π and ω rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10298
_diffrn_reflns_av_unetI/netI     0.0574
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         3.193
_diffrn_reflns_theta_max         32.556
_diffrn_reflns_theta_full        32.555
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measured_fraction_theta_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_point_group_measured_fraction_full 0.971
_reflns_number_total             4283
_reflns_number_gt                3514
_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       'Bruker APEX 2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2017 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically. The lattice
 hydrazine molecule is disordered over two equivalent positions,
 that are further disordered by symmetry. Hydrogens on the 
 pyrazole N, phenol O and hydrazine molecule were found in 
 difference Fourier maps and refined freely with their thermal
 parameter 1.5 times that of their carrier atom. N H distance 
 restraints were used for those on the hydrazine molecule. The
 rest of hydrogens were placed geometrically on their carrier
 carbon and refined with a riding model.
;

_vrf_PLAT417_H4L_ibxx81_OR2      
;
PROBLEM:  Short Inter D-H..H-D       H1     ..  H5B     ..       2.03 Ang.
RESPONSE: This short contact is likely due to the
hydrogen bond formed by O1 with N5, and the relatively
long O1-H1 bond.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0737P)²+1.8765P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4283
_refine_ls_number_parameters     259
_refine_ls_number_restraints     10
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0514
_refine_ls_wR_factor_ref         0.1454
_refine_ls_wR_factor_gt          0.1369
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_restrained_S_all      1.035
_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
O1 O 0.06396(4) 1.0861(2) 0.34095(5) 0.0358(3) Uani 1 1 d . . . . .
H1 H 0.0490(8) 1.239(5) 0.3133(10) 0.054 Uiso 1 1 d . U . . .
O2 O 0.04653(4) -0.4199(2) 0.65396(5) 0.0331(3) Uani 1 1 d . . . . .
H2 H 0.0354(8) -0.286(5) 0.6233(9) 0.050 Uiso 1 1 d . U . . .
N1 N 0.06497(4) 0.7592(2) 0.42952(5) 0.0236(2) Uani 1 1 d . . . . .
H1N H 0.0427(7) 0.880(4) 0.4070(8) 0.035 Uiso 1 1 d . U . . .
N2 N 0.05023(4) 0.5929(2) 0.46421(4) 0.0229(2) Uani 1 1 d . . . . .
N3 N 0.04644(4) 0.1764(2) 0.54563(5) 0.0217(2) Uani 1 1 d . . . . .
H3N H 0.0172(7) 0.266(4) 0.5331(8) 0.032 Uiso 1 1 d . U . . .
N4 N 0.05544(4) -0.0218(2) 0.58682(5) 0.0220(2) Uani 1 1 d . . . . .
C1 C 0.11574(5) 1.0613(3) 0.36126(6) 0.0270(3) Uani 1 1 d . . . . .
C2 C 0.14400(6) 1.2224(3) 0.33764(7) 0.0315(3) Uani 1 1 d . . . . .
H2A H 0.127013 1.350459 0.307217 0.038 Uiso 1 1 calc R U . . .
C3 C 0.19630(6) 1.1964(3) 0.35826(7) 0.0330(3) Uani 1 1 d . . . . .
H3 H 0.215157 1.308545 0.342429 0.040 Uiso 1 1 calc R U . . .
C4 C 0.22156(6) 1.0063(3) 0.40222(7) 0.0337(3) Uani 1 1 d . . . . .
H4 H 0.257522 0.986831 0.416120 0.040 Uiso 1 1 calc R U . . .
C5 C 0.19362(5) 0.8453(3) 0.42551(6) 0.0283(3) Uani 1 1 d . . . . .
H5 H 0.210882 0.714660 0.455175 0.034 Uiso 1 1 calc R U . . .
C6 C 0.14052(5) 0.8711(3) 0.40629(6) 0.0232(3) Uani 1 1 d . . . . .
C7 C 0.11362(5) 0.7084(3) 0.43550(5) 0.0214(2) Uani 1 1 d . . . . .
C8 C 0.13096(5) 0.4941(3) 0.47577(5) 0.0217(2) Uani 1 1 d . . . . .
H8 H 0.163406 0.408958 0.488995 0.026 Uiso 1 1 calc R U . . .
C9 C 0.09047(4) 0.4311(2) 0.49255(5) 0.0195(2) Uani 1 1 d . . . . .
C10 C 0.08881(4) 0.2256(2) 0.53480(5) 0.0192(2) Uani 1 1 d . . . . .
C11 C 0.12685(4) 0.0512(2) 0.56998(5) 0.0203(2) Uani 1 1 d . . . . .
H11 H 0.160728 0.037422 0.571843 0.024 Uiso 1 1 calc R U . . .
C12 C 0.10431(4) -0.1008(2) 0.60231(5) 0.0196(2) Uani 1 1 d . . . . .
C13 C 0.12686(5) -0.3133(3) 0.64702(5) 0.0206(2) Uani 1 1 d . . . . .
C14 C 0.17914(5) -0.3705(3) 0.66756(6) 0.0241(3) Uani 1 1 d . . . . .
H14 H 0.199872 -0.268833 0.652468 0.029 Uiso 1 1 calc R U . . .
C15 C 0.20132(5) -0.5725(3) 0.70950(6) 0.0264(3) Uani 1 1 d . . . . .
H15 H 0.236823 -0.607794 0.722804 0.032 Uiso 1 1 calc R U . . .
C16 C 0.17139(5) -0.7224(3) 0.73187(6) 0.0263(3) Uani 1 1 d . . . . .
H16 H 0.186440 -0.860337 0.760608 0.032 Uiso 1 1 calc R U . . .
C17 C 0.11970(5) -0.6712(3) 0.71235(6) 0.0264(3) Uani 1 1 d . . . . .
H17 H 0.099268 -0.776030 0.727352 0.032 Uiso 1 1 calc R U . . .
C18 C 0.09738(5) -0.4668(3) 0.67080(5) 0.0236(3) Uani 1 1 d . . . . .
N5 N 0.01315(15) 1.5483(7) 0.28310(13) 0.0373(8) Uani 0.5 1 d D U P A 1
H5A H 0.035(3) 1.701(11) 0.289(3) 0.056 Uiso 0.5 1 d D U P B 1
H5B H -0.0029(16) 1.530(9) 0.3090(17) 0.056 Uiso 0.5 1 d D U P C 1
N6 N 0.02649(11) 1.5048(6) 0.26580(16) 0.0388(6) Uani 0.5 1 d D U P D 2
H6A H 0.030(4) 1.656(11) 0.292(4) 0.058 Uiso 0.5 1 d D U P E 2
H6B H 0.0321(18) 1.538(10) 0.2296(14) 0.058 Uiso 0.5 1 d D U P F 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
O1 C1 1.3660(17) . ?
O1 H1 0.99(2) . ?
O2 C18 1.3622(16) . ?
O2 H2 0.95(2) . ?
N1 N2 1.3547(16) . ?
N1 C7 1.3584(16) . ?
N1 H1N 0.89(2) . ?
N2 C9 1.3459(15) . ?
N3 N4 1.3508(15) . ?
N3 C10 1.3522(16) . ?
N3 H3N 0.886(19) . ?
N4 C12 1.3500(15) . ?
C1 C2 1.402(2) . ?
C1 C6 1.4062(19) . ?
C2 C3 1.380(2) . ?
C2 H2A 0.9500 . ?
C3 C4 1.394(2) . ?
C3 H3 0.9500 . ?
C4 C5 1.390(2) . ?
C4 H4 0.9500 . ?
C5 C6 1.4037(19) . ?
C5 H5 0.9500 . ?
C6 C7 1.4684(18) . ?
C7 C8 1.3944(17) . ?
C8 C9 1.3983(17) . ?
C8 H8 0.9500 . ?
C9 C10 1.4571(17) . ?
C10 C11 1.3876(16) . ?
C11 C12 1.4080(17) . ?
C11 H11 0.9500 . ?
C12 C13 1.4668(17) . ?
C13 C14 1.4023(17) . ?
C13 C18 1.4099(18) . ?
C14 C15 1.3898(18) . ?
C14 H14 0.9500 . ?
C15 C16 1.388(2) . ?
C15 H15 0.9500 . ?
C16 C17 1.3827(19) . ?
C16 H16 0.9500 . ?
C17 C18 1.3942(18) . ?
C17 H17 0.9500 . ?
N5 N5 1.489(6) 2 ?
N5 H5A 0.95(2) . ?
N5 H5B 0.913(19) . ?
N6 N6 1.402(6) 2 ?
N6 H6A 0.96(2) . ?
N6 H6B 0.969(19) . ?

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 O1 H1 115.6(13) . . ?
C18 O2 H2 110.2(13) . . ?
N2 N1 C7 111.74(10) . . ?
N2 N1 H1N 118.2(12) . . ?
C7 N1 H1N 130.1(12) . . ?
C9 N2 N1 105.69(10) . . ?
N4 N3 C10 110.33(10) . . ?
N4 N3 H3N 119.8(12) . . ?
C10 N3 H3N 129.4(12) . . ?
C12 N4 N3 107.11(10) . . ?
O1 C1 C2 120.72(13) . . ?
O1 C1 C6 119.10(12) . . ?
C2 C1 C6 120.19(13) . . ?
C3 C2 C1 120.50(14) . . ?
C3 C2 H2A 119.8 . . ?
C1 C2 H2A 119.8 . . ?
C2 C3 C4 120.28(13) . . ?
C2 C3 H3 119.9 . . ?
C4 C3 H3 119.9 . . ?
C5 C4 C3 119.33(14) . . ?
C5 C4 H4 120.3 . . ?
C3 C4 H4 120.3 . . ?
C4 C5 C6 121.65(14) . . ?
C4 C5 H5 119.2 . . ?
C6 C5 H5 119.2 . . ?
C5 C6 C1 118.03(12) . . ?
C5 C6 C7 119.02(12) . . ?
C1 C6 C7 122.90(12) . . ?
N1 C7 C8 106.47(11) . . ?
N1 C7 C6 123.25(11) . . ?
C8 C7 C6 130.17(12) . . ?
C7 C8 C9 105.44(11) . . ?
C7 C8 H8 127.3 . . ?
C9 C8 H8 127.3 . . ?
N2 C9 C8 110.65(11) . . ?
N2 C9 C10 121.31(11) . . ?
C8 C9 C10 128.03(11) . . ?
N3 C10 C11 108.07(11) . . ?
N3 C10 C9 122.51(11) . . ?
C11 C10 C9 129.42(11) . . ?
C10 C11 C12 105.00(11) . . ?
C10 C11 H11 127.5 . . ?
C12 C11 H11 127.5 . . ?
N4 C12 C11 109.49(11) . . ?
N4 C12 C13 121.36(11) . . ?
C11 C12 C13 129.15(11) . . ?
C14 C13 C18 117.62(12) . . ?
C14 C13 C12 120.45(11) . . ?
C18 C13 C12 121.93(11) . . ?
C15 C14 C13 121.54(13) . . ?
C15 C14 H14 119.2 . . ?
C13 C14 H14 119.2 . . ?
C16 C15 C14 119.74(12) . . ?
C16 C15 H15 120.1 . . ?
C14 C15 H15 120.1 . . ?
C17 C16 C15 120.07(12) . . ?
C17 C16 H16 120.0 . . ?
C15 C16 H16 120.0 . . ?
C16 C17 C18 120.39(13) . . ?
C16 C17 H17 119.8 . . ?
C18 C17 H17 119.8 . . ?
O2 C18 C17 118.23(12) . . ?
O2 C18 C13 121.15(12) . . ?
C17 C18 C13 120.62(12) . . ?
N5 N5 H5A 100(5) 2 . ?
N5 N5 H5B 125(3) 2 . ?
H5A N5 H5B 117(4) . . ?
N6 N6 H6A 100(6) 2 . ?
N6 N6 H6B 91(3) 2 . ?
H6A N6 H6B 118(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
_geom_hbond_publ_flag
O1 H1 N5 0.99(2) 1.82(2) 2.773(4) 159.4(19) . yes
O1 H1 N6 0.99(2) 1.70(2) 2.689(3) 177(2) . yes
O2 H2 N4 0.95(2) 1.79(2) 2.6280(16) 145.0(18) . yes
N1 H1N O1 0.89(2) 2.175(19) 2.6814(16) 115.7(15) . yes
N3 H3N N2 0.886(19) 2.065(19) 2.9001(17) 156.7(16) 5_566 yes
N5 H5B O2 0.913(19) 1.88(2) 2.765(3) 164(4) 5_566 yes
N5 H5A O1 0.95(2) 2.26(3) 3.087(4) 146(4) 1_565 yes
N6 H6B O2 0.969(19) 2.12(3) 3.017(4) 154(4) 6_565 yes
N6 H6A O1 0.96(2) 2.45(3) 3.344(4) 156(5) 1_565 yes

_refine_diff_density_max         0.353
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.052

####################################################################### 
# 
# 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_ibcc1050
_database_code_depnum_ccdc_archive 'CCDC 1962567'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2019-10-30 deposited with the CCDC.	2020-02-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H22 N8 O6 Ti2, 2(C16 H36 N)'
_chemical_formula_sum            'C68 H94 N10 O6 Ti2'
_chemical_formula_weight         1243.33

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   12.3192(8)
_cell_length_b                   17.5994(11)
_cell_length_c                   14.9947(8)
_cell_angle_alpha                90
_cell_angle_beta                 96.710(4)
_cell_angle_gamma                90
_cell_volume                     3228.7(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3286
_cell_measurement_theta_min      2.31
_cell_measurement_theta_max      23.94

_exptl_crystal_description       plate
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_F_000             1328
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.270
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.060
_exptl_absorpt_coefficient_mu    0.307
_shelx_estimated_absorpt_T_min   0.922
_shelx_estimated_absorpt_T_max   0.982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.662
_exptl_absorpt_correction_T_max  0.745
_exptl_absorpt_process_details   'SADABS-2008/1, Bruker AXS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'multilayer monochromator ImuS'
_diffrn_measurement_device_type  'Bruker APEX II QUAZAR'
_diffrn_measurement_method       'φ and ω rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            22291
_diffrn_reflns_av_unetI/netI     0.0791
_diffrn_reflns_av_R_equivalents  0.0674
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.552
_diffrn_reflns_theta_max         25.563
_diffrn_reflns_theta_full        25.563
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             5976
_reflns_number_gt                4074
_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       'Bruker APEX 2'
_computing_cell_refinement       'SAINT (Bruker)'
_computing_data_reduction        'SAINT (Bruker)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically.
 Hydrogens were placed geometrically on their carrier atom and refined
 with a riding model, except those on the pyrazole N that were found in a
 difference Fourier map and refined with their thermal parameter 1.5 times
 that of their carrier N.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0527P)²+4.6388P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5976
_refine_ls_number_parameters     395
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1040
_refine_ls_R_factor_gt           0.0659
_refine_ls_wR_factor_ref         0.1571
_refine_ls_wR_factor_gt          0.1396
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_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 0.09632(5) 0.00325(4) 0.23564(4) 0.02086(19) Uani 1 1 d . . . . .
O1 O 0.0650(2) -0.08575(14) 0.21134(17) 0.0371(7) Uani 1 1 d . . . . .
O2 O 0.02867(18) 0.06379(14) 0.14020(15) 0.0236(6) Uani 1 1 d . . . . .
O3 O 0.24282(18) 0.02153(14) 0.21036(15) 0.0249(6) Uani 1 1 d . . . . .
N1 N -0.0478(2) 0.04093(16) 0.29478(18) 0.0214(7) Uani 1 1 d . . . . .
N2 N -0.0641(2) 0.03215(17) 0.38228(19) 0.0208(7) Uani 1 1 d . . . . .
H2 H -0.011(3) 0.012(2) 0.418(2) 0.031 Uiso 1 1 d . U . . .
N3 N 0.1270(2) -0.01925(16) 0.44623(18) 0.0209(7) Uani 1 1 d . . . . .
N4 N 0.1803(2) -0.01000(16) 0.37133(18) 0.0202(6) Uani 1 1 d . . . . .
C1 C -0.0739(3) 0.07523(19) 0.1026(2) 0.0206(8) Uani 1 1 d . . . . .
C2 C -0.0949(3) 0.0843(2) 0.0096(2) 0.0241(8) Uani 1 1 d . . . . .
H2A H -0.036557 0.080589 -0.026430 0.029 Uiso 1 1 calc R U . . .
C3 C -0.1994(3) 0.0987(2) -0.0304(2) 0.0272(9) Uani 1 1 d . . . . .
H3A H -0.212458 0.104838 -0.093727 0.033 Uiso 1 1 calc R U . . .
C4 C -0.2860(3) 0.1042(2) 0.0212(2) 0.0276(9) Uani 1 1 d . . . . .
H4A H -0.357717 0.114848 -0.006531 0.033 Uiso 1 1 calc R U . . .
C5 C -0.2668(3) 0.0941(2) 0.1130(2) 0.0252(8) Uani 1 1 d . . . . .
H5A H -0.326036 0.097454 0.148023 0.030 Uiso 1 1 calc R U . . .
C6 C -0.1613(3) 0.07896(19) 0.1556(2) 0.0209(8) Uani 1 1 d . . . . .
C7 C -0.1448(3) 0.06582(19) 0.2518(2) 0.0197(8) Uani 1 1 d . . . . .
C8 C -0.2207(3) 0.0724(2) 0.3147(2) 0.0230(8) Uani 1 1 d . . . . .
H8A H -0.294354 0.089144 0.303335 0.028 Uiso 1 1 calc R U . . .
C9 C -0.1667(3) 0.04970(19) 0.3963(2) 0.0206(8) Uani 1 1 d . . . . .
C10 C 0.2016(3) -0.0395(2) 0.5148(2) 0.0201(8) Uani 1 1 d . . . . .
C11 C 0.3042(3) -0.0450(2) 0.4856(2) 0.0223(8) Uani 1 1 d . . . . .
H11A H 0.370798 -0.058646 0.520226 0.027 Uiso 1 1 calc R U . . .
C12 C 0.2888(3) -0.02610(19) 0.3947(2) 0.0204(8) Uani 1 1 d . . . . .
C13 C 0.3699(3) -0.02527(19) 0.3311(2) 0.0203(8) Uani 1 1 d . . . . .
C14 C 0.4785(3) -0.0460(2) 0.3595(2) 0.0243(8) Uani 1 1 d . . . . .
H14A H 0.498740 -0.058473 0.420788 0.029 Uiso 1 1 calc R U . . .
C15 C 0.5566(3) -0.0488(2) 0.3007(2) 0.0272(9) Uani 1 1 d . . . . .
H15A H 0.629760 -0.062311 0.321855 0.033 Uiso 1 1 calc R U . . .
C16 C 0.5282(3) -0.0317(2) 0.2112(3) 0.0263(9) Uani 1 1 d . . . . .
H16A H 0.581353 -0.035025 0.170264 0.032 Uiso 1 1 calc R U . . .
C17 C 0.4218(3) -0.0098(2) 0.1807(2) 0.0241(8) Uani 1 1 d . . . . .
H17A H 0.402686 0.001572 0.118925 0.029 Uiso 1 1 calc R U . . .
C18 C 0.3429(3) -0.00443(19) 0.2402(2) 0.0210(8) Uani 1 1 d . . . . .
N5 N 0.3563(2) 0.23237(17) 0.1628(2) 0.0263(7) Uani 1 1 d . . . . .
C19 C 0.3279(3) 0.1726(2) 0.0912(3) 0.0309(9) Uani 1 1 d . . . . .
H19A H 0.394302 0.142105 0.085887 0.037 Uiso 1 1 calc R U . . .
H19B H 0.272890 0.138065 0.112519 0.037 Uiso 1 1 calc R U . . .
C20 C 0.2841(3) 0.2001(2) -0.0013(3) 0.0353(10) Uani 1 1 d . . . . .
H20A H 0.341459 0.228914 -0.027766 0.042 Uiso 1 1 calc R U . . .
H20B H 0.221100 0.234298 0.002654 0.042 Uiso 1 1 calc R U . . .
C21 C 0.2485(4) 0.1320(3) -0.0608(3) 0.0487(12) Uani 1 1 d . . . . .
H21A H 0.310251 0.095862 -0.059211 0.058 Uiso 1 1 calc R U . . .
H21B H 0.187819 0.105717 -0.035591 0.058 Uiso 1 1 calc R U . . .
C22 C 0.2114(4) 0.1528(3) -0.1578(3) 0.0532(13) Uani 1 1 d . . . . .
H22A H 0.149951 0.188426 -0.160083 0.080 Uiso 1 1 calc R U . . .
H22B H 0.188260 0.106815 -0.191595 0.080 Uiso 1 1 calc R U . . .
H22C H 0.271987 0.176674 -0.184219 0.080 Uiso 1 1 calc R U . . .
C23 C 0.4311(3) 0.2935(2) 0.1317(3) 0.0287(9) Uani 1 1 d . . . . .
H23A H 0.389643 0.321710 0.081779 0.034 Uiso 1 1 calc R U . . .
H23B H 0.448495 0.329757 0.181795 0.034 Uiso 1 1 calc R U . . .
C24 C 0.5376(3) 0.2676(2) 0.1008(3) 0.0355(10) Uani 1 1 d . . . . .
H24A H 0.522981 0.231008 0.050700 0.043 Uiso 1 1 calc R U . . .
H24B H 0.583237 0.242058 0.150675 0.043 Uiso 1 1 calc R U . . .
C25 C 0.5980(3) 0.3370(2) 0.0696(3) 0.0395(11) Uani 1 1 d . . . . .
H25A H 0.551764 0.361361 0.019152 0.047 Uiso 1 1 calc R U . . .
H25B H 0.608391 0.374199 0.119458 0.047 Uiso 1 1 calc R U . . .
C26 C 0.7085(4) 0.3188(3) 0.0397(4) 0.0525(13) Uani 1 1 d . . . . .
H26A H 0.755845 0.296173 0.089838 0.079 Uiso 1 1 calc R U . . .
H26B H 0.742091 0.365578 0.020484 0.079 Uiso 1 1 calc R U . . .
H26C H 0.699048 0.282807 -0.010466 0.079 Uiso 1 1 calc R U . . .
C27 C 0.2558(3) 0.2743(2) 0.1864(3) 0.0282(9) Uani 1 1 d . . . . .
H27A H 0.222047 0.301075 0.132068 0.034 Uiso 1 1 calc R U . . .
H27B H 0.279675 0.313433 0.231982 0.034 Uiso 1 1 calc R U . . .
C28 C 0.1686(3) 0.2252(2) 0.2224(3) 0.0340(10) Uani 1 1 d . . . . .
H28A H 0.203273 0.185897 0.263506 0.041 Uiso 1 1 calc R U . . .
H28B H 0.123550 0.199541 0.172210 0.041 Uiso 1 1 calc R U . . .
C29 C 0.0971(3) 0.2778(2) 0.2727(3) 0.0401(11) Uani 1 1 d . . . . .
H29A H 0.142645 0.300707 0.324544 0.048 Uiso 1 1 calc R U . . .
H29B H 0.068854 0.319531 0.232198 0.048 Uiso 1 1 calc R U . . .
C30 C 0.0018(4) 0.2369(3) 0.3060(4) 0.0570(14) Uani 1 1 d . . . . .
H30A H -0.045185 0.215663 0.254812 0.085 Uiso 1 1 calc R U . . .
H30B H -0.040362 0.272755 0.338250 0.085 Uiso 1 1 calc R U . . .
H30C H 0.029162 0.195745 0.346590 0.085 Uiso 1 1 calc R U . . .
C31 C 0.4110(3) 0.1899(2) 0.2441(3) 0.0328(10) Uani 1 1 d . . . . .
H31A H 0.367693 0.143581 0.252477 0.039 Uiso 1 1 calc R U . . .
H31B H 0.484118 0.173206 0.230744 0.039 Uiso 1 1 calc R U . . .
C32 C 0.4249(3) 0.2331(2) 0.3317(3) 0.0320(9) Uani 1 1 d . . . . .
H32A H 0.352223 0.244566 0.350442 0.038 Uiso 1 1 calc R U . . .
H32B H 0.462619 0.281789 0.323541 0.038 Uiso 1 1 calc R U . . .
C33 C 0.4913(3) 0.1864(2) 0.4044(3) 0.0390(11) Uani 1 1 d . . . . .
H33A H 0.457525 0.135593 0.407482 0.047 Uiso 1 1 calc R U . . .
H33B H 0.566116 0.179373 0.387959 0.047 Uiso 1 1 calc R U . . .
C34 C 0.4979(3) 0.2237(3) 0.4963(3) 0.0416(11) Uani 1 1 d . . . . .
H34A H 0.529319 0.274719 0.493287 0.062 Uiso 1 1 calc R U . . .
H34B H 0.544331 0.193037 0.539996 0.062 Uiso 1 1 calc R U . . .
H34C H 0.424461 0.227537 0.514902 0.062 Uiso 1 1 calc R U . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O1 1.644(3) . ?
Ti1 O2 1.897(2) . ?
Ti1 O3 1.914(2) . ?
Ti1 N1 2.179(3) . ?
Ti1 N4 2.185(3) . ?
O2 C1 1.337(4) . ?
O3 C18 1.342(4) . ?
N1 N2 1.359(4) . ?
N1 C7 1.361(4) . ?
N2 C9 1.342(4) . ?
N2 H2 0.88(4) . ?
N3 C10 1.344(4) . ?
N3 N4 1.375(4) . ?
N4 C12 1.371(4) . ?
C1 C2 1.397(5) . ?
C1 C6 1.413(5) . ?
C2 C3 1.379(5) . ?
C2 H2A 0.9500 . ?
C3 C4 1.393(5) . ?
C3 H3A 0.9500 . ?
C4 C5 1.380(5) . ?
C4 H4A 0.9500 . ?
C5 C6 1.405(5) . ?
C5 H5A 0.9500 . ?
C6 C7 1.453(5) . ?
C7 C8 1.409(5) . ?
C8 C9 1.382(5) . ?
C8 H8A 0.9500 . ?
C9 C10 1.458(5) 3_556 ?
C10 C11 1.388(5) . ?
C11 C12 1.393(5) . ?
C11 H11A 0.9500 . ?
C12 C13 1.461(5) . ?
C13 C14 1.404(5) . ?
C13 C18 1.412(5) . ?
C14 C15 1.379(5) . ?
C14 H14A 0.9500 . ?
C15 C16 1.381(5) . ?
C15 H15A 0.9500 . ?
C16 C17 1.390(5) . ?
C16 H16A 0.9500 . ?
C17 C18 1.398(5) . ?
C17 H17A 0.9500 . ?
N5 C19 1.514(5) . ?
N5 C27 1.519(4) . ?
N5 C31 1.519(5) . ?
N5 C23 1.524(4) . ?
C19 C20 1.508(5) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C21 1.527(6) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.518(6) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 C24 1.512(5) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.531(5) . ?
C24 H24A 0.9900 . ?
C24 H24B 0.9900 . ?
C25 C26 1.517(6) . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C27 C28 1.526(5) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C28 C29 1.536(5) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 C30 1.510(6) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
C31 C32 1.510(5) . ?
C31 H31A 0.9900 . ?
C31 H31B 0.9900 . ?
C32 C33 1.523(5) . ?
C32 H32A 0.9900 . ?
C32 H32B 0.9900 . ?
C33 C34 1.520(6) . ?
C33 H33A 0.9900 . ?
C33 H33B 0.9900 . ?
C34 H34A 0.9800 . ?
C34 H34B 0.9800 . ?
C34 H34C 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
O1 Ti1 O2 107.26(12) . . ?
O1 Ti1 O3 108.59(13) . . ?
O2 Ti1 O3 95.59(10) . . ?
O1 Ti1 N1 101.46(13) . . ?
O2 Ti1 N1 80.15(10) . . ?
O3 Ti1 N1 149.49(11) . . ?
O1 Ti1 N4 100.26(12) . . ?
O2 Ti1 N4 151.76(11) . . ?
O3 Ti1 N4 81.23(10) . . ?
N1 Ti1 N4 88.47(10) . . ?
C1 O2 Ti1 135.5(2) . . ?
C18 O3 Ti1 136.7(2) . . ?
N2 N1 C7 105.9(3) . . ?
N2 N1 Ti1 125.2(2) . . ?
C7 N1 Ti1 128.1(2) . . ?
C9 N2 N1 111.9(3) . . ?
C9 N2 H2 130(2) . . ?
N1 N2 H2 117(2) . . ?
C10 N3 N4 107.9(3) . . ?
C12 N4 N3 108.1(3) . . ?
C12 N4 Ti1 127.0(2) . . ?
N3 N4 Ti1 123.6(2) . . ?
O2 C1 C2 119.6(3) . . ?
O2 C1 C6 120.9(3) . . ?
C2 C1 C6 119.4(3) . . ?
C3 C2 C1 120.7(3) . . ?
C3 C2 H2A 119.7 . . ?
C1 C2 H2A 119.7 . . ?
C2 C3 C4 120.5(3) . . ?
C2 C3 H3A 119.7 . . ?
C4 C3 H3A 119.7 . . ?
C5 C4 C3 119.5(3) . . ?
C5 C4 H4A 120.3 . . ?
C3 C4 H4A 120.3 . . ?
C4 C5 C6 121.3(3) . . ?
C4 C5 H5A 119.3 . . ?
C6 C5 H5A 119.3 . . ?
C5 C6 C1 118.6(3) . . ?
C5 C6 C7 119.8(3) . . ?
C1 C6 C7 121.6(3) . . ?
N1 C7 C8 108.9(3) . . ?
N1 C7 C6 122.3(3) . . ?
C8 C7 C6 128.7(3) . . ?
C9 C8 C7 106.3(3) . . ?
C9 C8 H8A 126.9 . . ?
C7 C8 H8A 126.9 . . ?
N2 C9 C8 107.0(3) . . ?
N2 C9 C10 119.9(3) . 3_556 ?
C8 C9 C10 133.0(3) . 3_556 ?
N3 C10 C11 110.1(3) . . ?
N3 C10 C9 118.9(3) . 3_556 ?
C11 C10 C9 131.0(3) . 3_556 ?
C10 C11 C12 105.5(3) . . ?
C10 C11 H11A 127.2 . . ?
C12 C11 H11A 127.2 . . ?
N4 C12 C11 108.5(3) . . ?
N4 C12 C13 123.5(3) . . ?
C11 C12 C13 128.0(3) . . ?
C14 C13 C18 118.0(3) . . ?
C14 C13 C12 120.0(3) . . ?
C18 C13 C12 122.1(3) . . ?
C15 C14 C13 121.8(3) . . ?
C15 C14 H14A 119.1 . . ?
C13 C14 H14A 119.1 . . ?
C14 C15 C16 119.8(3) . . ?
C14 C15 H15A 120.1 . . ?
C16 C15 H15A 120.1 . . ?
C15 C16 C17 120.1(3) . . ?
C15 C16 H16A 119.9 . . ?
C17 C16 H16A 119.9 . . ?
C16 C17 C18 120.5(3) . . ?
C16 C17 H17A 119.7 . . ?
C18 C17 H17A 119.7 . . ?
O3 C18 C17 119.4(3) . . ?
O3 C18 C13 120.9(3) . . ?
C17 C18 C13 119.7(3) . . ?
C19 N5 C27 112.0(3) . . ?
C19 N5 C31 105.7(3) . . ?
C27 N5 C31 110.4(3) . . ?
C19 N5 C23 111.8(3) . . ?
C27 N5 C23 105.5(3) . . ?
C31 N5 C23 111.4(3) . . ?
C20 C19 N5 117.2(3) . . ?
C20 C19 H19A 108.0 . . ?
N5 C19 H19A 108.0 . . ?
C20 C19 H19B 108.0 . . ?
N5 C19 H19B 108.0 . . ?
H19A C19 H19B 107.2 . . ?
C19 C20 C21 109.5(3) . . ?
C19 C20 H20A 109.8 . . ?
C21 C20 H20A 109.8 . . ?
C19 C20 H20B 109.8 . . ?
C21 C20 H20B 109.8 . . ?
H20A C20 H20B 108.2 . . ?
C22 C21 C20 113.8(4) . . ?
C22 C21 H21A 108.8 . . ?
C20 C21 H21A 108.8 . . ?
C22 C21 H21B 108.8 . . ?
C20 C21 H21B 108.8 . . ?
H21A C21 H21B 107.7 . . ?
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 . . ?
C24 C23 N5 117.4(3) . . ?
C24 C23 H23A 108.0 . . ?
N5 C23 H23A 108.0 . . ?
C24 C23 H23B 108.0 . . ?
N5 C23 H23B 108.0 . . ?
H23A C23 H23B 107.2 . . ?
C23 C24 C25 108.9(3) . . ?
C23 C24 H24A 109.9 . . ?
C25 C24 H24A 109.9 . . ?
C23 C24 H24B 109.9 . . ?
C25 C24 H24B 109.9 . . ?
H24A C24 H24B 108.3 . . ?
C26 C25 C24 114.0(3) . . ?
C26 C25 H25A 108.8 . . ?
C24 C25 H25A 108.8 . . ?
C26 C25 H25B 108.8 . . ?
C24 C25 H25B 108.8 . . ?
H25A C25 H25B 107.7 . . ?
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 . . ?
N5 C27 C28 115.7(3) . . ?
N5 C27 H27A 108.3 . . ?
C28 C27 H27A 108.3 . . ?
N5 C27 H27B 108.3 . . ?
C28 C27 H27B 108.3 . . ?
H27A C27 H27B 107.4 . . ?
C27 C28 C29 107.5(3) . . ?
C27 C28 H28A 110.2 . . ?
C29 C28 H28A 110.2 . . ?
C27 C28 H28B 110.2 . . ?
C29 C28 H28B 110.2 . . ?
H28A C28 H28B 108.5 . . ?
C30 C29 C28 112.8(4) . . ?
C30 C29 H29A 109.0 . . ?
C28 C29 H29A 109.0 . . ?
C30 C29 H29B 109.0 . . ?
C28 C29 H29B 109.0 . . ?
H29A C29 H29B 107.8 . . ?
C29 C30 H30A 109.5 . . ?
C29 C30 H30B 109.5 . . ?
H30A C30 H30B 109.5 . . ?
C29 C30 H30C 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
C32 C31 N5 116.5(3) . . ?
C32 C31 H31A 108.2 . . ?
N5 C31 H31A 108.2 . . ?
C32 C31 H31B 108.2 . . ?
N5 C31 H31B 108.2 . . ?
H31A C31 H31B 107.3 . . ?
C31 C32 C33 110.4(3) . . ?
C31 C32 H32A 109.6 . . ?
C33 C32 H32A 109.6 . . ?
C31 C32 H32B 109.6 . . ?
C33 C32 H32B 109.6 . . ?
H32A C32 H32B 108.1 . . ?
C34 C33 C32 112.6(3) . . ?
C34 C33 H33A 109.1 . . ?
C32 C33 H33A 109.1 . . ?
C34 C33 H33B 109.1 . . ?
C32 C33 H33B 109.1 . . ?
H33A C33 H33B 107.8 . . ?
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 . . ?

