# Electronic Supplementary Material (ESI) for Polymer Chemistry.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_Ligand_1
_database_code_depnum_ccdc_archive 'CCDC 1562812'
_audit_update_record             
;
2017-07-18 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H32 N2 O3 S2'
_chemical_formula_weight         436.61

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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                   9.2586(2)
_cell_length_b                   9.6167(2)
_cell_length_c                   15.5862(4)
_cell_angle_alpha                89.2238(12)
_cell_angle_beta                 75.0508(11)
_cell_angle_gamma                65.7927(10)
_cell_volume                     1216.17(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    8982
_cell_measurement_theta_min      2.72
_cell_measurement_theta_max      27.11

_exptl_crystal_description       BLock
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_F_000             468
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.242
_shelx_estimated_absorpt_T_min   0.920
_shelx_estimated_absorpt_T_max   0.976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.920
_exptl_absorpt_correction_T_max  0.976
_exptl_absorpt_process_details   'SADABS V2014/5(Bruker AXS.Inc)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16707
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.335
_diffrn_reflns_theta_max         24.992
_diffrn_reflns_theta_full        24.992
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4271
_reflns_number_gt                3519
_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1366P)²+1.0974P] 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         4271
_refine_ls_number_parameters     278
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0850
_refine_ls_R_factor_gt           0.0737
_refine_ls_wR_factor_ref         0.2338
_refine_ls_wR_factor_gt          0.2182
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.037
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.001

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C -0.1556(6) 0.0146(6) 1.2672(3) 0.0863(14) Uani 1 1 d . . . . .
H1 H -0.2668 0.0746 1.2942 0.104 Uiso 1 1 calc R U . . .
C2 C -0.0613(7) -0.0950(7) 1.3066(3) 0.0938(15) Uani 1 1 d . . . . .
H2 H -0.1012 -0.1203 1.3628 0.113 Uiso 1 1 calc R U . . .
C3 C 0.1007(4) -0.0704(4) 1.1637(2) 0.0492(7) Uani 1 1 d . . . . .
C4 C 0.2421(4) -0.0998(3) 1.0854(2) 0.0476(7) Uani 1 1 d . . . . .
C5 C 0.3289(4) 0.0812(3) 0.8960(2) 0.0489(7) Uani 1 1 d . . . . .
H5 H 0.2395 0.1767 0.9107 0.059 Uiso 1 1 calc R U . . .
C6 C 0.4523(4) 0.0472(3) 0.8102(2) 0.0438(7) Uani 1 1 d . . . . .
C7 C 0.5869(4) -0.0974(3) 0.7840(2) 0.0420(6) Uani 1 1 d . . . . .
C8 C 0.6976(3) -0.1299(3) 0.6991(2) 0.0413(6) Uani 1 1 d . . . . .
C9 C 0.6692(4) -0.0143(3) 0.6426(2) 0.0442(7) Uani 1 1 d . . . . .
H9 H 0.7418 -0.0349 0.5857 0.053 Uiso 1 1 calc R U . . .
C10 C 0.5377(4) 0.1315(3) 0.6663(2) 0.0455(7) Uani 1 1 d . . . . .
C11 C 0.4316(4) 0.1586(3) 0.7499(2) 0.0467(7) Uani 1 1 d . . . . .
H11 H 0.3429 0.2540 0.7673 0.056 Uiso 1 1 calc R U . . .
C12 C 0.8430(4) -0.2884(3) 0.6688(2) 0.0496(7) Uani 1 1 d . . . . .
C13 C 0.9558(5) -0.3224(5) 0.7316(3) 0.0782(12) Uani 1 1 d . . . . .
H13A H 1.0055 -0.2513 0.7255 0.117 Uiso 1 1 calc R U . . .
H13B H 1.0405 -0.4251 0.7159 0.117 Uiso 1 1 calc R U . . .
H13C H 0.8916 -0.3120 0.7923 0.117 Uiso 1 1 calc R U . . .
C14 C 0.7773(5) -0.4112(4) 0.6702(3) 0.0719(11) Uani 1 1 d . . . . .