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
_geom_hbond_publ_flag
N2 H2 N3 0.88(4) 1.79(4) 2.598(4) 153(4) . yes

_refine_diff_density_max         0.926
_refine_diff_density_min         -0.593
_refine_diff_density_rms         0.072

####################################################################### 
# 
# 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_orz2080
_database_code_depnum_ccdc_archive 'CCDC 1969357'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2019-12-02 deposited with the CCDC.	2020-02-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H22 N8 O6 Ti2, 2(C16 H36 N)'
_chemical_formula_sum            'C68 H94 N10 O6 Ti2'
_chemical_formula_weight         1243.33

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0040 0.0020
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
H H 0.0000 0.0000
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
N N 0.0076 0.0040
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
O O 0.0132 0.0074
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
Ti Ti 0.3064 0.5283
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'

_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                   9.9438(4)
_cell_length_b                   12.8964(10)
_cell_length_c                   13.5489(6)
_cell_angle_alpha                86.435(5)
_cell_angle_beta                 79.518(4)
_cell_angle_gamma                74.129(5)
_cell_volume                     1643.24(17)
_cell_formula_units_Z            1
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    15553
_cell_measurement_theta_min      2.548
_cell_measurement_theta_max      33.944

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_F_000             664
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.376
_shelx_estimated_absorpt_T_min   0.971
_shelx_estimated_absorpt_T_max   0.985
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.7749
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'ALBA XALOC beamline'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'MD2M - Maatel + Dectris PILATUS 6M'
_diffrn_measurement_method       'ω rotation at various κ'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19352
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         1.667
_diffrn_reflns_theta_max         29.783
_diffrn_reflns_theta_full        27.706
_diffrn_measured_fraction_theta_max 0.899
_diffrn_measured_fraction_theta_full 0.909
_diffrn_reflns_Laue_measured_fraction_max 0.899
_diffrn_reflns_Laue_measured_fraction_full 0.909
_diffrn_reflns_point_group_measured_fraction_max 0.899
_diffrn_reflns_point_group_measured_fraction_full 0.909
_reflns_number_total             6528
_reflns_number_gt                6089
_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       'Global Phasing autoPROC package'
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically. The tetrabutyl ammonium
 cation is heavily disordered and was refined over two positions with
 relative occupancies 0.460 (N5 > C34):0.540 (N5B > C34B), using 1,2 and 
 1,3 distances restraints (SADI and SAME) and displacement parameters 
 restraints (SIMU and DELU). Hydrogens were placed geometrically on their 
 carrier atom and refined with a riding model. Due to the centrosymmetric 
 nature of the complex anion, hydrogens on the pyrazole N atom are disordered 
 over two equivalent positions, by symmetry.
;

_vrf_PLAT029_orz2080             
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.909       
RESPONSE: Data were acquired at a synchrotron beamline dedicated to
protein crystallography that only allows high-accuracy omega scan and a
mini-kappa (0 to 90 degrees). Although, three full omega scans at
three different kappa angles were acquired, these conditions put 
limitations on the completeness, especially for a triclinic space 
group as here. This results in a relatively low completeness at 
theta_full as well as missing reflections.
;

_vrf_PLAT911_orz2080             
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.600        537       
RESPONSE: Data were acquired at a synchrotron beamline dedicated to
protein crystallography that only allows high-accuracy omega scan and a
mini-kappa (0 to 90 degrees). Although, three full omega scans at
three different kappa angles were acquired, these conditions put 
limitations on the completeness, especially for a triclinic space 
group as here. This results in a relatively low completeness at 
theta_full as well as missing reflections.
;