H14A H 0.7232 -0.4177 0.7306 0.108 Uiso 1 1 calc R U . . .
H14B H 0.8673 -0.5085 0.6457 0.108 Uiso 1 1 calc R U . . .
H14C H 0.7002 -0.3844 0.6351 0.108 Uiso 1 1 calc R U . . .
C15 C 0.9480(5) -0.2974(4) 0.5739(3) 0.0694(10) Uani 1 1 d . . . . .
H15A H 0.8816 -0.2796 0.5332 0.104 Uiso 1 1 calc R U . . .
H15B H 1.0380 -0.3972 0.5579 0.104 Uiso 1 1 calc R U . . .
H15C H 0.9904 -0.2210 0.5710 0.104 Uiso 1 1 calc R U . . .
C16 C 0.5142(4) 0.2538(4) 0.6000(2) 0.0590(9) Uani 1 1 d . . . . .
C17 C 0.6677(9) 0.2294(9) 0.5327(6) 0.229(7) Uani 1 1 d . . . . .
H17A H 0.6815 0.1648 0.4820 0.343 Uiso 1 1 calc R U . . .
H17B H 0.7588 0.1811 0.5576 0.343 Uiso 1 1 calc R U . . .
H17C H 0.6636 0.3263 0.5142 0.343 Uiso 1 1 calc R U . . .
C18 C 0.3725(11) 0.2733(9) 0.5673(6) 0.157(4) Uani 1 1 d . . . . .
H18A H 0.3307 0.3723 0.5460 0.235 Uiso 1 1 calc R U . . .
H18B H 0.2877 0.2655 0.6151 0.235 Uiso 1 1 calc R U . . .
H18C H 0.4063 0.1950 0.5195 0.235 Uiso 1 1 calc R U . . .
C19 C 0.4633(10) 0.4111(6) 0.6509(4) 0.123(2) Uani 1 1 d . . . . .
H19A H 0.5403 0.4020 0.6841 0.184 Uiso 1 1 calc R U . . .
H19B H 0.3550 0.4435 0.6912 0.184 Uiso 1 1 calc R U . . .
H19C H 0.4631 0.4852 0.6091 0.184 Uiso 1 1 calc R U . . .
C20 C 0.6344(5) 0.4236(5) 0.1114(3) 0.0785(12) Uani 1 1 d . . . . .
H20A H 0.6233 0.3561 0.0712 0.118 Uiso 1 1 calc R U . . .
H20B H 0.5402 0.5207 0.1226 0.118 Uiso 1 1 calc R U . . .
H20C H 0.6416 0.3795 0.1666 0.118 Uiso 1 1 calc R U . . .
C21 C 0.7644(6) 0.5222(6) -0.0359(4) 0.0881(14) Uani 1 1 d . . . . .
H21A H 0.8525 0.5428 -0.0728 0.132 Uiso 1 1 calc R U . . .
H21B H 0.6649 0.6152 -0.0205 0.132 Uiso 1 1 calc R U . . .
H21C H 0.7483 0.4476 -0.0680 0.132 Uiso 1 1 calc R U . . .
C22 C -0.0720(4) 0.0336(4) 1.1790(2) 0.0522(8) Uani 1 1 d . . . . .
H22 H -0.1192 0.0992 1.1398 0.063 Uiso 1 1 calc R U . . .
N2 N 0.2213(3) 0.0102(3) 1.02915(18) 0.0513(7) Uani 1 1 d . . . . .
O1 O 0.3685(3) -0.2181(3) 1.07180(17) 0.0668(7) Uani 1 1 d . . . . .
N3 N 0.3430(3) -0.0191(3) 0.95112(17) 0.0489(6) Uani 1 1 d . . . . .
O3 O 0.6102(3) -0.2071(3) 0.84140(17) 0.0584(7) Uani 1 1 d . . . . .
O4 O 0.9531(3) 0.2955(3) 0.0341(2) 0.0876(10) Uani 1 1 d . . . . .
S1 S 0.13313(19) -0.18281(17) 1.24732(9) 0.1004(5) Uani 1 1 d . . . . .