_vrf_DIFMN03_orz2080             
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.      
RESPONSE: The remaining electron density max. and min. at the
end of the refinement are in the vicinity of the two components
of the disordered tetrabutylammonium cation, likely associated
with this disorder. Specifically, the minimum density peak is
close to C25B.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2274P)²+3.8900P] 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         6528
_refine_ls_number_parameters     542
_refine_ls_number_restraints     733
_refine_ls_R_factor_all          0.1203
_refine_ls_R_factor_gt           0.1166
_refine_ls_wR_factor_ref         0.3350
_refine_ls_wR_factor_gt          0.3285
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_restrained_S_all      1.128
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_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 0.25495(7) 0.40747(6) 0.76478(5) 0.0308(3) Uani 1 1 d . . . . .
O1 O 0.3668(4) 0.4033(3) 0.8414(3) 0.0457(8) Uani 1 1 d . . . . .
O2 O 0.0705(3) 0.4932(3) 0.8214(2) 0.0418(8) Uani 1 1 d . . . . .
O3 O 0.8024(3) 0.7226(3) 0.2212(2) 0.0383(7) Uani 1 1 d . . . . .
N1 N 0.2520(4) 0.5599(3) 0.6833(2) 0.0330(8) Uani 1 1 d . . . . .
N2 N 0.3517(3) 0.5727(3) 0.6046(2) 0.0332(7) Uani 1 1 d . . . . .
H2B H 0.418257 0.519167 0.573833 0.040 Uiso 0.5 1 calc R U P . .
N3 N 0.5215(3) 0.6305(3) 0.4346(2) 0.0296(7) Uani 1 1 d . . . . .
H3B H 0.523720 0.561652 0.438569 0.036 Uiso 0.5 1 calc R U P . .
N4 N 0.6059(3) 0.6768(3) 0.3657(2) 0.0308(7) Uani 1 1 d . . . . .
C1 C 0.0110(5) 0.5952(4) 0.8488(3) 0.0434(11) Uani 1 1 d . . . . .
C2 C -0.0971(6) 0.6185(4) 0.9325(4) 0.0539(14) Uani 1 1 d . . . . .
H2A H -0.126873 0.561162 0.969318 0.065 Uiso 1 1 calc R U . . .
C3 C -0.1613(7) 0.7233(5) 0.9625(4) 0.071(2) Uani 1 1 d . . . . .
H3A H -0.234651 0.737361 1.019511 0.086 Uiso 1 1 calc R U . . .
C4 C -0.1196(8) 0.8088(5) 0.9099(4) 0.071(2) Uani 1 1 d . . . . .
H4A H -0.163759 0.880906 0.930870 0.086 Uiso 1 1 calc R U . . .
C5 C -0.0124(6) 0.7872(4) 0.8262(4) 0.0584(16) Uani 1 1 d . . . . .
H5A H 0.015491 0.845300 0.789449 0.070 Uiso 1 1 calc R U . . .
C6 C 0.0551(5) 0.6810(4) 0.7951(3) 0.0427(11) Uani 1 1 d . . . . .
C7 C 0.1706(4) 0.6606(4) 0.7092(3) 0.0370(9) Uani 1 1 d . . . . .
C8 C 0.2209(5) 0.7364(4) 0.6445(3) 0.0372(9) Uani 1 1 d . . . . .
H8A H 0.183490 0.812575 0.645252 0.045 Uiso 1 1 calc R U . . .
C9 C 0.3366(4) 0.6769(3) 0.5793(3) 0.0324(8) Uani 1 1 d . . . . .
C10 C 0.4345(4) 0.7079(3) 0.4955(3) 0.0313(8) Uani 1 1 d . . . . .
C11 C 0.4590(4) 0.8071(4) 0.4664(3) 0.0340(8) Uani 1 1 d . . . . .
H11A H 0.411408 0.875094 0.496066 0.041 Uiso 1 1 calc R U . . .
C12 C 0.5690(4) 0.7850(3) 0.3839(3) 0.0315(8) Uani 1 1 d . . . . .
C13 C 0.6352(4) 0.8611(4) 0.3230(3) 0.0383(9) Uani 1 1 d . . . . .
C14 C 0.5854(6) 0.9720(4) 0.3420(4) 0.0497(12) Uani 1 1 d . . . . .
H14A H 0.508159 0.996513 0.395077 0.060 Uiso 1 1 calc R U . . .
C15 C 0.6445(7) 1.0463(5) 0.2864(5) 0.071(2) Uani 1 1 d . . . . .
H15A H 0.610600 1.120839 0.301763 0.085 Uiso 1 1 calc R U . . .
C16 C 0.7553(8) 1.0099(6) 0.2070(6) 0.085(3) Uani 1 1 d . . . . .
H16A H 0.795848 1.060430 0.166858 0.101 Uiso 1 1 calc R U . . .
C17 C 0.8067(6) 0.9019(5) 0.1860(5) 0.0644(17) Uani 1 1 d . . . . .
H17A H 0.883255 0.878649 0.132106 0.077 Uiso 1 1 calc R U . . .
C18 C 0.7482(5) 0.8265(4) 0.2423(4) 0.0431(10) Uani 1 1 d . . . . .
N5 N 0.1902(9) 0.7192(8) 0.2550(7) 0.0618(16) Uani 0.460(4) 1 d D U P A 1
C19 C 0.2555(12) 0.6158(9) 0.3082(11) 0.071(2) Uani 0.460(4) 1 d D U P A 1
H19A H 0.350306 0.582776 0.268855 0.086 Uiso 0.460(4) 1 calc R U P A 1
H19B H 0.270442 0.635172 0.374241 0.086 Uiso 0.460(4) 1 calc R U P A 1
C20 C 0.1766(17) 0.5333(12) 0.3254(15) 0.086(2) Uani 0.460(4) 1 d D U P A 1
H20A H 0.173194 0.505074 0.259841 0.103 Uiso 0.460(4) 1 calc R U P A 1
H20B H 0.077788 0.567120 0.357739 0.103 Uiso 0.460(4) 1 calc R U P A 1
C21 C 0.241(2) 0.4406(14) 0.3903(18) 0.099(3) Uani 0.460(4) 1 d D U P A 1
H21A H 0.339575 0.406394 0.357324 0.118 Uiso 0.460(4) 1 calc R U P A 1
H21B H 0.246281 0.469302 0.455278 0.118 Uiso 0.460(4) 1 calc R U P A 1
C22 C 0.163(3) 0.3579(17) 0.410(2) 0.127(7) Uani 0.460(4) 1 d D U P A 1
H22A H 0.210777 0.300524 0.452354 0.190 Uiso 0.460(4) 1 calc R U P A 1
H22B H 0.065985 0.390576 0.444227 0.190 Uiso 0.460(4) 1 calc R U P A 1
H22C H 0.159399 0.327587 0.346146 0.190 Uiso 0.460(4) 1 calc R U P A 1
C23 C 0.1623(11) 0.6956(10) 0.1546(7) 0.0593(19) Uani 0.460(4) 1 d D U P A 1
H23A H 0.079840 0.664618 0.167479 0.071 Uiso 0.460(4) 1 calc R U P A 1
H23B H 0.131730 0.765748 0.119968 0.071 Uiso 0.460(4) 1 calc R U P A 1
C24 C 0.2698(18) 0.6264(14) 0.0844(9) 0.069(3) Uani 0.460(4) 1 d D U P A 1
H24A H 0.265123 0.551352 0.100276 0.083 Uiso 0.460(4) 1 calc R U P A 1
H24B H 0.363191 0.631146 0.096501 0.083 Uiso 0.460(4) 1 calc R U P A 1
C25 C 0.2665(14) 0.6458(11) -0.0250(8) 0.071(2) Uani 0.460(4) 1 d D U P A 1
H25A H 0.336424 0.584290 -0.061600 0.085 Uiso 0.460(4) 1 calc R U P A 1
H25B H 0.171601 0.644309 -0.036580 0.085 Uiso 0.460(4) 1 calc R U P A 1
C26 C 0.2944(18) 0.7423(12) -0.0694(10) 0.072(3) Uani 0.460(4) 1 d D U P A 1
H26A H 0.288682 0.744284 -0.140959 0.108 Uiso 0.460(4) 1 calc R U P A 1
H26B H 0.224003 0.804647 -0.036327 0.108 Uiso 0.460(4) 1 calc R U P A 1
H26C H 0.389610 0.744343 -0.061466 0.108 Uiso 0.460(4) 1 calc R U P A 1
C27 C 0.2973(10) 0.7854(9) 0.2414(9) 0.0504(18) Uani 0.460(4) 1 d D U P A 1
H27A H 0.385210 0.744117 0.198880 0.060 Uiso 0.460(4) 1 calc R U P A 1
H27B H 0.320939 0.793061 0.307955 0.060 Uiso 0.460(4) 1 calc R U P A 1
C28 C 0.2531(12) 0.8977(10) 0.1950(10) 0.057(2) Uani 0.460(4) 1 d D U P A 1
H28A H 0.217156 0.892757 0.132383 0.068 Uiso 0.460(4) 1 calc R U P A 1
H28B H 0.175073 0.944085 0.242031 0.068 Uiso 0.460(4) 1 calc R U P A 1
C29 C 0.3763(14) 0.9486(9) 0.1716(11) 0.061(2) Uani 0.460(4) 1 d D U P A 1
H29A H 0.341208 1.023952 0.148566 0.073 Uiso 0.460(4) 1 calc R U P A 1
H29B H 0.414814 0.950219 0.233698 0.073 Uiso 0.460(4) 1 calc R U P A 1
C30 C 0.4939(15) 0.8885(13) 0.0920(14) 0.073(4) Uani 0.460(4) 1 d D U P A 1
H30A H 0.570653 0.924303 0.079552 0.110 Uiso 0.460(4) 1 calc R U P A 1
H30B H 0.530530 0.814190 0.114916 0.110 Uiso 0.460(4) 1 calc R U P A 1
H30C H 0.456915 0.887931 0.029774 0.110 Uiso 0.460(4) 1 calc R U P A 1
C31 C 0.0493(10) 0.7830(12) 0.3157(9) 0.079(2) Uani 0.460(4) 1 d D U P A 1
H31A H -0.016150 0.771208 0.273133 0.095 Uiso 0.460(4) 1 calc R U P A 1
H31B H 0.056997 0.856912 0.297479 0.095 Uiso 0.460(4) 1 calc R U P A 1
C32 C -0.057(2) 0.8079(15) 0.4173(13) 0.114(3) Uani 0.460(4) 1 d D U P A 1
H32A H -0.148910 0.794827 0.410483 0.137 Uiso 0.460(4) 1 calc R U P A 1
H32B H -0.018767 0.759595 0.471076 0.137 Uiso 0.460(4) 1 calc R U P A 1
C33 C -0.082(2) 0.9277(13) 0.4456(11) 0.097(4) Uani 0.460(4) 1 d D U P A 1
H33A H 0.000688 0.953554 0.412389 0.117 Uiso 0.460(4) 1 calc R U P A 1
H33B H -0.167112 0.972645 0.420942 0.117 Uiso 0.460(4) 1 calc R U P A 1
C34 C -0.1007(12) 0.9400(14) 0.5604(10) 0.086(4) Uani 0.460(4) 1 d D U P A 1
H34A H -0.115689 1.015856 0.576070 0.129 Uiso 0.460(4) 1 calc R U P A 1
H34B H -0.183093 0.915435 0.593170 0.129 Uiso 0.460(4) 1 calc R U P A 1
H34C H -0.015476 0.896364 0.584626 0.129 Uiso 0.460(4) 1 calc R U P A 1
N5B N 0.2381(8) 0.6433(7) 0.2289(7) 0.0678(15) Uani 0.540(4) 1 d D U P A 2
C19B C 0.3380(12) 0.5349(8) 0.2547(12) 0.077(2) Uani 0.540(4) 1 d D U P A 2
H19C H 0.431857 0.527382 0.211543 0.093 Uiso 0.540(4) 1 calc R U P A 2
H19D H 0.351219 0.537211 0.325107 0.093 Uiso 0.540(4) 1 calc R U P A 2
C20B C 0.2911(15) 0.4379(9) 0.2429(14) 0.089(3) Uani 0.540(4) 1 d D U P A 2
H20C H 0.307981 0.421299 0.170590 0.106 Uiso 0.540(4) 1 calc R U P A 2
H20D H 0.187651 0.453640 0.267620 0.106 Uiso 0.540(4) 1 calc R U P A 2
C21B C 0.3650(14) 0.3411(9) 0.2977(14) 0.093(3) Uani 0.540(4) 1 d D U P A 2
H21C H 0.468856 0.329126 0.277401 0.112 Uiso 0.540(4) 1 calc R U P A 2
H21D H 0.341143 0.355311 0.370677 0.112 Uiso 0.540(4) 1 calc R U P A 2
C22B C 0.3263(17) 0.2419(11) 0.2784(17) 0.120(6) Uani 0.540(4) 1 d D U P A 2
H22D H 0.377736 0.181315 0.316068 0.180 Uiso 0.540(4) 1 calc R U P A 2
H22E H 0.223949 0.252590 0.299767 0.180 Uiso 0.540(4) 1 calc R U P A 2
H22F H 0.351725 0.226393 0.206444 0.180 Uiso 0.540(4) 1 calc R U P A 2
C23B C 0.1893(13) 0.6367(12) 0.1328(9) 0.075(2) Uani 0.540(4) 1 d D U P A 2
H23C H 0.143232 0.577436 0.134358 0.090 Uiso 0.540(4) 1 calc R U P A 2
H23D H 0.122889 0.705413 0.116231 0.090 Uiso 0.540(4) 1 calc R U P A 2
C24B C 0.3160(13) 0.6162(15) 0.0665(11) 0.077(2) Uani 0.540(4) 1 d D U P A 2
H24C H 0.336662 0.686361 0.071244 0.093 Uiso 0.540(4) 1 calc R U P A 2
H24D H 0.375960 0.567696 0.110478 0.093 Uiso 0.540(4) 1 calc R U P A 2
C25B C 0.401(2) 0.5850(14) -0.0231(12) 0.107(3) Uani 0.540(4) 1 d D U P A 2
H25C H 0.368766 0.528881 -0.051514 0.129 Uiso 0.540(4) 1 calc R U P A 2
H25D H 0.499026 0.552032 -0.011269 0.129 Uiso 0.540(4) 1 calc R U P A 2
C26B C 0.403(2) 0.6725(16) -0.0972(15) 0.116(5) Uani 0.540(4) 1 d D U P A 2
H26D H 0.465995 0.643792 -0.159372 0.174 Uiso 0.540(4) 1 calc R U P A 2
H26E H 0.306607 0.704490 -0.111043 0.174 Uiso 0.540(4) 1 calc R U P A 2
H26F H 0.437073 0.727679 -0.070734 0.174 Uiso 0.540(4) 1 calc R U P A 2
C27B C 0.3137(10) 0.7298(9) 0.2281(10) 0.0617(18) Uani 0.540(4) 1 d D U P A 2
H27C H 0.399922 0.712300 0.175914 0.074 Uiso 0.540(4) 1 calc R U P A 2
H27D H 0.344970 0.727847 0.293679 0.074 Uiso 0.540(4) 1 calc R U P A 2
C28B C 0.2262(10) 0.8461(8) 0.2085(9) 0.0555(18) Uani 0.540(4) 1 d D U P A 2
H28C H 0.193260 0.849388 0.143430 0.067 Uiso 0.540(4) 1 calc R U P A 2
H28D H 0.141580 0.866144 0.261846 0.067 Uiso 0.540(4) 1 calc R U P A 2
C29B C 0.3154(9) 0.9265(7) 0.2067(7) 0.0416(16) Uani 0.540(4) 1 d D U P A 2
H29C H 0.251917 1.000609 0.209162 0.050 Uiso 0.540(4) 1 calc R U P A 2
H29D H 0.360193 0.914768 0.267472 0.050 Uiso 0.540(4) 1 calc R U P A 2
C30B C 0.4299(10) 0.9166(8) 0.1148(8) 0.045(2) Uani 0.540(4) 1 d D U P A 2
H30D H 0.483108 0.969739 0.117842 0.068 Uiso 0.540(4) 1 calc R U P A 2
H30E H 0.494618 0.843907 0.112669 0.068 Uiso 0.540(4) 1 calc R U P A 2
H30F H 0.386272 0.929804 0.054321 0.068 Uiso 0.540(4) 1 calc R U P A 2
C31B C 0.0972(10) 0.6691(11) 0.3020(9) 0.0772(18) Uani 0.540(4) 1 d D U P A 2
H31C H 0.056535 0.606940 0.303073 0.093 Uiso 0.540(4) 1 calc R U P A 2
H31D H 0.031674 0.731528 0.274097 0.093 Uiso 0.540(4) 1 calc R U P A 2
C32B C 0.0976(14) 0.6953(12) 0.4141(10) 0.096(2) Uani 0.540(4) 1 d D U P A 2
H32C H 0.028956 0.664922 0.460936 0.115 Uiso 0.540(4) 1 calc R U P A 2
H32D H 0.193198 0.665253 0.431695 0.115 Uiso 0.540(4) 1 calc R U P A 2
C33B C 0.0536(13) 0.8209(12) 0.4190(12) 0.093(3) Uani 0.540(4) 1 d D U P A 2
H33C H 0.063792 0.850400 0.349647 0.111 Uiso 0.540(4) 1 calc R U P A 2
H33D H 0.120185 0.843572 0.453616 0.111 Uiso 0.540(4) 1 calc R U P A 2
C34B C -0.1036(16) 0.872(2) 0.4748(14) 0.115(5) Uani 0.540(4) 1 d D U P A 2
H34D H -0.122581 0.950947 0.474541 0.172 Uiso 0.540(4) 1 calc R U P A 2
H34E H -0.170942 0.852200 0.440113 0.172 Uiso 0.540(4) 1 calc R U P A 2
H34F H -0.114444 0.845359 0.544276 0.172 Uiso 0.540(4) 1 calc R U P A 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 O1 1.643(3) . ?
Ti1 O3 1.902(3) 2_666 ?
Ti1 O2 1.913(3) . ?
Ti1 N4 2.178(3) 2_666 ?
Ti1 N1 2.189(4) . ?
O2 C1 1.332(6) . ?
O3 C18 1.328(6) . ?
N1 N2 1.352(5) . ?
N1 C7 1.357(5) . ?
N2 C9 1.341(6) . ?
N2 H2B 0.8800 . ?
N3 C10 1.341(5) . ?
N3 N4 1.362(5) . ?
N3 H3B 0.8800 . ?
N4 C12 1.367(5) . ?
C1 C2 1.398(6) . ?
C1 C6 1.412(7) . ?
C2 C3 1.379(8) . ?
C2 H2A 0.9500 . ?
C3 C4 1.393(9) . ?
C3 H3A 0.9500 . ?
C4 C5 1.392(7) . ?
C4 H4A 0.9500 . ?
C5 C6 1.404(7) . ?
C5 H5A 0.9500 . ?
C6 C7 1.459(6) . ?
C7 C8 1.407(6) . ?
C8 C9 1.387(5) . ?
C8 H8A 0.9500 . ?
C9 C10 1.467(6) . ?
C10 C11 1.386(6) . ?
C11 C12 1.397(5) . ?
C11 H11A 0.9500 . ?
C12 C13 1.460(6) . ?
C13 C14 1.402(7) . ?
C13 C18 1.414(6) . ?
C14 C15 1.375(8) . ?
C14 H14A 0.9500 . ?
C15 C16 1.392(8) . ?
C15 H15A 0.9500 . ?
C16 C17 1.375(9) . ?
C16 H16A 0.9500 . ?
C17 C18 1.386(7) . ?
C17 H17A 0.9500 . ?
N5 C23 1.502(11) . ?
N5 C19 1.516(10) . ?
N5 C27 1.518(10) . ?
N5 C31 1.533(11) . ?
C19 C20 1.471(11) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C21 1.506(12) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.470(13) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 C24 1.434(13) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.492(11) . ?
C24 H24A 0.9900 . ?
C24 H24B 0.9900 . ?
C25 C26 1.422(12) . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C26 H26A 0.9800 . ?
C26 H26B 0.9800 . ?
C26 H26C 0.9800 . ?
C27 C28 1.524(11) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C28 C29 1.518(11) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 C30 1.510(13) . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C30 H30A 0.9800 . ?
C30 H30B 0.9800 . ?
C30 H30C 0.9800 . ?
C31 C32 1.569(13) . ?
C31 H31A 0.9900 . ?
C31 H31B 0.9900 . ?
C32 C33 1.558(14) . ?
C32 H32A 0.9900 . ?
C32 H32B 0.9900 . ?
C33 C34 1.545(13) . ?
C33 H33A 0.9900 . ?
C33 H33B 0.9900 . ?
C34 H34A 0.9800 . ?
C34 H34B 0.9800 . ?
C34 H34C 0.9800 . ?
N5B C23B 1.485(11) . ?
N5B C27B 1.504(10) . ?
N5B C31B 1.528(11) . ?
N5B C19B 1.539(10) . ?
C19B C20B 1.476(11) . ?
C19B H19C 0.9900 . ?
C19B H19D 0.9900 . ?
C20B C21B 1.495(10) . ?
C20B H20C 0.9900 . ?
C20B H20D 0.9900 . ?
C21B C22B 1.484(13) . ?
C21B H21C 0.9900 . ?
C21B H21D 0.9900 . ?
C22B H22D 0.9800 . ?
C22B H22E 0.9800 . ?
C22B H22F 0.9800 . ?
C23B C24B 1.378(12) . ?
C23B H23C 0.9900 . ?
C23B H23D 0.9900 . ?
C24B C25B 1.361(13) . ?
C24B H24C 0.9900 . ?
C24B H24D 0.9900 . ?
C25B C26B 1.464(13) . ?
C25B H25C 0.9900 . ?
C25B H25D 0.9900 . ?
C26B H26D 0.9800 . ?
C26B H26E 0.9800 . ?
C26B H26F 0.9800 . ?
C27B C28B 1.549(10) . ?
C27B H27C 0.9900 . ?
C27B H27D 0.9900 . ?
C28B C29B 1.533(10) . ?
C28B H28C 0.9900 . ?
C28B H28D 0.9900 . ?
C29B C30B 1.513(10) . ?
C29B H29C 0.9900 . ?
C29B H29D 0.9900 . ?
C30B H30D 0.9800 . ?
C30B H30E 0.9800 . ?
C30B H30F 0.9800 . ?
C31B C32B 1.578(13) . ?
C31B H31C 0.9900 . ?
C31B H31D 0.9900 . ?
C32B C33B 1.560(13) . ?
C32B H32C 0.9900 . ?
C32B H32D 0.9900 . ?
C33B C34B 1.588(13) . ?
C33B H33C 0.9900 . ?
C33B H33D 0.9900 . ?
C34B H34D 0.9800 . ?
C34B H34E 0.9800 . ?
C34B H34F 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
O1 Ti1 O3 109.20(17) . 2_666 ?
O1 Ti1 O2 109.78(17) . . ?
O3 Ti1 O2 93.20(14) 2_666 . ?
O1 Ti1 N4 102.07(16) . 2_666 ?
O3 Ti1 N4 81.16(13) 2_666 2_666 ?
O2 Ti1 N4 147.68(14) . 2_666 ?
O1 Ti1 N1 102.58(16) . . ?
O3 Ti1 N1 147.97(14) 2_666 . ?
O2 Ti1 N1 79.44(13) . . ?
N4 Ti1 N1 88.62(13) 2_666 . ?
C1 O2 Ti1 137.1(3) . . ?
C18 O3 Ti1 139.1(3) . 2_666 ?
N2 N1 C7 106.1(3) . . ?
N2 N1 Ti1 124.3(3) . . ?
C7 N1 Ti1 128.7(3) . . ?
C9 N2 N1 111.7(3) . . ?
C9 N2 H2B 124.1 . . ?
N1 N2 H2B 124.1 . . ?
C10 N3 N4 108.1(3) . . ?
C10 N3 H3B 126.0 . . ?
N4 N3 H3B 126.0 . . ?
N3 N4 C12 108.3(3) . . ?
N3 N4 Ti1 123.4(3) . 2_666 ?
C12 N4 Ti1 127.5(3) . 2_666 ?
O2 C1 C2 119.7(5) . . ?
O2 C1 C6 121.3(4) . . ?
C2 C1 C6 119.0(4) . . ?
C3 C2 C1 121.0(5) . . ?
C3 C2 H2A 119.5 . . ?
C1 C2 H2A 119.5 . . ?
C2 C3 C4 120.7(5) . . ?
C2 C3 H3A 119.7 . . ?
C4 C3 H3A 119.7 . . ?
C5 C4 C3 119.1(5) . . ?
C5 C4 H4A 120.4 . . ?
C3 C4 H4A 120.4 . . ?
C4 C5 C6 121.1(5) . . ?
C4 C5 H5A 119.5 . . ?
C6 C5 H5A 119.5 . . ?
C5 C6 C1 119.1(4) . . ?
C5 C6 C7 119.8(5) . . ?
C1 C6 C7 121.1(4) . . ?
N1 C7 C8 109.3(3) . . ?
N1 C7 C6 122.6(4) . . ?
C8 C7 C6 128.0(4) . . ?
C9 C8 C7 105.6(4) . . ?
C9 C8 H8A 127.2 . . ?
C7 C8 H8A 127.2 . . ?
N2 C9 C8 107.3(4) . . ?
N2 C9 C10 120.2(3) . . ?
C8 C9 C10 132.5(4) . . ?
N3 C10 C11 110.3(3) . . ?
N3 C10 C9 118.3(4) . . ?
C11 C10 C9 131.3(4) . . ?
C10 C11 C12 104.8(4) . . ?
C10 C11 H11A 127.6 . . ?
C12 C11 H11A 127.6 . . ?
N4 C12 C11 108.5(4) . . ?
N4 C12 C13 123.6(4) . . ?
C11 C12 C13 127.9(4) . . ?
C14 C13 C18 117.9(4) . . ?
C14 C13 C12 120.5(4) . . ?
C18 C13 C12 121.6(4) . . ?
C15 C14 C13 122.3(5) . . ?
C15 C14 H14A 118.8 . . ?
C13 C14 H14A 118.8 . . ?
C14 C15 C16 118.5(6) . . ?
C14 C15 H15A 120.8 . . ?
C16 C15 H15A 120.8 . . ?
C17 C16 C15 120.9(6) . . ?
C17 C16 H16A 119.6 . . ?
C15 C16 H16A 119.6 . . ?
C16 C17 C18 120.9(5) . . ?
C16 C17 H17A 119.6 . . ?
C18 C17 H17A 119.6 . . ?
O3 C18 C17 119.3(4) . . ?
O3 C18 C13 121.2(4) . . ?
C17 C18 C13 119.5(5) . . ?
C23 N5 C19 110.8(8) . . ?
C23 N5 C27 110.1(7) . . ?
C19 N5 C27 106.3(6) . . ?
C23 N5 C31 107.9(7) . . ?
C19 N5 C31 112.1(8) . . ?
C27 N5 C31 109.8(8) . . ?
C20 C19 N5 117.5(8) . . ?
C20 C19 H19A 107.9 . . ?
N5 C19 H19A 107.9 . . ?
C20 C19 H19B 107.9 . . ?
N5 C19 H19B 107.9 . . ?
H19A C19 H19B 107.2 . . ?
C19 C20 C21 113.0(9) . . ?
C19 C20 H20A 109.0 . . ?
C21 C20 H20A 109.0 . . ?
C19 C20 H20B 109.0 . . ?
C21 C20 H20B 109.0 . . ?
H20A C20 H20B 107.8 . . ?
C22 C21 C20 114.0(11) . . ?
C22 C21 H21A 108.8 . . ?
C20 C21 H21A 108.8 . . ?
C22 C21 H21B 108.8 . . ?
C20 C21 H21B 108.8 . . ?
H21A C21 H21B 107.6 . . ?
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 . . ?
C24 C23 N5 121.5(9) . . ?
C24 C23 H23A 107.0 . . ?
N5 C23 H23A 107.0 . . ?
C24 C23 H23B 107.0 . . ?
N5 C23 H23B 107.0 . . ?
H23A C23 H23B 106.7 . . ?
C23 C24 C25 118.4(10) . . ?
C23 C24 H24A 107.7 . . ?
C25 C24 H24A 107.7 . . ?
C23 C24 H24B 107.7 . . ?
C25 C24 H24B 107.7 . . ?
H24A C24 H24B 107.1 . . ?
C26 C25 C24 118.3(11) . . ?
C26 C25 H25A 107.7 . . ?
C24 C25 H25A 107.7 . . ?
C26 C25 H25B 107.7 . . ?
C24 C25 H25B 107.7 . . ?
H25A C25 H25B 107.1 . . ?
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 . . ?
N5 C27 C28 116.9(8) . . ?
N5 C27 H27A 108.1 . . ?
C28 C27 H27A 108.1 . . ?
N5 C27 H27B 108.1 . . ?
C28 C27 H27B 108.1 . . ?
H27A C27 H27B 107.3 . . ?
C29 C28 C27 111.5(8) . . ?
C29 C28 H28A 109.3 . . ?
C27 C28 H28A 109.3 . . ?
C29 C28 H28B 109.3 . . ?
C27 C28 H28B 109.3 . . ?
H28A C28 H28B 108.0 . . ?
C30 C29 C28 112.6(9) . . ?
C30 C29 H29A 109.1 . . ?
C28 C29 H29A 109.1 . . ?
C30 C29 H29B 109.1 . . ?
C28 C29 H29B 109.1 . . ?
H29A C29 H29B 107.8 . . ?
C29 C30 H30A 109.5 . . ?
C29 C30 H30B 109.5 . . ?
H30A C30 H30B 109.5 . . ?
C29 C30 H30C 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
N5 C31 C32 150.8(12) . . ?
N5 C31 H31A 99.0 . . ?
C32 C31 H31A 99.0 . . ?
N5 C31 H31B 99.0 . . ?
C32 C31 H31B 99.0 . . ?
H31A C31 H31B 103.9 . . ?
C33 C32 C31 109.4(12) . . ?
C33 C32 H32A 109.8 . . ?
C31 C32 H32A 109.8 . . ?
C33 C32 H32B 109.8 . . ?
C31 C32 H32B 109.8 . . ?
H32A C32 H32B 108.2 . . ?
C34 C33 C32 111.1(12) . . ?
C34 C33 H33A 109.4 . . ?
C32 C33 H33A 109.4 . . ?
C34 C33 H33B 109.4 . . ?
C32 C33 H33B 109.4 . . ?
H33A C33 H33B 108.0 . . ?
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 . . ?
C23B N5B C27B 113.2(8) . . ?
C23B N5B C31B 101.1(8) . . ?
C27B N5B C31B 111.6(9) . . ?
C23B N5B C19B 110.8(9) . . ?
C27B N5B C19B 108.4(6) . . ?
C31B N5B C19B 111.8(9) . . ?
C20B C19B N5B 116.0(7) . . ?
C20B C19B H19C 108.3 . . ?
N5B C19B H19C 108.3 . . ?
C20B C19B H19D 108.3 . . ?
N5B C19B H19D 108.3 . . ?
H19C C19B H19D 107.4 . . ?
C19B C20B C21B 113.4(9) . . ?
C19B C20B H20C 108.9 . . ?
C21B C20B H20C 108.9 . . ?
C19B C20B H20D 108.9 . . ?
C21B C20B H20D 108.9 . . ?
H20C C20B H20D 107.7 . . ?
C22B C21B C20B 113.0(10) . . ?
C22B C21B H21C 109.0 . . ?
C20B C21B H21C 109.0 . . ?
C22B C21B H21D 109.0 . . ?
C20B C21B H21D 109.0 . . ?
H21C C21B H21D 107.8 . . ?
C21B C22B H22D 109.5 . . ?
C21B C22B H22E 109.5 . . ?
H22D C22B H22E 109.5 . . ?
C21B C22B H22F 109.5 . . ?
H22D C22B H22F 109.5 . . ?
H22E C22B H22F 109.5 . . ?
C24B C23B N5B 101.1(10) . . ?
C24B C23B H23C 111.6 . . ?
N5B C23B H23C 111.6 . . ?
C24B C23B H23D 111.6 . . ?
N5B C23B H23D 111.6 . . ?
H23C C23B H23D 109.4 . . ?
C25B C24B C23B 154.1(16) . . ?
C25B C24B H24C 97.9 . . ?
C23B C24B H24C 97.9 . . ?
C25B C24B H24D 97.9 . . ?
C23B C24B H24D 97.9 . . ?
H24C C24B H24D 103.7 . . ?
C24B C25B C26B 114.4(16) . . ?
C24B C25B H25C 108.7 . . ?
C26B C25B H25C 108.7 . . ?
C24B C25B H25D 108.7 . . ?
C26B C25B H25D 108.7 . . ?
H25C C25B H25D 107.6 . . ?
C25B C26B H26D 109.5 . . ?
C25B C26B H26E 109.5 . . ?
H26D C26B H26E 109.5 . . ?
C25B C26B H26F 109.5 . . ?
H26D C26B H26F 109.5 . . ?
H26E C26B H26F 109.5 . . ?
N5B C27B C28B 115.7(7) . . ?
N5B C27B H27C 108.3 . . ?
C28B C27B H27C 108.3 . . ?
N5B C27B H27D 108.3 . . ?
C28B C27B H27D 108.3 . . ?
H27C C27B H27D 107.4 . . ?
C29B C28B C27B 110.9(7) . . ?
C29B C28B H28C 109.4 . . ?
C27B C28B H28C 109.4 . . ?
C29B C28B H28D 109.4 . . ?
C27B C28B H28D 109.4 . . ?
H28C C28B H28D 108.0 . . ?
C30B C29B C28B 113.2(9) . . ?
C30B C29B H29C 108.9 . . ?
C28B C29B H29C 108.9 . . ?
C30B C29B H29D 108.9 . . ?
C28B C29B H29D 108.9 . . ?
H29C C29B H29D 107.7 . . ?
C29B C30B H30D 109.5 . . ?
C29B C30B H30E 109.5 . . ?
H30D C30B H30E 109.5 . . ?
C29B C30B H30F 109.5 . . ?
H30D C30B H30F 109.5 . . ?
H30E C30B H30F 109.5 . . ?
N5B C31B C32B 118.4(8) . . ?
N5B C31B H31C 107.7 . . ?
C32B C31B H31C 107.7 . . ?
N5B C31B H31D 107.7 . . ?
C32B C31B H31D 107.7 . . ?
H31C C31B H31D 107.1 . . ?
C33B C32B C31B 105.1(11) . . ?
C33B C32B H32C 110.7 . . ?
C31B C32B H32C 110.7 . . ?
C33B C32B H32D 110.7 . . ?
C31B C32B H32D 110.7 . . ?
H32C C32B H32D 108.8 . . ?
C32B C33B C34B 114.7(14) . . ?
C32B C33B H33C 108.6 . . ?
C34B C33B H33C 108.6 . . ?
C32B C33B H33D 108.6 . . ?
C34B C33B H33D 108.6 . . ?
H33C C33B H33D 107.6 . . ?
C33B C34B H34D 109.5 . . ?
C33B C34B H34E 109.5 . . ?
H34D C34B H34E 109.5 . . ?
C33B C34B H34F 109.5 . . ?
H34D C34B H34F 109.5 . . ?
H34E C34B H34F 109.5 . . ?

_refine_diff_density_max         1.423
_refine_diff_density_min         -1.909
_refine_diff_density_rms         0.154

####################################################################### 
# 
# 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_ibcc1077
_database_code_depnum_ccdc_archive 'CCDC 1962568'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2019-10-30 deposited with the CCDC.	2020-02-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         
'C36 H22 N8 O5.97 Ti2, 2(C16 H36 N), 4(C5 H5 N)'
_chemical_formula_sum            'C88 H114 N14 O6 Ti2'
_chemical_formula_weight         1559.73

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'
V V 0.3005 0.5294 '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                   12.7936(6)
_cell_length_b                   18.1210(10)
_cell_length_c                   19.6033(10)
_cell_angle_alpha                98.602(3)
_cell_angle_beta                 108.452(3)
_cell_angle_gamma                101.429(3)
_cell_volume                     4113.9(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    7427
_cell_measurement_theta_min      3.25
_cell_measurement_theta_max      26.13

_exptl_crystal_description       block
_exptl_crystal_colour            'light yellow-violet'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_F_000             1664
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.090
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.060
_exptl_absorpt_coefficient_mu    0.256
_shelx_estimated_absorpt_T_min   0.977
_shelx_estimated_absorpt_T_max   0.985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.681
_exptl_absorpt_correction_T_max  0.745
_exptl_absorpt_process_details   'SADABS-2008/1, Bruker AXS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'multilayer monochromator ImuS'
_diffrn_measurement_device_type  'Bruker APEX II QUAZAR'
_diffrn_measurement_method       'φ and ω rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            62966
_diffrn_reflns_av_unetI/netI     0.0665
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.952
_diffrn_reflns_theta_max         26.442
_diffrn_reflns_theta_full        26.442
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.989
_reflns_number_total             16760
_reflns_number_gt                10766
_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       'Bruker APEX 2'
_computing_cell_refinement       'SAINT (Bruker)'
_computing_data_reduction        'SAINT (Bruker)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically. Both titanyl sites
 are disordered over two opposite orientations, although there is
 on main component (ca. 0.97:0.03 relative occupancies for both sites).
 These were refined with EADP. Attempts at refining a heterometallic
 compositions were not successful, although the crystal color, elemental
 analysis and magnetic properties fully support a T_V heterometallic 
 composition. Ti-O and Ti-N bond lengths are actually intermediate between
 those of the pure vanadyl and titanyl crystals.
 The TBA cations and lattice pyridine molecules were refined with 
 displacement parameters restraints due to some disorder.
 Hydrogens were placed geometrically on their carrier atom and refined
 with a riding model, except those on the pyrazole N that were found in a
 difference Fourier map and refined with their thermal parameter 1.5 times
 that of their carrier N.
;