S2 S 0.81507(11) 0.45020(10) 0.06280(7) 0.0626(3) Uani 1 1 d . . . . .
H1N H 0.147(5) 0.094(5) 1.038(3) 0.060(11) Uiso 1 1 d . . . . .
H3O H 0.536(6) -0.173(5) 0.883(3) 0.071(13) Uiso 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.325(7) . ?
C1 C22 1.443(5) . ?
C1 H1 0.9300 . ?
C2 S1 1.650(6) . ?
C2 H2 0.9300 . ?
C3 C22 1.453(5) . ?
C3 C4 1.471(5) . ?
C3 S1 1.690(3) . ?
C4 O1 1.223(4) . ?
C4 N2 1.350(4) . ?
C5 N3 1.272(4) . ?
C5 C6 1.455(4) . ?
C5 H5 0.9300 . ?
C6 C11 1.403(4) . ?
C6 C7 1.409(4) . ?
C7 O3 1.359(4) . ?
C7 C8 1.396(4) . ?
C8 C9 1.391(4) . ?
C8 C12 1.539(4) . ?
C9 C10 1.402(4) . ?
C9 H9 0.9300 . ?
C10 C11 1.367(4) . ?
C10 C16 1.540(4) . ?
C11 H11 0.9300 . ?
C12 C15 1.528(5) . ?
C12 C14 1.532(5) . ?
C12 C13 1.547(5) . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 C17 1.463(7) . ?
C16 C18 1.468(7) . ?
C16 C19 1.548(7) . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 S2 1.769(4) . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 S2 1.773(4) . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22 0.9300 . ?
N2 N3 1.367(4) . ?
N2 H1N 0.80(4) . ?
O3 H3O 0.77(5) . ?
O4 S2 1.487(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 C1 C22 114.6(4) . . ?
C2 C1 H1 122.7 . . ?
C22 C1 H1 122.7 . . ?
C1 C2 S1 114.2(3) . . ?
C1 C2 H2 122.9 . . ?
S1 C2 H2 122.9 . . ?
C22 C3 C4 130.2(3) . . ?
C22 C3 S1 112.1(2) . . ?
C4 C3 S1 117.5(2) . . ?
O1 C4 N2 122.6(3) . . ?
O1 C4 C3 121.8(3) . . ?
N2 C4 C3 115.6(3) . . ?
N3 C5 C6 120.2(3) . . ?
N3 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C11 C6 C7 119.0(3) . . ?
C11 C6 C5 119.0(3) . . ?
C7 C6 C5 121.9(3) . . ?
O3 C7 C8 119.2(3) . . ?
O3 C7 C6 120.1(3) . . ?
C8 C7 C6 120.6(3) . . ?
C9 C8 C7 117.3(3) . . ?
C9 C8 C12 121.5(3) . . ?
C7 C8 C12 121.2(3) . . ?
C8 C9 C10 123.9(3) . . ?
C8 C9 H9 118.0 . . ?
C10 C9 H9 118.0 . . ?
C11 C10 C9 117.0(3) . . ?
C11 C10 C16 122.1(3) . . ?
C9 C10 C16 120.9(3) . . ?
C10 C11 C6 122.2(3) . . ?
C10 C11 H11 118.9 . . ?
C6 C11 H11 118.9 . . ?
C15 C12 C14 107.6(3) . . ?
C15 C12 C8 112.0(3) . . ?
C14 C12 C8 109.5(3) . . ?
C15 C12 C13 107.7(3) . . ?
C14 C12 C13 110.1(3) . . ?
C8 C12 C13 109.8(3) . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C12 C14 H14A 109.5 . . ?
C12 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C12 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C12 C15 H15A 109.5 . . ?
C12 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C17 C16 C18 116.9(6) . . ?
C17 C16 C10 112.8(3) . . ?
C18 C16 C10 109.4(3) . . ?
C17 C16 C19 103.7(6) . . ?
C18 C16 C19 104.5(5) . . ?
C10 C16 C19 108.9(3) . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C16 C18 H18A 109.5 . . ?
C16 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C16 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
S2 C20 H20A 109.5 . . ?
S2 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
S2 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
S2 C21 H21A 109.5 . . ?
S2 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
S2 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C1 C22 C3 106.3(3) . . ?
C1 C22 H22 126.8 . . ?
C3 C22 H22 126.8 . . ?
C4 N2 N3 117.5(3) . . ?
C4 N2 H1N 127(3) . . ?
N3 N2 H1N 115(3) . . ?
C5 N3 N2 119.8(3) . . ?
C7 O3 H3O 106(3) . . ?
C2 S1 C3 92.5(2) . . ?
O4 S2 C20 107.26(19) . . ?
O4 S2 C21 105.8(2) . . ?
C20 S2 C21 97.3(2) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C22 C1 C2 S1 1.8(6) . . . . ?
C22 C3 C4 O1 -159.0(3) . . . . ?
S1 C3 C4 O1 14.7(4) . . . . ?
C22 C3 C4 N2 19.6(5) . . . . ?
S1 C3 C4 N2 -166.8(2) . . . . ?
N3 C5 C6 C11 178.5(3) . . . . ?
N3 C5 C6 C7 2.0(5) . . . . ?
C11 C6 C7 O3 179.7(3) . . . . ?
C5 C6 C7 O3 -3.9(5) . . . . ?
C11 C6 C7 C8 -0.5(4) . . . . ?
C5 C6 C7 C8 175.9(3) . . . . ?
O3 C7 C8 C9 -179.9(3) . . . . ?
C6 C7 C8 C9 0.2(4) . . . . ?
O3 C7 C8 C12 1.2(4) . . . . ?
C6 C7 C8 C12 -178.7(3) . . . . ?
C7 C8 C9 C10 0.4(4) . . . . ?
C12 C8 C9 C10 179.2(3) . . . . ?
C8 C9 C10 C11 -0.7(5) . . . . ?
C8 C9 C10 C16 -180.0(3) . . . . ?
C9 C10 C11 C6 0.4(5) . . . . ?
C16 C10 C11 C6 179.7(3) . . . . ?
C7 C6 C11 C10 0.2(5) . . . . ?
C5 C6 C11 C10 -176.4(3) . . . . ?
C9 C8 C12 C15 1.5(4) . . . . ?
C7 C8 C12 C15 -179.6(3) . . . . ?
C9 C8 C12 C14 -117.8(3) . . . . ?
C7 C8 C12 C14 61.0(4) . . . . ?
C9 C8 C12 C13 121.1(3) . . . . ?
C7 C8 C12 C13 -60.0(4) . . . . ?
C11 C10 C16 C17 156.3(6) . . . . ?
C9 C10 C16 C17 -24.4(7) . . . . ?
C11 C10 C16 C18 -71.8(6) . . . . ?
C9 C10 C16 C18 107.5(5) . . . . ?
C11 C10 C16 C19 41.8(5) . . . . ?
C9 C10 C16 C19 -138.9(4) . . . . ?
C2 C1 C22 C3 -4.8(5) . . . . ?
C4 C3 C22 C1 179.7(3) . . . . ?
S1 C3 C22 C1 5.8(4) . . . . ?
O1 C4 N2 N3 4.9(5) . . . . ?
C3 C4 N2 N3 -173.6(3) . . . . ?
C6 C5 N3 N2 -175.8(3) . . . . ?
C4 N2 N3 C5 -179.9(3) . . . . ?
C1 C2 S1 C3 1.6(4) . . . . ?
C22 C3 S1 C2 -4.4(3) . . . . ?
C4 C3 S1 C2 -179.2(3) . . . . ?