_vrf_PLAT112_ibcc1077            
;
PROBLEM:  ADDSYM Detects New (Pseudo) Symm. Elem       c/2         91 %Fit
RESPONSE: ADDSYM was used to modify the structural model along the detected
pseudo-symmetry element. There is no real difference with the present model,
the whole asymmetric unit is simply shifted by the pseudo-symmetry element.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1249P)²+4.4653P] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         16760
_refine_ls_number_parameters     1019
_refine_ls_number_restraints     50
_refine_ls_R_factor_all          0.1167
_refine_ls_R_factor_gt           0.0772
_refine_ls_wR_factor_ref         0.2489
_refine_ls_wR_factor_gt          0.2171
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_restrained_S_all      1.072
_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 1.17749(5) 0.71185(4) 0.21777(4) 0.0177(2) Uani 0.9657(17) 1 d D . P A 1
Ti1B Ti 1.1604(15) 0.6767(13) 0.1812(12) 0.0177(2) Uani 0.0343(17) 1 d D . P A
2
O1 O 1.2015(2) 0.76490(15) 0.29940(13) 0.0261(6) Uani 0.9657(17) 1 d D . P A 1
O1B O 1.148(6) 0.621(4) 0.104(2) 0.0261(6) Uani 0.0343(17) 1 d D . P A 2
Ti2 Ti 0.80862(5) 0.30179(4) 0.28161(4) 0.0175(2) Uani 0.9674(16) 1 d D . P B 1
Ti2B Ti 0.8381(16) 0.3360(13) 0.3210(12) 0.0175(2) Uani 0.0326(16) 1 d D . P B
2
O4 O 0.7847(2) 0.24624(14) 0.20138(13) 0.0247(6) Uani 0.9674(16) 1 d D . P B 1
O4B O 0.844(6) 0.395(4) 0.395(3) 0.0247(6) Uani 0.0326(16) 1 d D . P B 2
O2 O 1.1156(2) 0.76599(16) 0.14437(14) 0.0311(6) Uani 1 1 d . . . . .
O3 O 0.6701(2) 0.28934(15) 0.30068(13) 0.0250(6) Uani 1 1 d . . . . .
O5 O 1.31659(19) 0.72532(14) 0.19906(13) 0.0239(5) Uani 1 1 d . . . . .
O6 O 0.8717(2) 0.25043(15) 0.35728(13) 0.0253(6) Uani 1 1 d . . . . .
N1 N 0.9976(2) 0.65563(17) 0.18563(15) 0.0215(6) Uani 1 1 d . . . . .
N2 N 0.9555(2) 0.59074(17) 0.20564(16) 0.0215(6) Uani 1 1 d . . . . .
H2 H 1.001(4) 0.568(2) 0.232(2) 0.032 Uiso 1 1 d . U . . .
N3 N 0.8404(2) 0.46041(16) 0.23579(15) 0.0201(6) Uani 1 1 d . . . . .
N4 N 0.7687(2) 0.40541(17) 0.25247(15) 0.0197(6) Uani 1 1 d . . . . .
N5 N 1.2172(2) 0.60698(16) 0.24415(15) 0.0198(6) Uani 1 1 d . . . . .
N6 N 1.1447(2) 0.55150(16) 0.26020(15) 0.0204(6) Uani 1 1 d . . . . .
N7 N 1.0306(2) 0.42178(17) 0.29089(16) 0.0204(6) Uani 1 1 d . . . . .
H7 H 0.988(4) 0.441(2) 0.266(2) 0.031 Uiso 1 1 d . U . . .
N8 N 0.9888(2) 0.35765(16) 0.31238(15) 0.0209(6) Uani 1 1 d . . . . .
C1 C 1.0246(3) 0.7956(2) 0.1288(2) 0.0287(9) Uani 1 1 d . . . . .
C2 C 1.0339(3) 0.8663(3) 0.1086(2) 0.0441(12) Uani 1 1 d . . . . .
H2A H 1.104260 0.892787 0.106259 0.053 Uiso 1 1 calc R U . . .
C3 C 0.9414(4) 0.8990(3) 0.0916(3) 0.0457(12) Uani 1 1 d . . . . .
H3A H 0.949243 0.947633 0.078446 0.055 Uiso 1 1 calc R U . . .
C4 C 0.8390(3) 0.8607(2) 0.0940(2) 0.0350(10) Uani 1 1 d . . . . .
H4A H 0.775579 0.882457 0.082169 0.042 Uiso 1 1 calc R U . . .
C5 C 0.8290(3) 0.7906(2) 0.1138(2) 0.0279(8) Uani 1 1 d . . . . .
H5A H 0.757835 0.764448 0.115238 0.033 Uiso 1 1 calc R U . . .
C6 C 0.9201(3) 0.7565(2) 0.13178(18) 0.0225(7) Uani 1 1 d . . . . .
C7 C 0.9072(3) 0.6842(2) 0.15642(18) 0.0204(7) Uani 1 1 d . . . . .
C8 C 0.8084(3) 0.6360(2) 0.15931(18) 0.0218(7) Uani 1 1 d . . . . .
H8A H 0.733162 0.642400 0.142851 0.026 Uiso 1 1 calc R U . . .
C9 C 0.8428(3) 0.5775(2) 0.19087(18) 0.0195(7) Uani 1 1 d . . . . .
C10 C 0.7824(3) 0.51072(19) 0.20964(18) 0.0191(7) Uani 1 1 d . . . . .
C11 C 0.6709(3) 0.4885(2) 0.20772(17) 0.0197(7) Uani 1 1 d . . . . .
H11A H 0.611874 0.513400 0.191134 0.024 Uiso 1 1 calc R U . . .
C12 C 0.6644(3) 0.42188(19) 0.23538(17) 0.0176(7) Uani 1 1 d . . . . .
C13 C 0.5655(3) 0.3743(2) 0.24488(17) 0.0191(7) Uani 1 1 d . . . . .
C14 C 0.4602(3) 0.3935(2) 0.22263(18) 0.0227(7) Uani 1 1 d . . . . .
H14A H 0.454988 0.437813 0.202635 0.027 Uiso 1 1 calc R U . . .
C15 C 0.3640(3) 0.3489(2) 0.22934(19) 0.0252(8) Uani 1 1 d . . . . .
H15A H 0.293465 0.362356 0.213401 0.030 Uiso 1 1 calc R U . . .
C16 C 0.3711(3) 0.2849(2) 0.25928(19) 0.0277(8) Uani 1 1 d . . . . .
H16A H 0.305220 0.254251 0.263731 0.033 Uiso 1 1 calc R U . . .
C17 C 0.4736(3) 0.2653(2) 0.28277(19) 0.0248(8) Uani 1 1 d . . . . .
H17A H 0.477886 0.221537 0.303800 0.030 Uiso 1 1 calc R U . . .
C18 C 0.5714(3) 0.3094(2) 0.27583(18) 0.0211(7) Uani 1 1 d . . . . .
C19 C 1.4150(3) 0.7053(2) 0.22396(18) 0.0209(7) Uani 1 1 d . . . . .
C20 C 1.5132(3) 0.7504(2) 0.21841(18) 0.0236(8) Uani 1 1 d . . . . .
H20A H 1.509541 0.795248 0.198991 0.028 Uiso 1 1 calc R U . . .
C21 C 1.6156(3) 0.7301(2) 0.24111(19) 0.0266(8) Uani 1 1 d . . . . .
H21A H 1.681784 0.761023 0.237293 0.032 Uiso 1 1 calc R U . . .
C22 C 1.6216(3) 0.6647(2) 0.2694(2) 0.0252(8) Uani 1 1 d . . . . .
H22A H 1.691833 0.650737 0.284755 0.030 Uiso 1 1 calc R U . . .
C23 C 1.5255(3) 0.6199(2) 0.27503(19) 0.0239(8) Uani 1 1 d . . . . .
H23A H 1.530360 0.575066 0.294200 0.029 Uiso 1 1 calc R U . . .
C24 C 1.4201(3) 0.6392(2) 0.25306(18) 0.0194(7) Uani 1 1 d . . . . .
C25 C 1.3215(3) 0.5909(2) 0.26187(17) 0.0194(7) Uani 1 1 d . . . . .
C26 C 1.3152(3) 0.5249(2) 0.29011(18) 0.0200(7) Uani 1 1 d . . . . .
H26A H 1.374762 0.500752 0.307943 0.024 Uiso 1 1 calc R U . . .
C27 C 1.2031(3) 0.50184(19) 0.28660(18) 0.0193(7) Uani 1 1 d . . . . .
C28 C 1.1430(3) 0.4357(2) 0.30606(18) 0.0213(7) Uani 1 1 d . . . . .
C29 C 1.1779(3) 0.3781(2) 0.33942(18) 0.0219(7) Uani 1 1 d . . . . .
H29A H 1.253362 0.372258 0.356878 0.026 Uiso 1 1 calc R U . . .
C30 C 1.0792(3) 0.3302(2) 0.34221(17) 0.0198(7) Uani 1 1 d . . . . .
C31 C 1.0669(3) 0.2595(2) 0.36959(18) 0.0223(7) Uani 1 1 d . . . . .
C32 C 1.1604(3) 0.2261(2) 0.38910(19) 0.0269(8) Uani 1 1 d . . . . .
H32A H 1.230991 0.251238 0.386223 0.032 Uiso 1 1 calc R U . . .
C33 C 1.1502(3) 0.1574(2) 0.4123(2) 0.0322(9) Uani 1 1 d . . . . .
H33A H 1.212859 0.134948 0.423965 0.039 Uiso 1 1 calc R U . . .
C34 C 1.0485(3) 0.1214(2) 0.4184(2) 0.0338(9) Uani 1 1 d . . . . .
H34A H 1.041868 0.074607 0.434929 0.041 Uiso 1 1 calc R U . . .
C35 C 0.9565(3) 0.1536(2) 0.40052(19) 0.0293(8) Uani 1 1 d . . . . .
H35A H 0.887340 0.128666 0.405275 0.035 Uiso 1 1 calc R U . . .
C36 C 0.9637(3) 0.2224(2) 0.37548(18) 0.0238(8) Uani 1 1 d . . . . .
N9 N 0.6970(2) 0.30374(18) 0.01350(15) 0.0245(7) Uani 1 1 d . . . . .
C37 C 0.6569(3) 0.3532(2) -0.04038(19) 0.0301(9) Uani 1 1 d . . . . .
H37A H 0.576739 0.327466 -0.072568 0.036 Uiso 1 1 calc R U . . .
H37B H 0.703349 0.355328 -0.072299 0.036 Uiso 1 1 calc R U . . .
C38 C 0.6633(3) 0.4355(2) -0.00550(19) 0.0281(8) Uani 1 1 d . . . . .
H38A H 0.744241 0.464977 0.020065 0.034 Uiso 1 1 calc R U . . .
H38B H 0.625710 0.434885 0.031516 0.034 Uiso 1 1 calc R U . . .
C39 C 0.6126(4) 0.5584(3) -0.0336(2) 0.0369(10) Uani 1 1 d . . . . .
H39A H 0.581458 0.560845 0.006102 0.055 Uiso 1 1 calc R U . . .
H39B H 0.568872 0.580109 -0.072713 0.055 Uiso 1 1 calc R U . . .
H39C H 0.692747 0.588243 -0.013960 0.055 Uiso 1 1 calc R U . . .
C40 C 0.6043(3) 0.4748(2) -0.0651(2) 0.0316(9) Uani 1 1 d . . . . .
H40A H 0.639903 0.472825 -0.103247 0.038 Uiso 1 1 calc R U . . .
H40B H 0.522900 0.445990 -0.089294 0.038 Uiso 1 1 calc R U . . .
C41 C 0.4930(3) 0.2576(3) 0.01446(19) 0.0319(9) Uani 1 1 d . . . . .
H41A H 0.481099 0.211066 -0.023647 0.038 Uiso 1 1 calc R U . . .
H41B H 0.462550 0.296284 -0.010846 0.038 Uiso 1 1 calc R U . . .
C42 C 0.6200(3) 0.2906(2) 0.05859(18) 0.0263(8) Uani 1 1 d . . . . .
H42A H 0.645703 0.255047 0.090158 0.032 Uiso 1 1 calc R U . . .
H42B H 0.630743 0.340571 0.091756 0.032 Uiso 1 1 calc R U . . .
C43 C 0.4290(3) 0.2361(3) 0.0659(2) 0.0415(11) Uani 1 1 d . . . . .
H43A H 0.448826 0.281532 0.106925 0.050 Uiso 1 1 calc R U . . .
H43B H 0.345972 0.223937 0.038052 0.050 Uiso 1 1 calc R U . . .
C44 C 0.4547(4) 0.1684(3) 0.0979(3) 0.0483(12) Uani 1 1 d . . . . .
H44A H 0.436219 0.123165 0.057815 0.072 Uiso 1 1 calc R U . . .
H44B H 0.408599 0.157011 0.128471 0.072 Uiso 1 1 calc R U . . .
H44C H 0.535863 0.181108 0.128417 0.072 Uiso 1 1 calc R U . . .
C45 C 0.6944(3) 0.2273(2) -0.03227(18) 0.0265(8) Uani 1 1 d . . . . .
H45A H 0.613944 0.200065 -0.062665 0.032 Uiso 1 1 calc R U . . .
H45B H 0.735049 0.238352 -0.066473 0.032 Uiso 1 1 calc R U . . .
C46 C 0.7470(4) 0.1736(2) 0.0119(2) 0.0395(10) Uani 1 1 d . . . . .
H46A H 0.830579 0.196060 0.035117 0.047 Uiso 1 1 calc R U . . .
H46B H 0.716045 0.169051 0.051873 0.047 Uiso 1 1 calc R U . . .
C47 C 0.7232(4) 0.0943(3) -0.0355(2) 0.0465(12) Uani 1 1 d . . . . .
H47A H 0.640680 0.068935 -0.051352 0.056 Uiso 1 1 calc R U . . .
H47B H 0.740374 0.100334 -0.080522 0.056 Uiso 1 1 calc R U . . .
C48 C 0.7891(4) 0.0419(3) 0.0006(3) 0.0471(11) Uani 1 1 d . . . . .
H48A H 0.870374 0.062371 0.009747 0.071 Uiso 1 1 calc R U . . .
H48B H 0.761449 -0.009905 -0.031982 0.071 Uiso 1 1 calc R U . . .
H48C H 0.778420 0.039040 0.047564 0.071 Uiso 1 1 calc R U . . .
C49 C 0.8159(3) 0.3430(2) 0.06801(19) 0.0264(8) Uani 1 1 d . . . . .
H49A H 0.838330 0.309499 0.102615 0.032 Uiso 1 1 calc R U . . .
H49B H 0.814062 0.391941 0.097243 0.032 Uiso 1 1 calc R U . . .
C50 C 0.9074(3) 0.3612(2) 0.0340(2) 0.0295(8) Uani 1 1 d . . . . .
H50A H 0.917043 0.312481 0.009373 0.035 Uiso 1 1 calc R U . . .
H50B H 0.883979 0.391528 -0.003522 0.035 Uiso 1 1 calc R U . . .
C51 C 1.0189(4) 0.4069(3) 0.0944(2) 0.0503(13) Uani 1 1 d . . . . .
H51A H 1.008137 0.455691 0.117986 0.060 Uiso 1 1 calc R U . . .
H51B H 1.039312 0.376853 0.132562 0.060 Uiso 1 1 calc R U . . .
C52 C 1.1163(4) 0.4260(4) 0.0667(3) 0.0722(18) Uani 1 1 d . . . . .
H52A H 1.125370 0.378107 0.041268 0.108 Uiso 1 1 calc R U . . .
H52B H 1.186950 0.452329 0.108554 0.108 Uiso 1 1 calc R U . . .
H52C H 1.099911 0.459791 0.032259 0.108 Uiso 1 1 calc R U . . .
N10 N 0.3050(2) 0.70301(18) 0.48603(15) 0.0239(7) Uani 1 1 d . . . . .
C53 C 0.3801(3) 0.7174(2) 0.43958(18) 0.0259(8) Uani 1 1 d . . . . .
H53A H 0.372219 0.667258 0.407716 0.031 Uiso 1 1 calc R U . . .
H53B H 0.350152 0.750777 0.406700 0.031 Uiso 1 1 calc R U . . .
C54 C 0.5061(3) 0.7546(3) 0.4821(2) 0.0397(11) Uani 1 1 d . . . . .
H54A H 0.542870 0.716236 0.504039 0.048 Uiso 1 1 calc R U . . .
H54B H 0.515779 0.798050 0.522631 0.048 Uiso 1 1 calc R U . . .
C55 C 0.5636(3) 0.7847(3) 0.4293(2) 0.0504(14) Uani 1 1 d . . . . .
H55A H 0.647393 0.800218 0.455360 0.061 Uiso 1 1 calc R U . . .
H55B H 0.545995 0.741761 0.386311 0.061 Uiso 1 1 calc R U . . .
C56 C 0.5273(4) 0.8523(3) 0.4014(3) 0.0613(15) Uani 1 1 d . . . . .
H56A H 0.445622 0.836278 0.371531 0.092 Uiso 1 1 calc R U . . .
H56B H 0.570872 0.869895 0.371145 0.092 Uiso 1 1 calc R U . . .
H56C H 0.541774 0.894629 0.443492 0.092 Uiso 1 1 calc R U . . .
C57 C 0.3077(3) 0.7787(2) 0.53263(18) 0.0246(8) Uani 1 1 d . . . . .
H57A H 0.267792 0.766958 0.567051 0.030 Uiso 1 1 calc R U . . .
H57B H 0.388248 0.806029 0.562776 0.030 Uiso 1 1 calc R U . . .
C58 C 0.2541(3) 0.8327(2) 0.4894(2) 0.0305(9) Uani 1 1 d . . . . .
H58A H 0.169875 0.813502 0.471698 0.037 Uiso 1 1 calc R U . . .
H58B H 0.276896 0.833158 0.445660 0.037 Uiso 1 1 calc R U . . .
C59 C 0.2908(3) 0.9153(2) 0.5369(2) 0.0341(9) Uani 1 1 d . . . . .
H59A H 0.284812 0.913220 0.585714 0.041 Uiso 1 1 calc R U . . .
H59B H 0.371830 0.938568 0.544933 0.041 Uiso 1 1 calc R U . . .
C60 C 0.2195(4) 0.9661(2) 0.5020(2) 0.0404(10) Uani 1 1 d . . . . .
H60A H 0.223158 0.967103 0.452960 0.061 Uiso 1 1 calc R U . . .
H60B H 0.248811 1.018680 0.533080 0.061 Uiso 1 1 calc R U . . .
H60C H 0.140038 0.945458 0.497281 0.061 Uiso 1 1 calc R U . . .
C61 C 0.1856(3) 0.6634(2) 0.43216(18) 0.0257(8) Uani 1 1 d . . . . .
H61A H 0.187584 0.615151 0.401954 0.031 Uiso 1 1 calc R U . . .
H61B H 0.161642 0.697400 0.398345 0.031 Uiso 1 1 calc R U . . .
C62 C 0.0962(3) 0.6436(2) 0.4669(2) 0.0290(8) Uani 1 1 d . . . . .
H62A H 0.122404 0.614205 0.504784 0.035 Uiso 1 1 calc R U . . .
H62B H 0.084712 0.691692 0.491222 0.035 Uiso 1 1 calc R U . . .
C63 C -0.0153(4) 0.5955(3) 0.4075(2) 0.0446(11) Uani 1 1 d . . . . .
H63A H -0.038864 0.624664 0.368908 0.053 Uiso 1 1 calc R U . . .
H63B H -0.002882 0.547325 0.384073 0.053 Uiso 1 1 calc R U . . .
C64 C -0.1105(4) 0.5748(3) 0.4368(3) 0.0642(16) Uani 1 1 d . . . . .
H64A H -0.091785 0.540762 0.470692 0.096 Uiso 1 1 calc R U . . .
H64B H -0.181795 0.548155 0.395531 0.096 Uiso 1 1 calc R U . . .
H64C H -0.119776 0.622054 0.463122 0.096 Uiso 1 1 calc R U . . .
C65 C 0.3484(3) 0.6532(2) 0.53889(19) 0.0290(8) Uani 1 1 d . . . . .
H65A H 0.429731 0.678430 0.568769 0.035 Uiso 1 1 calc R U . . .
H65B H 0.305866 0.652119 0.573188 0.035 Uiso 1 1 calc R U . . .
C66 C 0.3386(3) 0.5704(2) 0.50373(19) 0.0289(8) Uani 1 1 d . . . . .
H66A H 0.376787 0.569928 0.466996 0.035 Uiso 1 1 calc R U . . .
H66B H 0.257132 0.542312 0.477832 0.035 Uiso 1 1 calc R U . . .
C67 C 0.3945(3) 0.5302(2) 0.5635(2) 0.0320(9) Uani 1 1 d . . . . .
H67A H 0.476320 0.557808 0.588087 0.038 Uiso 1 1 calc R U . . .
H67B H 0.358296 0.533322 0.601298 0.038 Uiso 1 1 calc R U . . .
C68 C 0.3838(4) 0.4458(2) 0.5327(2) 0.0367(10) Uani 1 1 d . . . . .
H68A H 0.302908 0.417857 0.509292 0.055 Uiso 1 1 calc R U . . .
H68B H 0.420735 0.422748 0.572965 0.055 Uiso 1 1 calc R U . . .
H68C H 0.420936 0.442348 0.496063 0.055 Uiso 1 1 calc R U . . .
N11 N 0.8875(4) 0.9187(3) 0.3660(2) 0.0613(12) Uani 1 1 d . . . . .
C69 C 0.9535(5) 0.9161(3) 0.3246(3) 0.0617(14) Uani 1 1 d . . . . .
H69A H 0.971042 0.959205 0.304198 0.074 Uiso 1 1 calc R U . . .
C70 C 0.9961(4) 0.8556(4) 0.3106(3) 0.0588(15) Uani 1 1 d . . . . .
H70A H 1.042945 0.857129 0.281449 0.071 Uiso 1 1 calc R U . . .
C71 C 0.9731(4) 0.7944(3) 0.3372(3) 0.0547(14) Uani 1 1 d . . . . .
H71A H 1.001291 0.751066 0.326373 0.066 Uiso 1 1 calc R U . . .
C72 C 0.9065(4) 0.7943(3) 0.3815(3) 0.0523(13) Uani 1 1 d . . . . .
H72A H 0.890476 0.751819 0.403100 0.063 Uiso 1 1 calc R U . . .
C73 C 0.8652(4) 0.8572(3) 0.3928(2) 0.0417(10) Uani 1 1 d . . . . .
H73A H 0.817873 0.856665 0.421650 0.050 Uiso 1 1 calc R U . . .
N12 N 0.4275(4) 0.0885(2) 0.3385(2) 0.0544(11) Uani 1 1 d . . . . .
C74 C 0.3573(5) 0.0352(3) 0.3526(3) 0.0636(15) Uani 1 1 d . . . . .
H74 H 0.333693 0.049467 0.392866 0.076 Uiso 1 1 calc R U . . .
C75 C 0.4673(4) 0.0659(3) 0.2834(3) 0.0541(13) Uani 1 1 d . . . . .
H75 H 0.520606 0.103568 0.273765 0.065 Uiso 1 1 calc R U . . .
C76 C 0.3139(5) -0.0430(3) 0.3111(3) 0.0584(15) Uani 1 1 d . . . . .
H76 H 0.259763 -0.079297 0.321539 0.070 Uiso 1 1 calc R U . . .
C77 C 0.3530(5) -0.0636(3) 0.2561(3) 0.0641(15) Uani 1 1 d . . . . .
H77 H 0.326163 -0.115241 0.227296 0.077 Uiso 1 1 calc R U . . .
C78 C 0.4337(5) -0.0086(3) 0.2414(3) 0.0583(14) Uani 1 1 d . . . . .
H78 H 0.463471 -0.022537 0.204095 0.070 Uiso 1 1 calc R U . . .
N13 N 0.6020(4) -0.0831(3) 0.1426(3) 0.0705(14) Uani 1 1 d . . . . .
C79 C 0.6733(5) -0.0677(3) 0.2100(3) 0.0678(16) Uani 1 1 d . . . . .
H79 H 0.683222 -0.109978 0.232517 0.081 Uiso 1 1 calc R U . . .
C80 C 0.7355(5) 0.0050(3) 0.2514(3) 0.0632(15) Uani 1 1 d . . . . .
H80 H 0.784609 0.012638 0.301191 0.076 Uiso 1 1 calc R U . . .
C81 C 0.6021(5) -0.0236(4) 0.1117(3) 0.0653(16) Uani 1 1 d . . . . .
H81 H 0.559989 -0.032967 0.060308 0.078 Uiso 1 1 calc R U . . .
C82 C 0.7246(5) 0.0656(3) 0.2190(3) 0.0613(15) Uani 1 1 d . . . . .
H82 H 0.763354 0.117079 0.246445 0.074 Uiso 1 1 calc R U . . .
C83 C 0.6598(5) 0.0520(3) 0.1493(4) 0.0677(17) Uani 1 1 d . . . . .
H83 H 0.652543 0.093357 0.125037 0.081 Uiso 1 1 calc R U . . .
N14 N 0.0109(4) 0.1893(4) 0.1756(3) 0.0787(14) Uani 1 1 d . U . . .
C84 C 0.0425(6) 0.2187(4) 0.1251(3) 0.0783(15) Uani 1 1 d . U . . .
H84 H 0.014916 0.260375 0.108993 0.094 Uiso 1 1 calc R U . . .
C85 C 0.1242(7) 0.0991(4) 0.1658(5) 0.116(2) Uani 1 1 d . U . . .
H85 H 0.157740 0.058424 0.178401 0.139 Uiso 1 1 calc R U . . .
C86 C 0.0458(6) 0.1272(4) 0.2008(4) 0.0933(17) Uani 1 1 d . U . . .
H86 H 0.022732 0.104873 0.236361 0.112 Uiso 1 1 calc R U . . .
C87 C 0.1429(6) 0.1386(5) 0.1131(5) 0.111(2) Uani 1 1 d . U . . .
H87 H 0.187389 0.121842 0.086314 0.133 Uiso 1 1 calc R U . . .
C88 C 0.1044(7) 0.1941(5) 0.0996(5) 0.105(2) Uani 1 1 d . U . . .
H88 H 0.126525 0.219576 0.065445 0.126 Uiso 1 1 calc R U . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O1 1.640(2) . ?
Ti1 O5 1.905(2) . ?
Ti1 O2 1.915(2) . ?
Ti1 N5 2.156(3) . ?
Ti1 N1 2.167(3) . ?
Ti1B O1B 1.63(2) . ?
Ti1B O5 1.913(18) . ?
Ti1B N5 1.977(18) . ?
Ti1B O2 1.981(19) . ?
Ti1B N1 2.074(18) . ?
Ti2 O4 1.637(2) . ?
Ti2 O3 1.902(2) . ?
Ti2 O6 1.916(2) . ?
Ti2 N4 2.152(3) . ?
Ti2 N8 2.171(3) . ?
Ti2B O4B 1.63(2) . ?
Ti2B O6 1.871(19) . ?
Ti2B N8 1.956(18) . ?
Ti2B O3 2.032(19) . ?
Ti2B N4 2.089(19) . ?
O2 C1 1.344(4) . ?
O3 C18 1.345(4) . ?
O5 C19 1.342(4) . ?
O6 C36 1.340(4) . ?
N1 C7 1.357(4) . ?
N1 N2 1.359(4) . ?
N2 C9 1.342(4) . ?
N2 H2 0.86(4) . ?
N3 C10 1.346(4) . ?
N3 N4 1.366(4) . ?
N4 C12 1.374(4) . ?
N5 C25 1.371(4) . ?
N5 N6 1.371(4) . ?
N6 C27 1.341(4) . ?
N7 C28 1.335(4) . ?
N7 N8 1.362(4) . ?
N7 H7 0.79(4) . ?
N8 C30 1.348(4) . ?
C1 C2 1.393(6) . ?
C1 C6 1.406(5) . ?
C2 C3 1.396(6) . ?
C2 H2A 0.9500 . ?
C3 C4 1.375(6) . ?
C3 H3A 0.9500 . ?
C4 C5 1.377(5) . ?
C4 H4A 0.9500 . ?
C5 C6 1.398(5) . ?
C5 H5A 0.9500 . ?
C6 C7 1.460(5) . ?
C7 C8 1.410(5) . ?
C8 C9 1.381(5) . ?
C8 H8A 0.9500 . ?
C9 C10 1.462(5) . ?
C10 C11 1.391(4) . ?
C11 C12 1.394(5) . ?
C11 H11A 0.9500 . ?
C12 C13 1.465(4) . ?
C13 C18 1.405(5) . ?
C13 C14 1.409(5) . ?
C14 C15 1.387(5) . ?
C14 H14A 0.9500 . ?
C15 C16 1.382(5) . ?
C15 H15A 0.9500 . ?
C16 C17 1.382(5) . ?
C16 H16A 0.9500 . ?
C17 C18 1.402(5) . ?
C17 H17A 0.9500 . ?
C19 C20 1.401(5) . ?
C19 C24 1.406(5) . ?
C20 C21 1.386(5) . ?
C20 H20A 0.9500 . ?
C21 C22 1.387(5) . ?
C21 H21A 0.9500 . ?
C22 C23 1.379(5) . ?
C22 H22A 0.9500 . ?
C23 C24 1.411(5) . ?
C23 H23A 0.9500 . ?
C24 C25 1.460(5) . ?
C25 C26 1.389(5) . ?
C26 C27 1.389(4) . ?
C26 H26A 0.9500 . ?
C27 C28 1.459(5) . ?
C28 C29 1.386(5) . ?
C29 C30 1.406(5) . ?
C29 H29A 0.9500 . ?
C30 C31 1.460(5) . ?
C31 C36 1.406(5) . ?
C31 C32 1.418(5) . ?
C32 C33 1.385(5) . ?
C32 H32A 0.9500 . ?
C33 C34 1.384(6) . ?
C33 H33A 0.9500 . ?
C34 C35 1.386(5) . ?
C34 H34A 0.9500 . ?
C35 C36 1.403(5) . ?
C35 H35A 0.9500 . ?
N9 C49 1.509(4) . ?
N9 C37 1.519(5) . ?
N9 C45 1.522(4) . ?
N9 C42 1.527(4) . ?
C37 C38 1.519(5) . ?
C37 H37A 0.9900 . ?
C37 H37B 0.9900 . ?
C38 C40 1.532(5) . ?
C38 H38A 0.9900 . ?
C38 H38B 0.9900 . ?
C39 C40 1.518(6) . ?
C39 H39A 0.9800 . ?
C39 H39B 0.9800 . ?
C39 H39C 0.9800 . ?
C40 H40A 0.9900 . ?
C40 H40B 0.9900 . ?
C41 C42 1.522(5) . ?
C41 C43 1.533(5) . ?
C41 H41A 0.9900 . ?
C41 H41B 0.9900 . ?
C42 H42A 0.9900 . ?
C42 H42B 0.9900 . ?
C43 C44 1.504(7) . ?
C43 H43A 0.9900 . ?
C43 H43B 0.9900 . ?
C44 H44A 0.9800 . ?
C44 H44B 0.9800 . ?
C44 H44C 0.9800 . ?
C45 C46 1.514(5) . ?
C45 H45A 0.9900 . ?
C45 H45B 0.9900 . ?
C46 C47 1.506(6) . ?
C46 H46A 0.9900 . ?
C46 H46B 0.9900 . ?
C47 C48 1.502(6) . ?
C47 H47A 0.9900 . ?
C47 H47B 0.9900 . ?
C48 H48A 0.9800 . ?
C48 H48B 0.9800 . ?
C48 H48C 0.9800 . ?
C49 C50 1.526(5) . ?
C49 H49A 0.9900 . ?
C49 H49B 0.9900 . ?
C50 C51 1.514(5) . ?
C50 H50A 0.9900 . ?
C50 H50B 0.9900 . ?
C51 C52 1.511(6) . ?
C51 H51A 0.9900 . ?
C51 H51B 0.9900 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
N10 C61 1.510(4) . ?
N10 C57 1.518(4) . ?
N10 C65 1.520(5) . ?
N10 C53 1.531(4) . ?
C53 C54 1.516(5) . ?
C53 H53A 0.9900 . ?
C53 H53B 0.9900 . ?
C54 C55 1.549(6) . ?
C54 H54A 0.9900 . ?
C54 H54B 0.9900 . ?
C55 C56 1.510(7) . ?
C55 H55A 0.9900 . ?
C55 H55B 0.9900 . ?
C56 H56A 0.9800 . ?
C56 H56B 0.9800 . ?
C56 H56C 0.9800 . ?
C57 C58 1.514(5) . ?
C57 H57A 0.9900 . ?
C57 H57B 0.9900 . ?
C58 C59 1.534(5) . ?
C58 H58A 0.9900 . ?
C58 H58B 0.9900 . ?
C59 C60 1.508(6) . ?
C59 H59A 0.9900 . ?
C59 H59B 0.9900 . ?
C60 H60A 0.9800 . ?
C60 H60B 0.9800 . ?
C60 H60C 0.9800 . ?
C61 C62 1.518(5) . ?
C61 H61A 0.9900 . ?
C61 H61B 0.9900 . ?
C62 C63 1.518(5) . ?
C62 H62A 0.9900 . ?
C62 H62B 0.9900 . ?
C63 C64 1.510(6) . ?
C63 H63A 0.9900 . ?
C63 H63B 0.9900 . ?
C64 H64A 0.9800 . ?
C64 H64B 0.9800 . ?
C64 H64C 0.9800 . ?
C65 C66 1.518(5) . ?
C65 H65A 0.9900 . ?
C65 H65B 0.9900 . ?
C66 C67 1.532(5) . ?
C66 H66A 0.9900 . ?
C66 H66B 0.9900 . ?
C67 C68 1.520(6) . ?
C67 H67A 0.9900 . ?
C67 H67B 0.9900 . ?
C68 H68A 0.9800 . ?
C68 H68B 0.9800 . ?
C68 H68C 0.9800 . ?
N11 C73 1.322(6) . ?
N11 C69 1.345(6) . ?
C69 C70 1.348(8) . ?
C69 H69A 0.9500 . ?
C70 C71 1.313(8) . ?
C70 H70A 0.9500 . ?
C71 C72 1.397(7) . ?
C71 H71A 0.9500 . ?
C72 C73 1.365(7) . ?
C72 H72A 0.9500 . ?
C73 H73A 0.9500 . ?
N12 C74 1.307(7) . ?
N12 C75 1.375(6) . ?
C74 C76 1.427(7) . ?
C74 H74 0.9500 . ?
C75 C78 1.378(7) . ?
C75 H75 0.9500 . ?
C76 C77 1.360(7) . ?
C76 H76 0.9500 . ?
C77 C78 1.417(7) . ?
C77 H77 0.9500 . ?
C78 H78 0.9500 . ?
N13 C79 1.297(7) . ?
N13 C81 1.315(7) . ?
C79 C80 1.372(7) . ?
C79 H79 0.9500 . ?
C80 C82 1.358(7) . ?
C80 H80 0.9500 . ?
C81 C83 1.385(8) . ?
C81 H81 0.9500 . ?
C82 C83 1.309(8) . ?
C82 H82 0.9500 . ?
C83 H83 0.9500 . ?
N14 C84 1.323(8) . ?
N14 C86 1.392(9) . ?
C84 C88 1.182(9) . ?
C84 H84 0.9500 . ?
C85 C87 1.394(12) . ?
C85 C86 1.506(11) . ?
C85 H85 0.9500 . ?
C86 H86 0.9500 . ?
C87 C88 1.232(12) . ?
C87 H87 0.9500 . ?
C88 H88 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Ti1 O5 109.26(12) . . ?
O1 Ti1 O2 108.52(13) . . ?
O5 Ti1 O2 91.96(11) . . ?
O1 Ti1 N5 102.28(12) . . ?
O5 Ti1 N5 82.44(11) . . ?
O2 Ti1 N5 148.79(12) . . ?
O1 Ti1 N1 100.26(12) . . ?
O5 Ti1 N1 150.40(11) . . ?
O2 Ti1 N1 80.50(11) . . ?
N5 Ti1 N1 89.33(11) . . ?
O1B Ti1B O5 92(3) . . ?
O1B Ti1B N5 95(3) . . ?
O5 Ti1B N5 87.2(7) . . ?
O1B Ti1B O2 100(3) . . ?
O5 Ti1B O2 89.7(8) . . ?
N5 Ti1B O2 164.5(13) . . ?
O1B Ti1B N1 106(3) . . ?
O5 Ti1B N1 161.8(13) . . ?
N5 Ti1B N1 97.2(8) . . ?
O2 Ti1B N1 81.4(7) . . ?
O4 Ti2 O3 109.30(12) . . ?
O4 Ti2 O6 108.37(12) . . ?
O3 Ti2 O6 91.87(10) . . ?
O4 Ti2 N4 102.75(12) . . ?
O3 Ti2 N4 82.69(11) . . ?
O6 Ti2 N4 148.42(11) . . ?
O4 Ti2 N8 99.98(12) . . ?
O3 Ti2 N8 150.66(11) . . ?
O6 Ti2 N8 80.31(11) . . ?
N4 Ti2 N8 89.32(11) . . ?
O4B Ti2B O6 102(3) . . ?
O4B Ti2B N8 109(3) . . ?
O6 Ti2B N8 87.3(8) . . ?
O4B Ti2B O3 89(3) . . ?
O6 Ti2B O3 89.2(8) . . ?
N8 Ti2B O3 162.4(13) . . ?
O4B Ti2B N4 92(3) . . ?
O6 Ti2B N4 162.7(13) . . ?
N8 Ti2B N4 97.3(8) . . ?
O3 Ti2B N4 81.3(7) . . ?
C1 O2 Ti1 132.8(2) . . ?
C1 O2 Ti1B 138.6(6) . . ?
C18 O3 Ti2 137.4(2) . . ?
C18 O3 Ti2B 137.4(6) . . ?
C19 O5 Ti1 137.1(2) . . ?
C19 O5 Ti1B 134.5(6) . . ?
C36 O6 Ti2B 135.2(6) . . ?
C36 O6 Ti2 133.6(2) . . ?
C7 N1 N2 106.1(3) . . ?
C7 N1 Ti1B 132.5(6) . . ?
N2 N1 Ti1B 119.5(6) . . ?
C7 N1 Ti1 128.1(2) . . ?
N2 N1 Ti1 124.6(2) . . ?
C9 N2 N1 111.8(3) . . ?
C9 N2 H2 127(3) . . ?
N1 N2 H2 121(3) . . ?
C10 N3 N4 108.0(3) . . ?
N3 N4 C12 108.1(3) . . ?
N3 N4 Ti2B 119.0(6) . . ?
C12 N4 Ti2B 130.3(6) . . ?
N3 N4 Ti2 123.9(2) . . ?
C12 N4 Ti2 127.1(2) . . ?
C25 N5 N6 108.2(3) . . ?
C25 N5 Ti1B 127.8(6) . . ?
N6 N5 Ti1B 121.9(6) . . ?
C25 N5 Ti1 127.3(2) . . ?
N6 N5 Ti1 123.3(2) . . ?
C27 N6 N5 107.6(3) . . ?
C28 N7 N8 112.1(3) . . ?
C28 N7 H7 127(3) . . ?
N8 N7 H7 120(3) . . ?
C30 N8 N7 105.7(3) . . ?
C30 N8 Ti2B 130.0(6) . . ?
N7 N8 Ti2B 122.0(6) . . ?
C30 N8 Ti2 128.5(2) . . ?
N7 N8 Ti2 124.6(2) . . ?
O2 C1 C2 119.0(3) . . ?
O2 C1 C6 121.7(3) . . ?
C2 C1 C6 119.2(3) . . ?
C1 C2 C3 120.9(4) . . ?
C1 C2 H2A 119.5 . . ?
C3 C2 H2A 119.5 . . ?
C4 C3 C2 119.9(4) . . ?
C4 C3 H3A 120.1 . . ?
C2 C3 H3A 120.1 . . ?
C3 C4 C5 119.5(4) . . ?
C3 C4 H4A 120.2 . . ?
C5 C4 H4A 120.2 . . ?
C4 C5 C6 122.1(4) . . ?
C4 C5 H5A 119.0 . . ?
C6 C5 H5A 119.0 . . ?
C5 C6 C1 118.3(3) . . ?
C5 C6 C7 120.0(3) . . ?
C1 C6 C7 121.6(3) . . ?
N1 C7 C8 108.9(3) . . ?
N1 C7 C6 122.0(3) . . ?
C8 C7 C6 129.0(3) . . ?
C9 C8 C7 106.3(3) . . ?
C9 C8 H8A 126.9 . . ?
C7 C8 H8A 126.9 . . ?
N2 C9 C8 107.0(3) . . ?
N2 C9 C10 119.7(3) . . ?
C8 C9 C10 133.3(3) . . ?
N3 C10 C11 110.1(3) . . ?
N3 C10 C9 118.5(3) . . ?
C11 C10 C9 131.3(3) . . ?
C10 C11 C12 105.1(3) . . ?
C10 C11 H11A 127.4 . . ?
C12 C11 H11A 127.4 . . ?
N4 C12 C11 108.6(3) . . ?
N4 C12 C13 123.4(3) . . ?
C11 C12 C13 128.0(3) . . ?
C18 C13 C14 118.2(3) . . ?
C18 C13 C12 122.3(3) . . ?
C14 C13 C12 119.6(3) . . ?
C15 C14 C13 121.3(3) . . ?
C15 C14 H14A 119.4 . . ?
C13 C14 H14A 119.4 . . ?
C16 C15 C14 119.8(3) . . ?
C16 C15 H15A 120.1 . . ?
C14 C15 H15A 120.1 . . ?
C17 C16 C15 120.3(3) . . ?
C17 C16 H16A 119.8 . . ?
C15 C16 H16A 119.8 . . ?
C16 C17 C18 120.6(4) . . ?
C16 C17 H17A 119.7 . . ?
C18 C17 H17A 119.7 . . ?
O3 C18 C17 118.8(3) . . ?
O3 C18 C13 121.3(3) . . ?
C17 C18 C13 119.9(3) . . ?
O5 C19 C20 118.6(3) . . ?
O5 C19 C24 121.3(3) . . ?
C20 C19 C24 120.1(3) . . ?
C21 C20 C19 120.4(3) . . ?
C21 C20 H20A 119.8 . . ?
C19 C20 H20A 119.8 . . ?
C20 C21 C22 120.2(3) . . ?
C20 C21 H21A 119.9 . . ?
C22 C21 H21A 119.9 . . ?
C23 C22 C21 119.8(3) . . ?
C23 C22 H22A 120.1 . . ?
C21 C22 H22A 120.1 . . ?
C22 C23 C24 121.6(3) . . ?
C22 C23 H23A 119.2 . . ?
C24 C23 H23A 119.2 . . ?
C19 C24 C23 118.0(3) . . ?
C19 C24 C25 122.7(3) . . ?
C23 C24 C25 119.4(3) . . ?
N5 C25 C26 108.6(3) . . ?
N5 C25 C24 123.0(3) . . ?
C26 C25 C24 128.4(3) . . ?
C27 C26 C25 105.1(3) . . ?
C27 C26 H26A 127.5 . . ?
C25 C26 H26A 127.5 . . ?
N6 C27 C26 110.5(3) . . ?
N6 C27 C28 118.1(3) . . ?
C26 C27 C28 131.4(3) . . ?
N7 C28 C29 106.6(3) . . ?
N7 C28 C27 120.1(3) . . ?
C29 C28 C27 133.2(3) . . ?
C28 C29 C30 106.2(3) . . ?
C28 C29 H29A 126.9 . . ?
C30 C29 H29A 126.9 . . ?
N8 C30 C29 109.3(3) . . ?
N8 C30 C31 121.6(3) . . ?
C29 C30 C31 129.0(3) . . ?
C36 C31 C32 118.9(3) . . ?
C36 C31 C30 121.8(3) . . ?
C32 C31 C30 119.3(3) . . ?
C33 C32 C31 120.8(4) . . ?
C33 C32 H32A 119.6 . . ?
C31 C32 H32A 119.6 . . ?
C34 C33 C32 120.0(4) . . ?
C34 C33 H33A 120.0 . . ?
C32 C33 H33A 120.0 . . ?
C33 C34 C35 120.1(4) . . ?
C33 C34 H34A 120.0 . . ?
C35 C34 H34A 120.0 . . ?
C34 C35 C36 121.2(4) . . ?
C34 C35 H35A 119.4 . . ?
C36 C35 H35A 119.4 . . ?
O6 C36 C35 119.0(3) . . ?
O6 C36 C31 121.9(3) . . ?
C35 C36 C31 119.0(3) . . ?
C49 N9 C37 110.9(3) . . ?
C49 N9 C45 110.8(3) . . ?
C37 N9 C45 106.8(3) . . ?
C49 N9 C42 106.7(2) . . ?
C37 N9 C42 111.0(3) . . ?
C45 N9 C42 110.7(3) . . ?
N9 C37 C38 115.5(3) . . ?
N9 C37 H37A 108.4 . . ?
C38 C37 H37A 108.4 . . ?
N9 C37 H37B 108.4 . . ?
C38 C37 H37B 108.4 . . ?
H37A C37 H37B 107.5 . . ?
C37 C38 C40 109.9(3) . . ?
C37 C38 H38A 109.7 . . ?
C40 C38 H38A 109.7 . . ?
C37 C38 H38B 109.7 . . ?
C40 C38 H38B 109.7 . . ?
H38A C38 H38B 108.2 . . ?
C40 C39 H39A 109.5 . . ?
C40 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
C40 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?
C39 C40 C38 112.1(3) . . ?
C39 C40 H40A 109.2 . . ?
C38 C40 H40A 109.2 . . ?
C39 C40 H40B 109.2 . . ?
C38 C40 H40B 109.2 . . ?
H40A C40 H40B 107.9 . . ?
C42 C41 C43 110.1(3) . . ?
C42 C41 H41A 109.6 . . ?
C43 C41 H41A 109.6 . . ?
C42 C41 H41B 109.6 . . ?
C43 C41 H41B 109.6 . . ?
H41A C41 H41B 108.2 . . ?
C41 C42 N9 116.0(3) . . ?
C41 C42 H42A 108.3 . . ?
N9 C42 H42A 108.3 . . ?
C41 C42 H42B 108.3 . . ?
N9 C42 H42B 108.3 . . ?
H42A C42 H42B 107.4 . . ?
C44 C43 C41 114.3(3) . . ?
C44 C43 H43A 108.7 . . ?
C41 C43 H43A 108.7 . . ?
C44 C43 H43B 108.7 . . ?
C41 C43 H43B 108.7 . . ?
H43A C43 H43B 107.6 . . ?
C43 C44 H44A 109.5 . . ?
C43 C44 H44B 109.5 . . ?
H44A C44 H44B 109.5 . . ?
C43 C44 H44C 109.5 . . ?
H44A C44 H44C 109.5 . . ?
H44B C44 H44C 109.5 . . ?
C46 C45 N9 115.0(3) . . ?
C46 C45 H45A 108.5 . . ?
N9 C45 H45A 108.5 . . ?
C46 C45 H45B 108.5 . . ?
N9 C45 H45B 108.5 . . ?
H45A C45 H45B 107.5 . . ?
C47 C46 C45 111.9(3) . . ?
C47 C46 H46A 109.2 . . ?
C45 C46 H46A 109.2 . . ?
C47 C46 H46B 109.2 . . ?
C45 C46 H46B 109.2 . . ?
H46A C46 H46B 107.9 . . ?
C48 C47 C46 115.4(4) . . ?
C48 C47 H47A 108.4 . . ?
C46 C47 H47A 108.4 . . ?
C48 C47 H47B 108.4 . . ?
C46 C47 H47B 108.4 . . ?
H47A C47 H47B 107.5 . . ?
C47 C48 H48A 109.5 . . ?
C47 C48 H48B 109.5 . . ?
H48A C48 H48B 109.5 . . ?
C47 C48 H48C 109.5 . . ?
H48A C48 H48C 109.5 . . ?
H48B C48 H48C 109.5 . . ?
N9 C49 C50 115.2(3) . . ?
N9 C49 H49A 108.5 . . ?
C50 C49 H49A 108.5 . . ?
N9 C49 H49B 108.5 . . ?
C50 C49 H49B 108.5 . . ?
H49A C49 H49B 107.5 . . ?
C51 C50 C49 109.1(3) . . ?
C51 C50 H50A 109.9 . . ?
C49 C50 H50A 109.9 . . ?
C51 C50 H50B 109.9 . . ?
C49 C50 H50B 109.9 . . ?
H50A C50 H50B 108.3 . . ?
C52 C51 C50 113.3(4) . . ?
C52 C51 H51A 108.9 . . ?
C50 C51 H51A 108.9 . . ?
C52 C51 H51B 108.9 . . ?
C50 C51 H51B 108.9 . . ?
H51A C51 H51B 107.7 . . ?
C51 C52 H52A 109.5 . . ?
C51 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
C51 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
C61 N10 C57 110.8(3) . . ?
C61 N10 C65 111.3(3) . . ?
C57 N10 C65 107.1(3) . . ?
C61 N10 C53 106.4(2) . . ?
C57 N10 C53 110.7(3) . . ?
C65 N10 C53 110.7(3) . . ?
C54 C53 N10 116.2(3) . . ?
C54 C53 H53A 108.2 . . ?
N10 C53 H53A 108.2 . . ?
C54 C53 H53B 108.2 . . ?
N10 C53 H53B 108.2 . . ?
H53A C53 H53B 107.4 . . ?
C53 C54 C55 109.6(3) . . ?
C53 C54 H54A 109.7 . . ?
C55 C54 H54A 109.7 . . ?
C53 C54 H54B 109.7 . . ?
C55 C54 H54B 109.7 . . ?
H54A C54 H54B 108.2 . . ?
C56 C55 C54 114.6(4) . . ?
C56 C55 H55A 108.6 . . ?
C54 C55 H55A 108.6 . . ?
C56 C55 H55B 108.6 . . ?
C54 C55 H55B 108.6 . . ?
H55A C55 H55B 107.6 . . ?
C55 C56 H56A 109.5 . . ?
C55 C56 H56B 109.5 . . ?
H56A C56 H56B 109.5 . . ?
C55 C56 H56C 109.5 . . ?
H56A C56 H56C 109.5 . . ?
H56B C56 H56C 109.5 . . ?
C58 C57 N10 115.0(3) . . ?
C58 C57 H57A 108.5 . . ?
N10 C57 H57A 108.5 . . ?
C58 C57 H57B 108.5 . . ?
N10 C57 H57B 108.5 . . ?
H57A C57 H57B 107.5 . . ?
C57 C58 C59 111.4(3) . . ?
C57 C58 H58A 109.4 . . ?
C59 C58 H58A 109.4 . . ?
C57 C58 H58B 109.4 . . ?
C59 C58 H58B 109.4 . . ?
H58A C58 H58B 108.0 . . ?
C60 C59 C58 112.7(3) . . ?
C60 C59 H59A 109.1 . . ?
C58 C59 H59A 109.1 . . ?
C60 C59 H59B 109.1 . . ?
C58 C59 H59B 109.1 . . ?
H59A C59 H59B 107.8 . . ?
C59 C60 H60A 109.5 . . ?
C59 C60 H60B 109.5 . . ?
H60A C60 H60B 109.5 . . ?
C59 C60 H60C 109.5 . . ?
H60A C60 H60C 109.5 . . ?
H60B C60 H60C 109.5 . . ?
N10 C61 C62 115.3(3) . . ?
N10 C61 H61A 108.5 . . ?
C62 C61 H61A 108.5 . . ?
N10 C61 H61B 108.5 . . ?
C62 C61 H61B 108.5 . . ?
H61A C61 H61B 107.5 . . ?
C63 C62 C61 109.4(3) . . ?
C63 C62 H62A 109.8 . . ?
C61 C62 H62A 109.8 . . ?
C63 C62 H62B 109.8 . . ?
C61 C62 H62B 109.8 . . ?
H62A C62 H62B 108.2 . . ?
C64 C63 C62 113.1(4) . . ?
C64 C63 H63A 108.9 . . ?
C62 C63 H63A 108.9 . . ?
C64 C63 H63B 108.9 . . ?
C62 C63 H63B 108.9 . . ?
H63A C63 H63B 107.8 . . ?
C63 C64 H64A 109.5 . . ?
C63 C64 H64B 109.5 . . ?
H64A C64 H64B 109.5 . . ?
C63 C64 H64C 109.5 . . ?
H64A C64 H64C 109.5 . . ?
H64B C64 H64C 109.5 . . ?
C66 C65 N10 116.1(3) . . ?
C66 C65 H65A 108.3 . . ?
N10 C65 H65A 108.3 . . ?
C66 C65 H65B 108.3 . . ?
N10 C65 H65B 108.3 . . ?
H65A C65 H65B 107.4 . . ?
C65 C66 C67 109.6(3) . . ?
C65 C66 H66A 109.7 . . ?
C67 C66 H66A 109.7 . . ?
C65 C66 H66B 109.7 . . ?
C67 C66 H66B 109.7 . . ?
H66A C66 H66B 108.2 . . ?
C68 C67 C66 112.6(3) . . ?
C68 C67 H67A 109.1 . . ?
C66 C67 H67A 109.1 . . ?
C68 C67 H67B 109.1 . . ?
C66 C67 H67B 109.1 . . ?
H67A C67 H67B 107.8 . . ?
C67 C68 H68A 109.5 . . ?
C67 C68 H68B 109.5 . . ?
H68A C68 H68B 109.5 . . ?
C67 C68 H68C 109.5 . . ?
H68A C68 H68C 109.5 . . ?
H68B C68 H68C 109.5 . . ?
C73 N11 C69 115.9(5) . . ?
N11 C69 C70 123.5(6) . . ?
N11 C69 H69A 118.2 . . ?
C70 C69 H69A 118.2 . . ?
C71 C70 C69 120.3(5) . . ?
C71 C70 H70A 119.9 . . ?
C69 C70 H70A 119.9 . . ?
C70 C71 C72 118.8(5) . . ?
C70 C71 H71A 120.6 . . ?
C72 C71 H71A 120.6 . . ?
C73 C72 C71 117.8(5) . . ?
C73 C72 H72A 121.1 . . ?
C71 C72 H72A 121.1 . . ?
N11 C73 C72 123.7(5) . . ?
N11 C73 H73A 118.2 . . ?
C72 C73 H73A 118.2 . . ?
C74 N12 C75 117.4(5) . . ?
N12 C74 C76 124.0(5) . . ?
N12 C74 H74 118.0 . . ?
C76 C74 H74 118.0 . . ?
N12 C75 C78 123.4(5) . . ?
N12 C75 H75 118.3 . . ?
C78 C75 H75 118.3 . . ?
C77 C76 C74 117.4(5) . . ?
C77 C76 H76 121.3 . . ?
C74 C76 H76 121.3 . . ?
C76 C77 C78 120.4(5) . . ?
C76 C77 H77 119.8 . . ?
C78 C77 H77 119.8 . . ?
C75 C78 C77 117.4(5) . . ?
C75 C78 H78 121.3 . . ?
C77 C78 H78 121.3 . . ?
C79 N13 C81 114.5(5) . . ?
N13 C79 C80 125.1(6) . . ?
N13 C79 H79 117.4 . . ?
C80 C79 H79 117.4 . . ?
C82 C80 C79 117.9(6) . . ?
C82 C80 H80 121.1 . . ?
C79 C80 H80 121.1 . . ?
N13 C81 C83 124.1(6) . . ?
N13 C81 H81 118.0 . . ?
C83 C81 H81 118.0 . . ?
C83 C82 C80 119.0(6) . . ?
C83 C82 H82 120.5 . . ?
C80 C82 H82 120.5 . . ?
C82 C83 C81 118.9(6) . . ?
C82 C83 H83 120.6 . . ?
C81 C83 H83 120.6 . . ?
C84 N14 C86 122.7(6) . . ?
C88 C84 N14 121.4(8) . . ?
C88 C84 H84 119.3 . . ?
N14 C84 H84 119.3 . . ?
C87 C85 C86 113.7(7) . . ?
C87 C85 H85 123.2 . . ?
C86 C85 H85 123.2 . . ?
N14 C86 C85 112.7(7) . . ?
N14 C86 H86 123.6 . . ?
C85 C86 H86 123.6 . . ?
C88 C87 C85 123.2(8) . . ?
C88 C87 H87 118.4 . . ?
C85 C87 H87 118.4 . . ?
C84 C88 C87 126.2(10) . . ?
C84 C88 H88 116.9 . . ?
C87 C88 H88 116.9 . . ?

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
_geom_hbond_publ_flag
N2 H2 N6 0.86(4) 1.85(4) 2.603(4) 146(4) . yes
N7 H7 N3 0.79(4) 1.92(4) 2.610(4) 147(4) . yes

_refine_diff_density_max         1.080
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.097

####################################################################### 
# 
# 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_ibcc340
_database_code_depnum_ccdc_archive 'CCDC 1962566'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2019-10-30 deposited with the CCDC.	2020-02-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H22 N8 O6 V2, 2(C16 H36 N), 4.5(C5 H5 N)'
_chemical_formula_sum            'C90.50 H116.50 N14.50 O6 V2'
_chemical_formula_weight         1605.36

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0040 0.0020
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
H H 0.0000 0.0000
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
N N 0.0076 0.0040
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
O O 0.0132 0.0074
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'
V V 0.3275 0.6267
'XDisp Program in WinGX L.J. Farrugia, J.Appl.Cryst. 2012,45,849-854'

_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                   12.8070(10)
_cell_length_b                   18.384(2)
_cell_length_c                   20.411(2)
_cell_angle_alpha                73.0220(10)
_cell_angle_beta                 72.779(2)
_cell_angle_gamma                70.673(2)
_cell_volume                     4230.0(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9976
_cell_measurement_theta_min      2.78
_cell_measurement_theta_max      33.62

_exptl_crystal_description       block
_exptl_crystal_colour            violet
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_F_000             1710
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    0.354
_shelx_estimated_absorpt_T_min   0.914
_shelx_estimated_absorpt_T_max   0.976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.604
_exptl_absorpt_correction_T_max  0.745
_exptl_absorpt_process_details   'SADABS-2012/1, Bruker AXS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.7749
_diffrn_radiation_type           synchrotron
_diffrn_radiation_source         'Advanced Light Source station 11.3.1'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_measurement_device_type  'Bruker APEX II CCD diffractometer'
_diffrn_measurement_method       'ω rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            51603
_diffrn_reflns_av_unetI/netI     0.0847
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         2.618
_diffrn_reflns_theta_max         30.210
_diffrn_reflns_theta_full        30.210
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             19299
_reflns_number_gt                14568
_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       'Bruker APEX 2'
_computing_cell_refinement       'SAINT (Bruker)'
_computing_data_reduction        'SAINT (Bruker)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically. Both vanadyl sites
 are disordered over two opposite orientations, although there is
 on main component (ca. 0.93:0.07 relative occupancies for both sites).
 These were refined with EADP. In parallel with this disorder one butyl arm
 of both TBA cation is disordered over two equivalent positions (C51-C52 and
 C67-C68), while one of the lattice pyrdine molecules is only half occupied 
 (N4S). These were refined with displacement parameters restraints.
 Hydrogens were placed geometrically on their carrier atom and refined
 with a riding model.
;

_vrf_PLAT411_ibcc340             
;
PROBLEM:  Short Inter H...H Contact
RESPONSE: These short contacts involve hydrogens from partial carbon
atoms from disordered TBA and/or lattice pyridine atoms. They are thus
likely due to ill-defined calculated hydrogen position(s) due to
disorder.
;