_refine_diff_density_max         0.890
_refine_diff_density_min         -0.601
_refine_diff_density_rms         0.070


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Dimethyl sulfoxide'
####################################################################### 
# 
# 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_Complex_1
_database_code_depnum_ccdc_archive 'CCDC 1562817'
_audit_update_record             
;
2017-07-18 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C40.03 H46.03 N4 O4 S2 Ti '
_chemical_formula_sum            'C40.03 H46.03 N4 O4 S2 Ti '
_chemical_formula_weight         758.83

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

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

_cell_length_a                   17.7190(9)
_cell_length_b                   10.8186(5)
_cell_length_c                   21.7958(11)
_cell_angle_alpha                90
_cell_angle_beta                 93.293(2)
_cell_angle_gamma                90
_cell_volume                     4171.2(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    1918
_cell_measurement_theta_min      2.25
_cell_measurement_theta_max      19.70

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_F_000             1600
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.130
_exptl_absorpt_coefficient_mu    0.347
_shelx_estimated_absorpt_T_min   0.915
_shelx_estimated_absorpt_T_max   0.956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.915
_exptl_absorpt_correction_T_max  0.956
_exptl_absorpt_process_details   'SADABS V2014/5(Bruker AXS.Inc)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            14548
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_av_R_equivalents  0.0722
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         1.872
_diffrn_reflns_theta_max         19.940
_diffrn_reflns_theta_full        19.940
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             3837
_reflns_number_gt                2833
_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0801P)²+1.4016P] 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         3837
_refine_ls_number_parameters     535
_refine_ls_number_restraints     68
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0471
_refine_ls_wR_factor_ref         0.1493
_refine_ls_wR_factor_gt          0.1194
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.061
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.4229(3) 0.3298(5) 0.4009(2) 0.0453(14) Uani 1 1 d . . . . .
H1 H 0.4208 0.2441 0.4038 0.054 Uiso 1 1 calc R U . . .
C2 C 0.3614(3) 0.4066(6) 0.3803(2) 0.0586(16) Uani 1 1 d . . . . .
H2 H 0.3137 0.3763 0.3680 0.070 Uiso 1 1 calc R U . . .
C3 C 0.3795(3) 0.5293(6) 0.3803(2) 0.0554(15) Uani 1 1 d . . . . .
H3 H 0.3458 0.5915 0.3679 0.066 Uiso 1 1 calc R U . . .
C4 C 0.4861(3) 0.4005(5) 0.4161(2) 0.0429(14) Uani 1 1 d . . . . .
C5 C 0.5597(3) 0.3590(5) 0.4409(2) 0.0414(13) Uani 1 1 d . . . . .
C6 C 0.7283(3) 0.4513(5) 0.5024(2) 0.0466(14) Uani 1 1 d . . . . .
H6 H 0.7224 0.5353 0.4944 0.056 Uiso 1 1 calc R U . . .
C7 C 0.7960(3) 0.4133(5) 0.5359(2) 0.0457(14) Uani 1 1 d . . . . .
C8 C 0.8472(3) 0.5058(5) 0.5574(3) 0.0576(16) Uani 1 1 d . . . . .
H8 H 0.8366 0.5881 0.5483 0.069 Uiso 1 1 calc R U . . .
C9 C 0.9121(3) 0.4765(6) 0.5914(3) 0.0619(17) Uani 1 1 d . . . . .
C10 C 0.9255(3) 0.3503(6) 0.6022(3) 0.0637(17) Uani 1 1 d . . . . .
H10 H 0.9701 0.3287 0.6241 0.076 Uiso 1 1 calc R U . . .
C11 C 0.8772(3) 0.2551(5) 0.5828(2) 0.0498(14) Uani 1 1 d . . . . .
C12 C 0.8102(3) 0.2884(5) 0.5487(2) 0.0435(14) Uani 1 1 d . . . . .
C13 C 0.9692(4) 0.5751(7) 0.6133(4) 0.085(2) Uani 1 1 d . . . . .