_vrf_PLAT112_ibcc340             
;
PROBLEM:  ADDSYM Detects New (Pseudo) Symm. Elem       c/2         83 %Fit
RESPONSE: ADDSYM was used to modify the structural model along the detected
pseudo-symmetry element. The only difference with the reported model is that
the ligands are cut in two, i.e. the coordination sphere of the vanadium sites
is complete. To keep the chemical identity of the ligand in the asymmetric unit,
we have preferred to keep the original model.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1579P)²+3.2191P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         19299
_refine_ls_number_parameters     1105
_refine_ls_number_restraints     136
_refine_ls_R_factor_all          0.1008
_refine_ls_R_factor_gt           0.0851
_refine_ls_wR_factor_ref         0.2679
_refine_ls_wR_factor_gt          0.2503
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_restrained_S_all      1.044
_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
V1 V 0.15978(3) 0.30356(2) 1.13043(2) 0.01535(14) Uani 0.9289(10) 1 d . . P A 1
O1 O 0.18676(16) 0.24021(11) 1.08383(10) 0.0218(4) Uani 0.9289(10) 1 d . . P A
1
V1B V 0.1448(5) 0.3420(3) 1.1545(3) 0.01535(14) Uani 0.0711(10) 1 d . . P A 2
O1B O 0.118(2) 0.4031(14) 1.1996(12) 0.0218(4) Uani 0.0711(10) 1 d . . P A 2
O2 O 0.29175(15) 0.28713(10) 1.16468(9) 0.0231(4) Uani 1 1 d . . . . .
O3 O -0.10023(16) 0.74266(11) 0.77319(9) 0.0256(4) Uani 1 1 d . . . . .
N1 N 0.21171(16) 0.39843(11) 1.05775(10) 0.0163(4) Uani 1 1 d . . . . .
N2 N 0.14777(16) 0.45113(11) 1.01236(10) 0.0162(4) Uani 1 1 d . . . . .
N3 N 0.04670(16) 0.57864(11) 0.92008(10) 0.0179(4) Uani 1 1 d . . . . .
H3 H 0.001281 0.554555 0.954472 0.022 Uiso 1 1 calc R U . . .
N4 N 0.01119(17) 0.63872(11) 0.86758(10) 0.0182(4) Uani 1 1 d . . . . .
C1 C 0.3908(2) 0.30400(14) 1.13571(13) 0.0223(5) Uani 1 1 d . . . . .
C2 C 0.4828(2) 0.25970(16) 1.16752(15) 0.0279(5) Uani 1 1 d . . . . .
H2A H 0.472366 0.218916 1.208027 0.034 Uiso 1 1 calc R U . . .
C3 C 0.5878(3) 0.27453(17) 1.14084(17) 0.0347(6) Uani 1 1 d . . . . .
H3A H 0.648549 0.244120 1.163332 0.042 Uiso 1 1 calc R U . . .
C4 C 0.6056(2) 0.33343(17) 1.08146(17) 0.0336(6) Uani 1 1 d . . . . .
H4A H 0.678307 0.343078 1.062929 0.040 Uiso 1 1 calc R U . . .
C5 C 0.5160(2) 0.37796(15) 1.04959(15) 0.0270(5) Uani 1 1 d . . . . .
H5A H 0.527953 0.418824 1.009400 0.032 Uiso 1 1 calc R U . . .
C6 C 0.4081(2) 0.36444(13) 1.07495(13) 0.0206(5) Uani 1 1 d . . . . .
C7 C 0.31672(19) 0.41172(13) 1.03848(12) 0.0180(4) Uani 1 1 d . . . . .
C8 C 0.3195(2) 0.47410(14) 0.97928(13) 0.0214(5) Uani 1 1 d . . . . .
H8A H 0.381290 0.496037 0.954106 0.026 Uiso 1 1 calc R U . . .
C9 C 0.21150(19) 0.49680(13) 0.96557(12) 0.0171(4) Uani 1 1 d . . . . .
C10 C 0.15934(19) 0.56029(13) 0.91333(12) 0.0175(4) Uani 1 1 d . . . . .
C11 C 0.2011(2) 0.61098(14) 0.85292(12) 0.0211(5) Uani 1 1 d . . . . .
H11A H 0.277862 0.612390 0.833986 0.025 Uiso 1 1 calc R U . . .
C12 C 0.1056(2) 0.65979(14) 0.82570(12) 0.0193(5) Uani 1 1 d . . . . .
C13 C 0.0984(2) 0.72624(14) 0.76529(12) 0.0209(5) Uani 1 1 d . . . . .
C14 C 0.1945(2) 0.75421(15) 0.72937(13) 0.0270(5) Uani 1 1 d . . . . .
H14A H 0.264938 0.726804 0.742517 0.032 Uiso 1 1 calc R U . . .
C15 C 0.1889(3) 0.82069(16) 0.67535(15) 0.0326(6) Uani 1 1 d . . . . .
H15A H 0.254845 0.838468 0.651485 0.039 Uiso 1 1 calc R U . . .
C16 C 0.0854(3) 0.86126(16) 0.65639(14) 0.0322(6) Uani 1 1 d . . . . .
H16A H 0.080368 0.907683 0.620170 0.039 Uiso 1 1 calc R U . . .
C17 C -0.0100(2) 0.83434(15) 0.69000(13) 0.0272(5) Uani 1 1 d . . . . .
H17A H -0.079805 0.862263 0.676175 0.033 Uiso 1 1 calc R U . . .
C18 C -0.0053(2) 0.76620(14) 0.74435(12) 0.0219(5) Uani 1 1 d . . . . .
V2 V 0.15152(4) 0.30210(2) 0.63394(2) 0.01756(14) Uani 0.9278(10) 1 d . . P B 1
O4 O 0.18160(17) 0.23843(11) 0.58732(10) 0.0228(4) Uani 0.9278(10) 1 d . . P B
1
V2B V 0.1310(5) 0.3395(3) 0.6567(3) 0.01756(14) Uani 0.0722(10) 1 d . . P B 2
O4B O 0.100(2) 0.4024(14) 0.7005(12) 0.0228(4) Uani 0.0722(10) 1 d . . P B 2
O5 O 0.28072(16) 0.28464(11) 0.67094(9) 0.0265(4) Uani 1 1 d . . . . .
O6 O -0.08458(17) 0.74378(11) 0.27007(9) 0.0275(4) Uani 1 1 d . . . . .
N5 N 0.20813(17) 0.39541(11) 0.56151(10) 0.0179(4) Uani 1 1 d . . . . .
N6 N 0.14674(17) 0.44850(11) 0.51506(10) 0.0182(4) Uani 1 1 d . . . . .
N7 N 0.05063(17) 0.57690(11) 0.42105(10) 0.0192(4) Uani 1 1 d . . . . .
H7 H 0.003749 0.552784 0.454141 0.023 Uiso 1 1 calc R U . . .
N8 N 0.01824(18) 0.63822(11) 0.36858(10) 0.0202(4) Uani 1 1 d . . . . .
C19 C 0.3815(2) 0.29957(15) 0.64267(14) 0.0253(5) Uani 1 1 d . . . . .
C20 C 0.4720(3) 0.25372(16) 0.67594(15) 0.0312(6) Uani 1 1 d . . . . .
H20A H 0.458475 0.214276 0.717093 0.037 Uiso 1 1 calc R U . . .
C21 C 0.5787(3) 0.26473(18) 0.65031(17) 0.0371(7) Uani 1 1 d . . . . .
H21A H 0.638036 0.232851 0.673533 0.044 Uiso 1 1 calc R U . . .
C22 C 0.6001(3) 0.32248(19) 0.59039(18) 0.0377(7) Uani 1 1 d . . . . .
H22A H 0.674193 0.329877 0.572471 0.045 Uiso 1 1 calc R U . . .
C23 C 0.5127(2) 0.36944(17) 0.55675(16) 0.0312(6) Uani 1 1 d . . . . .
H23A H 0.527476 0.409377 0.516282 0.037 Uiso 1 1 calc R U . . .
C24 C 0.4026(2) 0.35869(14) 0.58176(14) 0.0235(5) Uani 1 1 d . . . . .
C25 C 0.3140(2) 0.40721(14) 0.54359(13) 0.0207(5) Uani 1 1 d . . . . .
C26 C 0.3194(2) 0.46942(14) 0.48486(13) 0.0232(5) Uani 1 1 d . . . . .
H26A H 0.382075 0.490772 0.460796 0.028 Uiso 1 1 calc R U . . .
C27 C 0.2125(2) 0.49329(13) 0.46934(12) 0.0191(4) Uani 1 1 d . . . . .
C28 C 0.1631(2) 0.55740(13) 0.41640(12) 0.0195(5) Uani 1 1 d . . . . .
C29 C 0.2078(2) 0.60820(14) 0.35800(13) 0.0229(5) Uani 1 1 d . . . . .
H29A H 0.285087 0.608837 0.340799 0.028 Uiso 1 1 calc R U . . .
C30 C 0.1147(2) 0.65868(14) 0.32948(12) 0.0214(5) Uani 1 1 d . . . . .
C31 C 0.1125(2) 0.72485(14) 0.26893(13) 0.0242(5) Uani 1 1 d . . . . .
C32 C 0.2117(3) 0.75060(16) 0.23667(14) 0.0315(6) Uani 1 1 d . . . . .
H32A H 0.278375 0.723882 0.254382 0.038 Uiso 1 1 calc R U . . .
C33 C 0.2140(3) 0.81380(17) 0.17991(15) 0.0357(7) Uani 1 1 d . . . . .
H33A H 0.281405 0.830481 0.158788 0.043 Uiso 1 1 calc R U . . .
C34 C 0.1173(3) 0.85216(17) 0.15449(15) 0.0373(7) Uani 1 1 d . . . . .
H34A H 0.118217 0.895642 0.115459 0.045 Uiso 1 1 calc R U . . .
C35 C 0.0182(3) 0.82822(16) 0.18508(14) 0.0324(6) Uani 1 1 d . . . . .
H35A H -0.047267 0.855532 0.166240 0.039 Uiso 1 1 calc R U . . .
C36 C 0.0126(2) 0.76469(15) 0.24310(13) 0.0252(5) Uani 1 1 d . . . . .
N9 N 0.2308(3) 0.28315(15) 1.38560(13) 0.0396(7) Uani 1 1 d . . . . .
C37 C 0.2537(3) 0.19910(18) 1.37846(17) 0.0431(8) Uani 1 1 d . . . . .
H37A H 0.328955 0.184312 1.346832 0.052 Uiso 1 1 calc R U . . .
H37B H 0.196177 0.197028 1.356112 0.052 Uiso 1 1 calc R U . . .
C38 C 0.2515(4) 0.1388(2) 1.44763(18) 0.0484(9) Uani 1 1 d . . . . .
H38A H 0.185114 0.159610 1.483280 0.058 Uiso 1 1 calc R U . . .
H38B H 0.320802 0.130274 1.464181 0.058 Uiso 1 1 calc R U . . .
C39 C 0.2452(3) 0.0605(2) 1.4404(2) 0.0525(9) Uani 1 1 d . . . . .
H39A H 0.309130 0.041221 1.402794 0.063 Uiso 1 1 calc R U . . .
H39B H 0.173682 0.068445 1.426596 0.063 Uiso 1 1 calc R U . . .
C40 C 0.2500(4) -0.0016(2) 1.5088(2) 0.0696(12) Uani 1 1 d . . . . .
H40A H 0.247872 -0.051563 1.501879 0.104 Uiso 1 1 calc R U . . .
H40B H 0.184807 0.016223 1.545671 0.104 Uiso 1 1 calc R U . . .
H40C H 0.320380 -0.009242 1.522906 0.104 Uiso 1 1 calc R U . . .
C41 C 0.3151(3) 0.28879(18) 1.42204(15) 0.0381(7) Uani 1 1 d . . . . .
H41A H 0.307073 0.253622 1.469292 0.046 Uiso 1 1 calc R U . . .
H41B H 0.294791 0.343490 1.428499 0.046 Uiso 1 1 calc R U . . .
C42 C 0.4395(3) 0.2671(3) 1.38333(18) 0.0562(11) Uani 1 1 d . . . . .
H42A H 0.460425 0.213475 1.374264 0.067 Uiso 1 1 calc R U . . .
H42B H 0.450601 0.304680 1.337541 0.067 Uiso 1 1 calc R U . . .
C43 C 0.5152(3) 0.2696(2) 1.4272(2) 0.0543(10) Uani 1 1 d . . . . .
H43A H 0.592521 0.267092 1.397479 0.065 Uiso 1 1 calc R U . . .
H43B H 0.486060 0.320734 1.441916 0.065 Uiso 1 1 calc R U . . .
C44 C 0.5228(4) 0.2038(2) 1.4917(2) 0.0592(11) Uani 1 1 d . . . . .
H44A H 0.574820 0.208115 1.516296 0.089 Uiso 1 1 calc R U . . .
H44B H 0.551005 0.152811 1.477732 0.089 Uiso 1 1 calc R U . . .
H44C H 0.447357 0.207669 1.522892 0.089 Uiso 1 1 calc R U . . .
C45 C 0.1124(3) 0.3106(2) 1.42975(17) 0.0434(8) Uani 1 1 d . . . . .
H45A H 0.110137 0.279606 1.478562 0.052 Uiso 1 1 calc R U . . .
H45B H 0.098508 0.366583 1.430687 0.052 Uiso 1 1 calc R U . . .
C46 C 0.0172(3) 0.3031(2) 1.40466(18) 0.0461(9) Uani 1 1 d . . . . .
H46A H 0.018428 0.246833 1.414890 0.055 Uiso 1 1 calc R U . . .
H46B H 0.028323 0.323326 1.353196 0.055 Uiso 1 1 calc R U . . .
C47 C -0.0978(3) 0.3497(2) 1.44104(17) 0.0428(8) Uani 1 1 d . . . . .
H47A H -0.108127 0.329905 1.492514 0.051 Uiso 1 1 calc R U . . .
H47B H -0.098922 0.406039 1.430407 0.051 Uiso 1 1 calc R U . . .
C48 C -0.1951(3) 0.3424(2) 1.4172(2) 0.0512(9) Uani 1 1 d . . . . .
H48A H -0.267039 0.374340 1.440244 0.077 Uiso 1 1 calc R U . . .
H48B H -0.196656 0.287008 1.429962 0.077 Uiso 1 1 calc R U . . .
H48C H -0.184408 0.361138 1.366181 0.077 Uiso 1 1 calc R U . . .
C49 C 0.2423(4) 0.3339(2) 1.31130(16) 0.0506(10) Uani 1 1 d . . . . .
H49A H 0.319825 0.314310 1.283935 0.061 Uiso 1 1 calc R U . . .
H49B H 0.188303 0.327337 1.288765 0.061 Uiso 1 1 calc R U . . .
C50 C 0.2206(4) 0.4213(2) 1.30746(18) 0.0537(10) Uani 1 1 d . . . . .
H50A H 0.263790 0.442282 1.316483 0.064 Uiso 1 1 d R U . C .
H50B H 0.142190 0.442782 1.337093 0.064 Uiso 1 1 d R U . . .
C51A C 0.1885(7) 0.4658(4) 1.2397(4) 0.0505(16) Uani 0.5 1 d . U P C 1
H51A H 0.243270 0.439603 1.202350 0.061 Uiso 0.5 1 calc R U P C 1
H51B H 0.198952 0.519230 1.230273 0.061 Uiso 0.5 1 calc R U P C 1
C52A C 0.0711(8) 0.4755(6) 1.2322(5) 0.071(2) Uani 0.5 1 d . U P C 1
H52A H 0.063414 0.503749 1.184340 0.106 Uiso 0.5 1 calc R U P C 1
H52B H 0.015086 0.505616 1.265839 0.106 Uiso 0.5 1 calc R U P C 1
H52C H 0.058226 0.423377 1.241499 0.106 Uiso 0.5 1 calc R U P C 1
C51B C 0.2660(9) 0.4723(5) 1.2281(4) 0.0596(19) Uani 0.5 1 d . U P C 2
H51C H 0.245039 0.454797 1.193363 0.072 Uiso 0.5 1 calc R U P C 2
H51D H 0.224476 0.528588 1.226040 0.072 Uiso 0.5 1 calc R U P C 2
C52B C 0.3916(9) 0.4664(5) 1.2053(4) 0.064(2) Uani 0.5 1 d . U P C 2
H52D H 0.414518 0.482609 1.239446 0.096 Uiso 0.5 1 calc R U P C 2
H52E H 0.407488 0.500936 1.159016 0.096 Uiso 0.5 1 calc R U P C 2
H52F H 0.434163 0.411702 1.202844 0.096 Uiso 0.5 1 calc R U P C 2
N10 N 0.2226(3) 0.28696(16) 0.88095(13) 0.0419(7) Uani 1 1 d . . . . .
C53 C 0.2490(3) 0.20536(19) 0.86671(17) 0.0454(8) Uani 1 1 d . . . . .
H53A H 0.189344 0.204848 0.845246 0.054 Uiso 1 1 calc R U . . .
H53B H 0.321876 0.195866 0.831851 0.054 Uiso 1 1 calc R U . . .
C54 C 0.2568(3) 0.1384(2) 0.92996(19) 0.0490(8) Uani 1 1 d . . . . .
H54A H 0.188669 0.149815 0.967982 0.059 Uiso 1 1 calc R U . . .
H54B H 0.324466 0.131707 0.947410 0.059 Uiso 1 1 calc R U . . .
C55 C 0.2654(4) 0.0623(2) 0.9085(2) 0.0595(10) Uani 1 1 d . . . . .
H55A H 0.189764 0.063976 0.904031 0.071 Uiso 1 1 calc R U . . .
H55B H 0.317682 0.060682 0.861927 0.071 Uiso 1 1 calc R U . . .
C56 C 0.3069(4) -0.0117(3) 0.9599(3) 0.0801(14) Uani 1 1 d . . . . .
H56A H 0.308664 -0.057607 0.944089 0.120 Uiso 1 1 calc R U . . .
H56B H 0.255737 -0.010524 1.006229 0.120 Uiso 1 1 calc R U . . .
H56C H 0.383469 -0.015155 0.962874 0.120 Uiso 1 1 calc R U . . .
C57 C 0.3076(3) 0.29058(19) 0.91788(16) 0.0395(7) Uani 1 1 d . . . . .
H57A H 0.302160 0.252327 0.963580 0.047 Uiso 1 1 calc R U . . .
H57B H 0.285191 0.343890 0.927844 0.047 Uiso 1 1 calc R U . . .
C58 C 0.4314(3) 0.2733(2) 0.87767(17) 0.0535(10) Uani 1 1 d . . . . .
H58A H 0.455741 0.220009 0.867360 0.064 Uiso 1 1 calc R U . . .
H58B H 0.439290 0.312220 0.832488 0.064 Uiso 1 1 calc R U . . .
C59 C 0.5057(3) 0.2777(2) 0.92110(18) 0.0462(8) Uani 1 1 d . . . . .
H59A H 0.473601 0.328364 0.936668 0.055 Uiso 1 1 calc R U . . .
H59B H 0.582058 0.277742 0.890882 0.055 Uiso 1 1 calc R U . . .
C60 C 0.5181(3) 0.2105(2) 0.9855(2) 0.0504(9) Uani 1 1 d . . . . .
H60A H 0.565196 0.218504 1.011517 0.076 Uiso 1 1 calc R U . . .
H60B H 0.553998 0.160183 0.970645 0.076 Uiso 1 1 calc R U . . .
H60C H 0.442953 0.209730 1.015886 0.076 Uiso 1 1 calc R U . . .
C61 C 0.1060(3) 0.3091(2) 0.92804(19) 0.0503(10) Uani 1 1 d . . . . .
H61A H 0.090590 0.363641 0.933565 0.060 Uiso 1 1 calc R U . . .
H61B H 0.106673 0.273741 0.975060 0.060 Uiso 1 1 calc R U . . .
C62 C 0.0099(3) 0.3042(2) 0.9016(2) 0.0544(10) Uani 1 1 d . . . . .
H62A H 0.007363 0.248615 0.912911 0.065 Uiso 1 1 calc R U . . .
H62B H 0.024103 0.322817 0.849902 0.065 Uiso 1 1 calc R U . . .
C63 C -0.1043(3) 0.3546(2) 0.93506(18) 0.0445(8) Uani 1 1 d . . . . .
H63A H -0.117889 0.336608 0.986799 0.053 Uiso 1 1 calc R U . . .
H63B H -0.102232 0.410350 0.923054 0.053 Uiso 1 1 calc R U . . .
C64 C -0.2012(4) 0.3487(2) 0.9095(2) 0.0546(10) Uani 1 1 d . . . . .
H64A H -0.272520 0.383935 0.929396 0.082 Uiso 1 1 calc R U . . .
H64B H -0.207287 0.294208 0.924688 0.082 Uiso 1 1 calc R U . . .
H64C H -0.186174 0.364082 0.858157 0.082 Uiso 1 1 calc R U . . .
C65 C 0.2293(4) 0.3428(2) 0.80882(18) 0.0540(11) Uani 1 1 d . . . . .
H65A H 0.306241 0.325817 0.779628 0.065 Uiso 1 1 calc R U . . .
H65B H 0.174645 0.337542 0.786054 0.065 Uiso 1 1 calc R U . . .
C66 C 0.2052(4) 0.4294(2) 0.8092(2) 0.0605(12) Uani 1 1 d . . . . .
H66A H 0.257872 0.442658 0.817058 0.073 Uiso 1 1 d R U . D .
H66B H 0.138772 0.447658 0.832968 0.073 Uiso 1 1 d R U . . .
C67A C 0.2523(8) 0.4841(4) 0.7278(4) 0.0530(17) Uani 0.5 1 d . U P D 2
H67A H 0.227218 0.469842 0.692871 0.064 Uiso 0.5 1 calc R U P D 2
H67B H 0.213112 0.540354 0.727955 0.064 Uiso 0.5 1 calc R U P D 2
C68A C 0.3796(9) 0.4766(5) 0.7018(5) 0.062(2) Uani 0.5 1 d . U P D 2
H68A H 0.393956 0.510208 0.654845 0.094 Uiso 0.5 1 calc R U P D 2
H68B H 0.420423 0.421531 0.699880 0.094 Uiso 0.5 1 calc R U P D 2
H68C H 0.405938 0.493239 0.734143 0.094 Uiso 0.5 1 calc R U P D 2
C67B C 0.1701(7) 0.4750(4) 0.7433(4) 0.0456(14) Uani 0.5 1 d . U P D 1
H67C H 0.227458 0.451977 0.704824 0.055 Uiso 0.5 1 calc R U P D 1
H67D H 0.176090 0.529137 0.736352 0.055 Uiso 0.5 1 calc R U P D 1
C68B C 0.0566(8) 0.4827(5) 0.7322(5) 0.064(2) Uani 0.5 1 d . U P D 1
H68D H 0.047807 0.516897 0.686261 0.097 Uiso 0.5 1 calc R U P D 1
H68E H -0.002825 0.505766 0.769155 0.097 Uiso 0.5 1 calc R U P D 1
H68F H 0.050177 0.430411 0.734091 0.097 Uiso 0.5 1 calc R U P D 1
N1S N 0.9928(3) 0.1293(2) 0.1355(2) 0.0617(9) Uani 1 1 d . . . . .
C1S C 1.0418(4) 0.0593(2) 0.1197(2) 0.0663(12) Uani 1 1 d . . . . .
H1SA H 1.097525 0.023539 0.144358 0.080 Uiso 1 1 calc R U . . .
C2S C 1.0177(4) 0.0361(2) 0.0713(2) 0.0612(11) Uani 1 1 d . . . . .
H2SA H 1.058256 -0.013221 0.058856 0.073 Uiso 1 1 calc R U . . .
C3S C 0.9336(4) 0.0855(2) 0.0411(2) 0.0627(11) Uani 1 1 d . . . . .
H3SA H 0.911127 0.068566 0.008918 0.075 Uiso 1 1 calc R U . . .
C4S C 0.8801(4) 0.1565(2) 0.0535(2) 0.0650(12) Uani 1 1 d . . . . .
H4SA H 0.823799 0.190634 0.028633 0.078 Uiso 1 1 calc R U . . .
C5S C 0.9069(4) 0.1805(2) 0.1030(3) 0.0742(13) Uani 1 1 d . . . . .
H5SA H 0.867771 0.230491 0.114522 0.089 Uiso 1 1 calc R U . . .
N2S N 1.0027(4) 0.1283(2) 0.6222(2) 0.0704(10) Uani 1 1 d . . . . .
C6S C 0.9535(4) 0.0827(3) 0.6788(2) 0.0692(12) Uani 1 1 d . . . . .
H6SA H 0.984518 0.063584 0.719491 0.083 Uiso 1 1 calc R U . . .
C7S C 0.8577(4) 0.0628(3) 0.6791(2) 0.0658(11) Uani 1 1 d . . . . .
H7SA H 0.822104 0.031037 0.719519 0.079 Uiso 1 1 calc R U . . .
C8S C 0.8162(4) 0.0906(3) 0.6192(3) 0.0710(12) Uani 1 1 d . . . . .
H8SA H 0.750816 0.078458 0.617014 0.085 Uiso 1 1 calc R U . . .
C9S C 0.8729(5) 0.1376(3) 0.5607(3) 0.0820(15) Uani 1 1 d . . . . .
H9SA H 0.845651 0.156012 0.518653 0.098 Uiso 1 1 calc R U . . .
C10S C 0.9607(4) 0.1563(3) 0.5626(3) 0.0711(12) Uani 1 1 d . . . . .
H10A H 0.995660 0.189340 0.522920 0.085 Uiso 1 1 calc R U . . .
N3S N 0.4419(3) -0.07545(17) 0.18744(18) 0.0596(9) Uani 1 1 d . . . . .
C11S C 0.3884(4) -0.0278(2) 0.1380(2) 0.0561(10) Uani 1 1 d . . . . .
H11B H 0.384777 -0.049903 0.102282 0.067 Uiso 1 1 calc R U . . .
C12S C 0.3376(4) 0.0513(2) 0.1347(2) 0.0546(9) Uani 1 1 d . . . . .
H12A H 0.299121 0.081991 0.098274 0.065 Uiso 1 1 calc R U . . .
C13S C 0.3429(4) 0.08512(19) 0.1836(2) 0.0544(9) Uani 1 1 d . . . . .
H13A H 0.307257 0.139562 0.182721 0.065 Uiso 1 1 calc R U . . .
C14S C 0.4019(3) 0.0383(2) 0.2353(2) 0.0521(8) Uani 1 1 d . . . . .
H14B H 0.408853 0.060134 0.270204 0.063 Uiso 1 1 calc R U . . .
C15S C 0.4497(4) -0.0404(2) 0.2345(2) 0.0589(10) Uani 1 1 d . . . . .
H15B H 0.490847 -0.072140 0.269417 0.071 Uiso 1 1 calc R U . . .
N4S N 0.2649(4) 1.0630(3) 0.7075(2) 0.0887(12) Uani 1 1 d . U . . .
C16S C 0.3483(4) 1.0722(3) 0.6498(3) 0.0766(14) Uani 1 1 d . U . . .
H16B H 0.352144 1.123709 0.623792 0.092 Uiso 1 1 calc R U . . .
C17S C 0.4269(5) 1.0081(3) 0.6290(3) 0.0939(16) Uani 1 1 d . U . . .
H17B H 0.481869 1.017516 0.586756 0.113 Uiso 1 1 calc R U . . .
C18S C 0.4339(5) 0.9362(3) 0.6608(3) 0.0835(13) Uani 1 1 d . U . . .
H18A H 0.494551 0.894197 0.645171 0.100 Uiso 1 1 calc R U . . .
C19S C 0.3564(6) 0.9240(3) 0.7139(4) 0.0971(15) Uani 1 1 d . U . . .
H19A H 0.357501 0.870729 0.736486 0.116 Uiso 1 1 calc R U . . .
C20S C 0.2645(4) 0.9863(3) 0.7432(3) 0.0952(15) Uani 1 1 d . U . . .
H20B H 0.208114 0.974817 0.784067 0.114 Uiso 1 1 calc R U . . .
N5S N 0.4571(5) 0.5936(4) 0.7348(3) 0.0468(11) Uani 0.5 1 d . U P E 1
C21S C 0.5159(6) 0.5440(5) 0.7828(4) 0.0559(15) Uani 0.5 1 d . U P E 1
H21S H 0.534832 0.566637 0.812553 0.067 Uiso 0.5 1 calc R U P E 1
C22S C 0.5499(8) 0.4644(6) 0.7919(5) 0.078(2) Uani 0.5 1 d . U P E 1
H22B H 0.594167 0.433978 0.825603 0.093 Uiso 0.5 1 calc R U P E 1
C23S C 0.5233(9) 0.4293(7) 0.7555(7) 0.091(2) Uani 0.5 1 d . U P E 1
H23B H 0.544366 0.373235 0.764300 0.109 Uiso 0.5 1 calc R U P E 1
C24S C 0.4653(9) 0.4719(7) 0.7050(6) 0.086(2) Uani 0.5 1 d . U P E 1
H24A H 0.447830 0.446863 0.676440 0.103 Uiso 0.5 1 calc R U P E 1
C25S C 0.4299(7) 0.5592(6) 0.6954(5) 0.0686(17) Uani 0.5 1 d . U P E 1
H25A H 0.387496 0.590698 0.661021 0.082 Uiso 0.5 1 calc R U P E 1


_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
V1 O1 1.6021(18) . ?
V1 O2 1.9169(18) . ?
V1 O3 1.9334(18) 2_567 ?
V1 N4 2.087(2) 2_567 ?
V1 N1 2.0874(19) . ?
V1B O1B 1.54(2) . ?
V1B O2 1.860(6) . ?
V1B O3 1.917(5) 2_567 ?
V1B N1 2.024(5) . ?
V1B N4 2.071(6) 2_567 ?
O2 C1 1.329(3) . ?
O3 C18 1.337(3) . ?
N1 N2 1.366(2) . ?
N1 C7 1.368(3) . ?
N2 C9 1.344(3) . ?
N3 C10 1.342(3) . ?
N3 N4 1.357(3) . ?
N3 H3 0.8800 . ?
N4 C12 1.359(3) . ?
C1 C2 1.407(3) . ?
C1 C6 1.420(3) . ?
C2 C3 1.379(4) . ?
C2 H2A 0.9500 . ?
C3 C4 1.388(4) . ?
C3 H3A 0.9500 . ?
C4 C5 1.386(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.403(3) . ?
C5 H5A 0.9500 . ?
C6 C7 1.464(3) . ?
C7 C8 1.403(3) . ?
C8 C9 1.394(3) . ?
C8 H8A 0.9500 . ?
C9 C10 1.457(3) . ?
C10 C11 1.394(3) . ?
C11 C12 1.412(3) . ?
C11 H11A 0.9500 . ?
C12 C13 1.461(3) . ?
C13 C14 1.407(3) . ?
C13 C18 1.412(4) . ?
C14 C15 1.384(4) . ?
C14 H14A 0.9500 . ?
C15 C16 1.395(4) . ?
C15 H15A 0.9500 . ?
C16 C17 1.384(4) . ?
C16 H16A 0.9500 . ?
C17 C18 1.408(3) . ?
C17 H17A 0.9500 . ?
V2 O4 1.5997(18) . ?
V2 O5 1.9125(19) . ?
V2 O6 1.9503(19) 2_566 ?
V2 N5 2.088(2) . ?
V2 N8 2.095(2) 2_566 ?
V2B O4B 1.55(2) . ?
V2B O5 1.912(6) . ?
V2B O6 1.915(6) 2_566 ?
V2B N8 2.008(6) 2_566 ?
V2B N5 2.044(6) . ?
O5 C19 1.332(3) . ?
O6 C36 1.337(3) . ?
N5 N6 1.365(3) . ?
N5 C25 1.369(3) . ?
N6 C27 1.343(3) . ?
N7 C28 1.345(3) . ?
N7 N8 1.356(3) . ?
N7 H7 0.8800 . ?
N8 C30 1.362(3) . ?
C19 C20 1.414(3) . ?
C19 C24 1.416(4) . ?
C20 C21 1.371(4) . ?
C20 H20A 0.9500 . ?
C21 C22 1.391(5) . ?
C21 H21A 0.9500 . ?
C22 C23 1.393(4) . ?
C22 H22A 0.9500 . ?
C23 C24 1.409(4) . ?
C23 H23A 0.9500 . ?
C24 C25 1.463(3) . ?
C25 C26 1.397(3) . ?
C26 C27 1.394(3) . ?
C26 H26A 0.9500 . ?
C27 C28 1.458(3) . ?
C28 C29 1.386(3) . ?
C29 C30 1.408(3) . ?
C29 H29A 0.9500 . ?
C30 C31 1.459(3) . ?
C31 C32 1.411(4) . ?
C31 C36 1.416(4) . ?
C32 C33 1.382(4) . ?
C32 H32A 0.9500 . ?
C33 C34 1.374(5) . ?
C33 H33A 0.9500 . ?
C34 C35 1.391(4) . ?
C34 H34A 0.9500 . ?
C35 C36 1.403(3) . ?
C35 H35A 0.9500 . ?
N9 C37 1.517(4) . ?
N9 C45 1.522(4) . ?
N9 C41 1.524(4) . ?
N9 C49 1.525(4) . ?
C37 C38 1.519(5) . ?
C37 H37A 0.9900 . ?
C37 H37B 0.9900 . ?
C38 C39 1.520(5) . ?
C38 H38A 0.9900 . ?
C38 H38B 0.9900 . ?
C39 C40 1.526(5) . ?
C39 H39A 0.9900 . ?
C39 H39B 0.9900 . ?
C40 H40A 0.9800 . ?
C40 H40B 0.9800 . ?
C40 H40C 0.9800 . ?
C41 C42 1.530(5) . ?
C41 H41A 0.9900 . ?
C41 H41B 0.9900 . ?
C42 C43 1.520(6) . ?
C42 H42A 0.9900 . ?
C42 H42B 0.9900 . ?
C43 C44 1.508(6) . ?
C43 H43A 0.9900 . ?
C43 H43B 0.9900 . ?
C44 H44A 0.9800 . ?
C44 H44B 0.9800 . ?
C44 H44C 0.9800 . ?
C45 C46 1.514(5) . ?
C45 H45A 0.9900 . ?
C45 H45B 0.9900 . ?
C46 C47 1.530(5) . ?
C46 H46A 0.9900 . ?
C46 H46B 0.9900 . ?
C47 C48 1.522(5) . ?
C47 H47A 0.9900 . ?
C47 H47B 0.9900 . ?
C48 H48A 0.9800 . ?
C48 H48B 0.9800 . ?
C48 H48C 0.9800 . ?
C49 C50 1.518(5) . ?
C49 H49A 0.9900 . ?
C49 H49B 0.9900 . ?
C50 C51A 1.484(8) . ?
C50 C51B 1.661(9) . ?
C50 H50A 0.8564 . ?
C50 H50B 1.0233 . ?
C51A C52A 1.504(12) . ?
C51A H51A 0.9900 . ?
C51A H51B 0.9900 . ?
C52A C68B 1.607(16) 2_567 ?
C52A H52A 0.9800 . ?
C52A H52B 0.9800 . ?
C52A H52C 0.9800 . ?
C52A H68E 0.83(2) 2_567 ?
C51B C52B 1.512(14) . ?
C51B H51C 0.9900 . ?
C51B H51D 0.9900 . ?
C52B H52D 0.9800 . ?
C52B H52E 0.9800 . ?
C52B H52F 0.9800 . ?
N10 C61 1.514(5) . ?
N10 C53 1.520(4) . ?
N10 C57 1.523(4) . ?
N10 C65 1.526(4) . ?
C53 C54 1.503(5) . ?
C53 H53A 0.9900 . ?
C53 H53B 0.9900 . ?
C54 C55 1.545(5) . ?
C54 H54A 0.9900 . ?
C54 H54B 0.9900 . ?
C55 C56 1.499(5) . ?
C55 H55A 0.9900 . ?
C55 H55B 0.9900 . ?
C56 H56A 0.9800 . ?
C56 H56B 0.9800 . ?
C56 H56C 0.9800 . ?
C57 C58 1.529(5) . ?
C57 H57A 0.9900 . ?
C57 H57B 0.9900 . ?
C58 C59 1.513(5) . ?
C58 H58A 0.9900 . ?
C58 H58B 0.9900 . ?
C59 C60 1.525(5) . ?
C59 H59A 0.9900 . ?
C59 H59B 0.9900 . ?
C60 H60A 0.9800 . ?
C60 H60B 0.9800 . ?
C60 H60C 0.9800 . ?
C61 C62 1.519(5) . ?
C61 H61A 0.9900 . ?
C61 H61B 0.9900 . ?
C62 C63 1.531(5) . ?
C62 H62A 0.9900 . ?
C62 H62B 0.9900 . ?
C63 C64 1.526(5) . ?
C63 H63A 0.9900 . ?
C63 H63B 0.9900 . ?
C64 H64A 0.9800 . ?
C64 H64B 0.9800 . ?
C64 H64C 0.9800 . ?
C65 C66 1.520(5) . ?
C65 H65A 0.9900 . ?
C65 H65B 0.9900 . ?
C66 C67B 1.472(7) . ?
C66 C67A 1.722(9) . ?
C66 H66A 0.8572 . ?
C66 H66B 0.8568 . ?
C67A C68A 1.530(13) . ?
C67A H67A 0.9900 . ?
C67A H67B 0.9900 . ?
C68A H68A 0.9800 . ?
C68A H68B 0.9800 . ?
C68A H68C 0.9800 . ?
C67B C68B 1.491(12) . ?
C67B H67C 0.9900 . ?
C67B H67D 0.9900 . ?
C68B H68D 0.9800 . ?
C68B H68E 0.9800 . ?
C68B H68F 0.9800 . ?
N1S C1S 1.318(5) . ?
N1S C5S 1.384(5) . ?
C1S C2S 1.330(5) . ?
C1S H1SA 0.9500 . ?
C2S C3S 1.336(5) . ?
C2S H2SA 0.9500 . ?
C3S C4S 1.316(5) . ?
C3S H3SA 0.9500 . ?
C4S C5S 1.380(6) . ?
C4S H4SA 0.9500 . ?
C5S H5SA 0.9500 . ?
N2S C6S 1.337(6) . ?
N2S C10S 1.369(6) . ?
C6S C7S 1.389(6) . ?
C6S H6SA 0.9500 . ?
C7S C8S 1.371(6) . ?
C7S H7SA 0.9500 . ?
C8S C9S 1.414(7) . ?
C8S H8SA 0.9500 . ?
C9S C10S 1.294(7) . ?
C9S H9SA 0.9500 . ?
C10S H10A 0.9500 . ?
N3S C11S 1.324(5) . ?
N3S C15S 1.344(5) . ?
C11S C12S 1.374(5) . ?
C11S H11B 0.9500 . ?
C12S C13S 1.347(5) . ?
C12S H12A 0.9500 . ?
C13S C14S 1.392(5) . ?
C13S H13A 0.9500 . ?
C14S C15S 1.377(5) . ?
C14S H14B 0.9500 . ?
C15S H15B 0.9500 . ?
N4S C16S 1.346(7) . ?
N4S C20S 1.387(7) . ?
C16S C17S 1.355(7) . ?
C16S H16B 0.9500 . ?
C17S C18S 1.277(8) . ?
C17S H17B 0.9500 . ?
C18S C19S 1.256(8) . ?
C18S H18A 0.9500 . ?
C19S C20S 1.465(8) . ?
C19S H19A 0.9500 . ?
C20S H20B 0.9500 . ?
N5S C25S 1.333(10) . ?
N5S C21S 1.349(10) . ?
C21S C22S 1.354(12) . ?
C21S H21S 0.9500 . ?
C22S C23S 1.289(16) . ?
C22S H22B 0.9500 . ?
C23S C24S 1.352(17) . ?
C23S H23B 0.9500 . ?
C24S C25S 1.486(15) . ?
C24S H24A 0.9500 . ?
C25S H25A 0.9500 . ?

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 V1 O2 108.48(9) . . ?
O1 V1 O3 108.15(9) . 2_567 ?
O2 V1 O3 83.44(8) . 2_567 ?
O1 V1 N4 103.02(9) . 2_567 ?
O2 V1 N4 148.19(8) . 2_567 ?
O3 V1 N4 82.72(8) 2_567 2_567 ?
O1 V1 N1 103.25(9) . . ?
O2 V1 N1 84.96(7) . . ?
O3 V1 N1 148.54(8) 2_567 . ?
N4 V1 N1 92.18(7) 2_567 . ?
O1B V1B O2 99.9(9) . . ?
O2 V1B O3 85.4(2) . 2_567 ?
O1B V1B N1 102.7(9) . . ?
O2 V1B N1 88.3(2) . . ?
O3 V1B N1 158.1(3) 2_567 . ?
O2 V1B N4 156.9(3) . 2_567 ?
O3 V1B N4 83.5(2) 2_567 2_567 ?
N1 V1B N4 94.5(2) . 2_567 ?
C1 O2 V1B 132.3(2) . . ?
C1 O2 V1 133.92(15) . . ?
C18 O3 V1B 136.5(2) . 2_567 ?
C18 O3 V1 130.21(15) . 2_567 ?
N2 N1 C7 108.27(18) . . ?
N2 N1 V1B 123.6(2) . . ?
C7 N1 V1B 124.5(2) . . ?
N2 N1 V1 122.81(14) . . ?
C7 N1 V1 128.05(15) . . ?
C9 N2 N1 108.23(18) . . ?
C10 N3 N4 111.97(18) . . ?
C10 N3 H3 124.0 . . ?
N4 N3 H3 124.0 . . ?
N3 N4 C12 106.12(19) . . ?
N3 N4 V1B 120.7(2) . 2_567 ?
C12 N4 V1B 129.8(2) . 2_567 ?
N3 N4 V1 122.81(15) . 2_567 ?
C12 N4 V1 129.89(16) . 2_567 ?
O2 C1 C2 117.9(2) . . ?
O2 C1 C6 123.4(2) . . ?
C2 C1 C6 118.7(2) . . ?
C3 C2 C1 121.1(2) . . ?
C3 C2 H2A 119.5 . . ?
C1 C2 H2A 119.5 . . ?
C2 C3 C4 120.7(2) . . ?
C2 C3 H3A 119.7 . . ?
C4 C3 H3A 119.7 . . ?
C5 C4 C3 119.1(3) . . ?
C5 C4 H4A 120.4 . . ?
C3 C4 H4A 120.4 . . ?
C4 C5 C6 121.9(2) . . ?
C4 C5 H5A 119.1 . . ?
C6 C5 H5A 119.1 . . ?
C5 C6 C1 118.5(2) . . ?
C5 C6 C7 119.9(2) . . ?
C1 C6 C7 121.6(2) . . ?
N1 C7 C8 108.6(2) . . ?
N1 C7 C6 123.0(2) . . ?
C8 C7 C6 128.4(2) . . ?
C9 C8 C7 104.8(2) . . ?
C9 C8 H8A 127.6 . . ?
C7 C8 H8A 127.6 . . ?
N2 C9 C8 110.10(19) . . ?
N2 C9 C10 118.2(2) . . ?
C8 C9 C10 131.6(2) . . ?
N3 C10 C11 107.0(2) . . ?
N3 C10 C9 119.0(2) . . ?
C11 C10 C9 134.0(2) . . ?
C10 C11 C12 105.7(2) . . ?
C10 C11 H11A 127.1 . . ?
C12 C11 H11A 127.1 . . ?
N4 C12 C11 109.18(19) . . ?
N4 C12 C13 121.3(2) . . ?
C11 C12 C13 129.5(2) . . ?
C14 C13 C18 118.9(2) . . ?
C14 C13 C12 119.9(2) . . ?
C18 C13 C12 121.1(2) . . ?
C15 C14 C13 121.6(3) . . ?
C15 C14 H14A 119.2 . . ?
C13 C14 H14A 119.2 . . ?
C14 C15 C16 119.2(3) . . ?
C14 C15 H15A 120.4 . . ?
C16 C15 H15A 120.4 . . ?
C17 C16 C15 120.4(2) . . ?
C17 C16 H16A 119.8 . . ?
C15 C16 H16A 119.8 . . ?
C16 C17 C18 121.0(3) . . ?
C16 C17 H17A 119.5 . . ?
C18 C17 H17A 119.5 . . ?
O3 C18 C17 117.6(2) . . ?
O3 C18 C13 123.5(2) . . ?
C17 C18 C13 118.8(2) . . ?
O4 V2 O5 107.82(9) . . ?
O4 V2 O6 107.78(9) . 2_566 ?
O5 V2 O6 84.47(8) . 2_566 ?
O4 V2 N5 102.59(9) . . ?
O5 V2 N5 84.98(8) . . ?
O6 V2 N5 149.60(8) 2_566 . ?
O4 V2 N8 103.31(9) . 2_566 ?
O5 V2 N8 148.65(8) . 2_566 ?
O6 V2 N8 82.61(8) 2_566 2_566 ?
N5 V2 N8 91.94(8) . 2_566 ?
O4B V2B O5 99.5(9) . . ?
O5 V2B O6 85.4(2) . 2_566 ?
O5 V2B N8 159.8(4) . 2_566 ?
O6 V2B N8 85.8(2) 2_566 2_566 ?
O4B V2B N5 100.8(9) . . ?
O5 V2B N5 86.2(2) . . ?
O6 V2B N5 159.7(4) 2_566 . ?
N8 V2B N5 95.8(2) 2_566 . ?
C19 O5 V2B 133.4(2) . . ?
C19 O5 V2 133.23(16) . . ?
C36 O6 V2B 134.5(2) . 2_566 ?
C36 O6 V2 130.94(16) . 2_566 ?
N6 N5 C25 108.27(19) . . ?
N6 N5 V2B 121.5(2) . . ?
C25 N5 V2B 127.0(2) . . ?
N6 N5 V2 122.66(15) . . ?
C25 N5 V2 128.22(16) . . ?
C27 N6 N5 108.14(19) . . ?
C28 N7 N8 111.81(19) . . ?
C28 N7 H7 124.1 . . ?
N8 N7 H7 124.1 . . ?
N7 N8 C30 105.75(19) . . ?
N7 N8 V2B 121.2(2) . 2_566 ?
C30 N8 V2B 130.0(2) . 2_566 ?
N7 N8 V2 123.50(15) . 2_566 ?
C30 N8 V2 129.69(16) . 2_566 ?
O5 C19 C20 117.7(2) . . ?
O5 C19 C24 123.8(2) . . ?
C20 C19 C24 118.5(3) . . ?
C21 C20 C19 121.7(3) . . ?
C21 C20 H20A 119.2 . . ?
C19 C20 H20A 119.2 . . ?
C20 C21 C22 120.1(3) . . ?
C20 C21 H21A 119.9 . . ?
C22 C21 H21A 119.9 . . ?
C21 C22 C23 119.8(3) . . ?
C21 C22 H22A 120.1 . . ?
C23 C22 H22A 120.1 . . ?
C22 C23 C24 121.1(3) . . ?
C22 C23 H23A 119.5 . . ?
C24 C23 H23A 119.5 . . ?
C23 C24 C19 118.8(2) . . ?
C23 C24 C25 119.5(2) . . ?
C19 C24 C25 121.6(2) . . ?
N5 C25 C26 108.6(2) . . ?
N5 C25 C24 122.5(2) . . ?
C26 C25 C24 128.8(2) . . ?
C27 C26 C25 104.8(2) . . ?
C27 C26 H26A 127.6 . . ?
C25 C26 H26A 127.6 . . ?
N6 C27 C26 110.1(2) . . ?
N6 C27 C28 118.2(2) . . ?
C26 C27 C28 131.6(2) . . ?
N7 C28 C29 107.3(2) . . ?
N7 C28 C27 119.2(2) . . ?
C29 C28 C27 133.4(2) . . ?
C28 C29 C30 105.6(2) . . ?
C28 C29 H29A 127.2 . . ?
C30 C29 H29A 127.2 . . ?
N8 C30 C29 109.5(2) . . ?
N8 C30 C31 121.5(2) . . ?
C29 C30 C31 129.0(2) . . ?
C32 C31 C36 119.6(2) . . ?
C32 C31 C30 119.0(2) . . ?
C36 C31 C30 121.5(2) . . ?
C33 C32 C31 121.5(3) . . ?
C33 C32 H32A 119.3 . . ?
C31 C32 H32A 119.3 . . ?
C34 C33 C32 119.0(3) . . ?
C34 C33 H33A 120.5 . . ?
C32 C33 H33A 120.5 . . ?
C33 C34 C35 120.9(3) . . ?
C33 C34 H34A 119.5 . . ?
C35 C34 H34A 119.5 . . ?
C34 C35 C36 121.6(3) . . ?
C34 C35 H35A 119.2 . . ?
C36 C35 H35A 119.2 . . ?
O6 C36 C35 119.0(2) . . ?
O6 C36 C31 123.5(2) . . ?
C35 C36 C31 117.4(3) . . ?
C37 N9 C45 110.7(3) . . ?
C37 N9 C41 110.7(2) . . ?
C45 N9 C41 107.5(2) . . ?
C37 N9 C49 106.5(2) . . ?
C45 N9 C49 110.7(2) . . ?
C41 N9 C49 110.9(3) . . ?
N9 C37 C38 114.1(2) . . ?
N9 C37 H37A 108.7 . . ?
C38 C37 H37A 108.7 . . ?
N9 C37 H37B 108.7 . . ?
C38 C37 H37B 108.7 . . ?
H37A C37 H37B 107.6 . . ?
C37 C38 C39 111.7(3) . . ?
C37 C38 H38A 109.3 . . ?
C39 C38 H38A 109.3 . . ?
C37 C38 H38B 109.3 . . ?
C39 C38 H38B 109.3 . . ?
H38A C38 H38B 107.9 . . ?
C38 C39 C40 111.7(3) . . ?
C38 C39 H39A 109.3 . . ?
C40 C39 H39A 109.3 . . ?
C38 C39 H39B 109.3 . . ?
C40 C39 H39B 109.3 . . ?
H39A C39 H39B 107.9 . . ?
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 . . ?
N9 C41 C42 115.1(2) . . ?
N9 C41 H41A 108.5 . . ?
C42 C41 H41A 108.5 . . ?
N9 C41 H41B 108.5 . . ?
C42 C41 H41B 108.5 . . ?
H41A C41 H41B 107.5 . . ?
C43 C42 C41 110.0(3) . . ?
C43 C42 H42A 109.7 . . ?
C41 C42 H42A 109.7 . . ?
C43 C42 H42B 109.7 . . ?
C41 C42 H42B 109.7 . . ?
H42A C42 H42B 108.2 . . ?
C44 C43 C42 114.1(4) . . ?
C44 C43 H43A 108.7 . . ?
C42 C43 H43A 108.7 . . ?
C44 C43 H43B 108.7 . . ?
C42 C43 H43B 108.7 . . ?
H43A C43 H43B 107.6 . . ?
C43 C44 H44A 109.5 . . ?
C43 C44 H44B 109.5 . . ?
H44A C44 H44B 109.5 . . ?
C43 C44 H44C 109.5 . . ?
H44A C44 H44C 109.5 . . ?
H44B C44 H44C 109.5 . . ?
C46 C45 N9 115.1(2) . . ?
C46 C45 H45A 108.5 . . ?
N9 C45 H45A 108.5 . . ?
C46 C45 H45B 108.5 . . ?
N9 C45 H45B 108.5 . . ?
H45A C45 H45B 107.5 . . ?
C45 C46 C47 110.6(2) . . ?
C45 C46 H46A 109.5 . . ?
C47 C46 H46A 109.5 . . ?
C45 C46 H46B 109.5 . . ?
C47 C46 H46B 109.5 . . ?
H46A C46 H46B 108.1 . . ?
C48 C47 C46 111.6(3) . . ?
C48 C47 H47A 109.3 . . ?
C46 C47 H47A 109.3 . . ?
C48 C47 H47B 109.3 . . ?
C46 C47 H47B 109.3 . . ?
H47A C47 H47B 108.0 . . ?
C47 C48 H48A 109.5 . . ?
C47 C48 H48B 109.5 . . ?
H48A C48 H48B 109.5 . . ?
C47 C48 H48C 109.5 . . ?
H48A C48 H48C 109.5 . . ?
H48B C48 H48C 109.5 . . ?
C50 C49 N9 114.4(2) . . ?
C50 C49 H49A 108.7 . . ?
N9 C49 H49A 108.7 . . ?
C50 C49 H49B 108.7 . . ?
N9 C49 H49B 108.7 . . ?
H49A C49 H49B 107.6 . . ?
C51A C50 C49 108.1(4) . . ?
C49 C50 C51B 114.2(4) . . ?
C51A C50 H50A 109.7 . . ?
C49 C50 H50A 125.8 . . ?
C51B C50 H50A 79.2 . . ?
C51A C50 H50B 93.9 . . ?
C49 C50 H50B 110.6 . . ?
C51B C50 H50B 120.6 . . ?
H50A C50 H50B 104.1 . . ?
C50 C51A C52A 118.6(7) . . ?
C50 C51A H51A 107.7 . . ?
C52A C51A H51A 107.7 . . ?
C50 C51A H51B 107.7 . . ?
C52A C51A H51B 107.7 . . ?
H51A C51A H51B 107.1 . . ?
C51A C52A C68B 136.7(11) . 2_567 ?
C51A C52A H52A 109.5 . . ?
C68B C52A H52A 94.1 2_567 . ?
C51A C52A H52B 109.5 . . ?
C68B C52A H52B 27.3 2_567 . ?
H52A C52A H52B 109.5 . . ?
C51A C52A H52C 109.5 . . ?
C68B C52A H52C 95.1 2_567 . ?
H52A C52A H52C 109.5 . . ?
H52B C52A H52C 109.5 . . ?
C51A C52A H68E 162(4) . 2_567 ?
C68B C52A H68E 30.1(12) 2_567 2_567 ?
H52A C52A H68E 69.8 . 2_567 ?
H52B C52A H68E 56.5 . 2_567 ?
H52C C52A H68E 86.8 . 2_567 ?
C52B C51B C50 116.9(7) . . ?
C52B C51B H51C 108.1 . . ?
C50 C51B H51C 108.1 . . ?
C52B C51B H51D 108.1 . . ?
C50 C51B H51D 108.1 . . ?
H51C C51B H51D 107.3 . . ?
C51B C52B H52D 109.5 . . ?
C51B C52B H52E 109.5 . . ?
H52D C52B H52E 109.5 . . ?
C51B C52B H52F 109.5 . . ?
H52D C52B H52F 109.5 . . ?
H52E C52B H52F 109.5 . . ?
C61 N10 C53 111.3(3) . . ?
C61 N10 C57 107.0(2) . . ?
C53 N10 C57 111.2(2) . . ?
C61 N10 C65 111.1(3) . . ?
C53 N10 C65 105.2(2) . . ?
C57 N10 C65 111.0(3) . . ?
C54 C53 N10 115.3(3) . . ?
C54 C53 H53A 108.4 . . ?
N10 C53 H53A 108.4 . . ?
C54 C53 H53B 108.4 . . ?
N10 C53 H53B 108.4 . . ?
H53A C53 H53B 107.5 . . ?
C53 C54 C55 108.5(3) . . ?
C53 C54 H54A 110.0 . . ?
C55 C54 H54A 110.0 . . ?
C53 C54 H54B 110.0 . . ?
C55 C54 H54B 110.0 . . ?
H54A C54 H54B 108.4 . . ?
C56 C55 C54 113.4(3) . . ?
C56 C55 H55A 108.9 . . ?
C54 C55 H55A 108.9 . . ?
C56 C55 H55B 108.9 . . ?
C54 C55 H55B 108.9 . . ?
H55A C55 H55B 107.7 . . ?
C55 C56 H56A 109.5 . . ?
C55 C56 H56B 109.5 . . ?
H56A C56 H56B 109.5 . . ?
C55 C56 H56C 109.5 . . ?
H56A C56 H56C 109.5 . . ?
H56B C56 H56C 109.5 . . ?
N10 C57 C58 115.7(2) . . ?
N10 C57 H57A 108.4 . . ?
C58 C57 H57A 108.4 . . ?
N10 C57 H57B 108.4 . . ?
C58 C57 H57B 108.4 . . ?
H57A C57 H57B 107.4 . . ?
C59 C58 C57 109.7(3) . . ?
C59 C58 H58A 109.7 . . ?
C57 C58 H58A 109.7 . . ?
C59 C58 H58B 109.7 . . ?
C57 C58 H58B 109.7 . . ?
H58A C58 H58B 108.2 . . ?
C58 C59 C60 114.5(3) . . ?
C58 C59 H59A 108.6 . . ?
C60 C59 H59A 108.6 . . ?
C58 C59 H59B 108.6 . . ?
C60 C59 H59B 108.6 . . ?
H59A C59 H59B 107.6 . . ?
C59 C60 H60A 109.5 . . ?
C59 C60 H60B 109.5 . . ?
H60A C60 H60B 109.5 . . ?
C59 C60 H60C 109.5 . . ?
H60A C60 H60C 109.5 . . ?
H60B C60 H60C 109.5 . . ?
N10 C61 C62 114.7(2) . . ?
N10 C61 H61A 108.6 . . ?
C62 C61 H61A 108.6 . . ?
N10 C61 H61B 108.6 . . ?
C62 C61 H61B 108.6 . . ?
H61A C61 H61B 107.6 . . ?
C61 C62 C63 111.1(3) . . ?
C61 C62 H62A 109.4 . . ?
C63 C62 H62A 109.4 . . ?
C61 C62 H62B 109.4 . . ?
C63 C62 H62B 109.4 . . ?
H62A C62 H62B 108.0 . . ?
C64 C63 C62 111.2(3) . . ?
C64 C63 H63A 109.4 . . ?
C62 C63 H63A 109.4 . . ?
C64 C63 H63B 109.4 . . ?
C62 C63 H63B 109.4 . . ?
H63A C63 H63B 108.0 . . ?
C63 C64 H64A 109.5 . . ?
C63 C64 H64B 109.5 . . ?
H64A C64 H64B 109.5 . . ?
C63 C64 H64C 109.5 . . ?
H64A C64 H64C 109.5 . . ?
H64B C64 H64C 109.5 . . ?
C66 C65 N10 115.3(3) . . ?
C66 C65 H65A 108.5 . . ?
N10 C65 H65A 108.5 . . ?
C66 C65 H65B 108.5 . . ?
N10 C65 H65B 108.5 . . ?
H65A C65 H65B 107.5 . . ?
C67B C66 C65 106.5(4) . . ?
C65 C66 C67A 112.4(4) . . ?
C67B C66 H66A 113.9 . . ?
C65 C66 H66A 116.1 . . ?
C67A C66 H66A 79.0 . . ?
C67B C66 H66B 90.6 . . ?
C65 C66 H66B 112.5 . . ?
C67A C66 H66B 118.9 . . ?
H66A C66 H66B 114.2 . . ?
C68A C67A C66 118.4(6) . . ?
C68A C67A H67A 107.7 . . ?
C66 C67A H67A 107.7 . . ?
C68A C67A H67B 107.7 . . ?
C66 C67A H67B 107.7 . . ?
H67A C67A H67B 107.1 . . ?
C67A C68A H68A 109.5 . . ?
C67A C68A H68B 109.5 . . ?
H68A C68A H68B 109.5 . . ?
C67A C68A H68C 109.5 . . ?
H68A C68A H68C 109.5 . . ?
H68B C68A H68C 109.5 . . ?
C66 C67B C68B 121.6(6) . . ?
C66 C67B H67C 106.9 . . ?
C68B C67B H67C 106.9 . . ?
C66 C67B H67D 106.9 . . ?
C68B C67B H67D 106.9 . . ?
H67C C67B H67D 106.7 . . ?
C67B C68B C52A 133.6(10) . 2_567 ?
C67B C68B H68D 109.5 . . ?
C52A C68B H68D 91.1 2_567 . ?
C67B C68B H68E 109.5 . . ?
C52A C68B H68E 25.2 2_567 . ?
H68D C68B H68E 109.5 . . ?
C67B C68B H68F 109.5 . . ?
C52A C68B H68F 101.3 2_567 . ?
H68D C68B H68F 109.5 . . ?
H68E C68B H68F 109.5 . . ?
C67B C68B H52B 165(3) . 2_567 ?
C52A C68B H52B 31(2) 2_567 2_567 ?
H68D C68B H52B 76.0 . 2_567 ?
H68E C68B H52B 55.8 . 2_567 ?
H68F C68B H52B 80.7 . 2_567 ?
C1S N1S C5S 118.9(3) . . ?
N1S C1S C2S 123.6(4) . . ?
N1S C1S H1SA 118.2 . . ?
C2S C1S H1SA 118.2 . . ?
C1S C2S C3S 116.8(3) . . ?
C1S C2S H2SA 121.6 . . ?
C3S C2S H2SA 121.6 . . ?
C4S C3S C2S 123.6(3) . . ?
C4S C3S H3SA 118.2 . . ?
C2S C3S H3SA 118.2 . . ?
C3S C4S C5S 119.1(4) . . ?
C3S C4S H4SA 120.5 . . ?
C5S C4S H4SA 120.5 . . ?
C4S C5S N1S 117.8(4) . . ?
C4S C5S H5SA 121.1 . . ?
N1S C5S H5SA 121.1 . . ?
C6S N2S C10S 121.0(4) . . ?
N2S C6S C7S 121.0(4) . . ?
N2S C6S H6SA 119.5 . . ?
C7S C6S H6SA 119.5 . . ?
C8S C7S C6S 117.9(4) . . ?
C8S C7S H7SA 121.0 . . ?
C6S C7S H7SA 121.0 . . ?
C7S C8S C9S 118.4(4) . . ?
C7S C8S H8SA 120.8 . . ?
C9S C8S H8SA 120.8 . . ?
C10S C9S C8S 122.2(5) . . ?
C10S C9S H9SA 118.9 . . ?
C8S C9S H9SA 118.9 . . ?
C9S C10S N2S 119.5(4) . . ?
C9S C10S H10A 120.3 . . ?
N2S C10S H10A 120.3 . . ?
C11S N3S C15S 115.3(3) . . ?
N3S C11S C12S 124.5(3) . . ?
N3S C11S H11B 117.8 . . ?
C12S C11S H11B 117.8 . . ?
C13S C12S C11S 119.5(3) . . ?
C13S C12S H12A 120.3 . . ?
C11S C12S H12A 120.3 . . ?
C12S C13S C14S 118.4(3) . . ?
C12S C13S H13A 120.8 . . ?
C14S C13S H13A 120.8 . . ?
C15S C14S C13S 117.9(3) . . ?
C15S C14S H14B 121.0 . . ?
C13S C14S H14B 121.0 . . ?
N3S C15S C14S 124.3(3) . . ?
N3S C15S H15B 117.9 . . ?
C14S C15S H15B 117.9 . . ?
C16S N4S C20S 117.1(4) . . ?
N4S C16S C17S 120.1(5) . . ?
N4S C16S H16B 120.0 . . ?
C17S C16S H16B 120.0 . . ?
C18S C17S C16S 126.0(6) . . ?
C18S C17S H17B 117.0 . . ?
C16S C17S H17B 117.0 . . ?
C19S C18S C17S 116.6(5) . . ?
C19S C18S H18A 121.7 . . ?
C17S C18S H18A 121.7 . . ?
C18S C19S C20S 124.4(5) . . ?
C18S C19S H19A 117.8 . . ?
C20S C19S H19A 117.8 . . ?
N4S C20S C19S 115.7(5) . . ?
N4S C20S H20B 122.1 . . ?
C19S C20S H20B 122.1 . . ?
C25S N5S C21S 115.4(7) . . ?
N5S C21S C22S 125.1(9) . . ?
N5S C21S H21S 117.5 . . ?
C22S C21S H21S 117.5 . . ?
C23S C22S C21S 121.0(11) . . ?
C23S C22S H22B 119.5 . . ?
C21S C22S H22B 119.5 . . ?
C22S C23S C24S 120.2(11) . . ?
C22S C23S H23B 119.9 . . ?
C24S C23S H23B 119.9 . . ?
C23S C24S C25S 117.8(9) . . ?
C23S C24S H24A 121.1 . . ?
C25S C24S H24A 121.1 . . ?
N5S C25S C24S 120.4(9) . . ?
N5S C25S H25A 119.8 . . ?
C24S C25S H25A 119.8 . . ?

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
_geom_hbond_publ_flag
N3 H3 N2 0.88 1.85 2.614(3) 143.4 2_567 yes
N7 H7 N6 0.88 1.85 2.604(3) 142.9 2_566 yes

_refine_diff_density_max         0.975
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.102