C14 C 0.9466(13) 0.7015(17) 0.6006(14) 0.150(9) Uani 0.520(14) 1 d . U P A 1
H14A H 0.8966 0.7148 0.6140 0.225 Uiso 0.520(14) 1 calc R U P A 1
H14B H 0.9469 0.7166 0.5572 0.225 Uiso 0.520(14) 1 calc R U P A 1
H14C H 0.9812 0.7568 0.6220 0.225 Uiso 0.520(14) 1 calc R U P A 1
C15 C 1.0498(7) 0.5422(16) 0.5817(7) 0.090(6) Uani 0.520(14) 1 d . U P A 1
H15A H 1.0404 0.5300 0.5383 0.135 Uiso 0.520(14) 1 calc R U P A 1
H15B H 1.0710 0.4682 0.5999 0.135 Uiso 0.520(14) 1 calc R U P A 1
H15C H 1.0847 0.6093 0.5887 0.135 Uiso 0.520(14) 1 calc R U P A 1
C16 C 1.0052(6) 0.5454(9) 0.6741(5) 0.171(5) Uani 1 1 d . . . B 1
H16A H 1.0428 0.6066 0.6851 0.257 Uiso 1 1 calc R U . B 1
H16B H 1.0287 0.4655 0.6727 0.257 Uiso 1 1 calc R U . B 1
H16C H 0.9677 0.5446 0.7041 0.257 Uiso 1 1 calc R U . B 1
C15A C 0.9927(13) 0.647(2) 0.5599(9) 0.127(8) Uani 0.491(14) 1 d . U P A 2
H15D H 1.0211 0.5949 0.5341 0.191 Uiso 0.491(14) 1 calc R U P A 2
H15E H 1.0235 0.7154 0.5740 0.191 Uiso 0.491(14) 1 calc R U P A 2
H15F H 0.9487 0.6775 0.5370 0.191 Uiso 0.491(14) 1 calc R U P A 2
C14A C 0.9196(12) 0.6739(18) 0.6522(9) 0.115(7) Uani 0.491(14) 1 d . U P A 2
H14D H 0.8767 0.7013 0.6270 0.173 Uiso 0.491(14) 1 calc R U P A 2
H14E H 0.9507 0.7436 0.6640 0.173 Uiso 0.491(14) 1 calc R U P A 2
H14F H 0.9027 0.6342 0.6884 0.173 Uiso 0.491(14) 1 calc R U P A 2
C17 C 0.8949(3) 0.1205(6) 0.5967(3) 0.0684(18) Uani 1 1 d . . . . .
C18 C 0.9730(4) 0.1044(7) 0.6328(4) 0.120(3) Uani 1 1 d . . . . .
H18A H 1.0124 0.1346 0.6083 0.180 Uiso 1 1 calc R U . . .
H18B H 0.9815 0.0184 0.6417 0.180 Uiso 1 1 calc R U . . .
H18C H 0.9732 0.1502 0.6705 0.180 Uiso 1 1 calc R U . . .
C19 C 0.8343(4) 0.0630(6) 0.6355(3) 0.094(2) Uani 1 1 d . . . . .
H19A H 0.8361 0.1016 0.6752 0.141 Uiso 1 1 calc R U . . .
H19B H 0.8438 -0.0239 0.6402 0.141 Uiso 1 1 calc R U . . .
H19C H 0.7853 0.0755 0.6153 0.141 Uiso 1 1 calc R U . . .
C20 C 0.8990(4) 0.0464(6) 0.5362(4) 0.096(2) Uani 1 1 d . . . . .
H20A H 0.8510 0.0503 0.5134 0.144 Uiso 1 1 calc R U . . .
H20B H 0.9112 -0.0382 0.5455 0.144 Uiso 1 1 calc R U . . .
H20C H 0.9373 0.0813 0.5120 0.144 Uiso 1 1 calc R U . . .
C21 C 0.4983(4) 0.1360(7) 0.7409(3) 0.080(2) Uani 1 1 d . . . . .
H21 H 0.4886 0.1781 0.7768 0.097 Uiso 1 1 calc R U . . .
C22 C 0.4663(4) 0.0276(7) 0.7271(3) 0.078(2) Uani 1 1 d . . . . .
H22 H 0.4333 -0.0146 0.7514 0.093 Uiso 1 1 calc R U . C 1
C23 C 0.4922(10) -0.0162(15) 0.6655(8) 0.050(5) Uani 1 1 d . U . D 1
H23 H 0.4784 -0.0887 0.6447 0.060 Uiso 1 1 calc R U . D 1
S2A S 0.4867(8) -0.0372(12) 0.6674(6) 0.041(3) Uani 0.315(4) 1 d . U P D 2
S2 S 0.55163(15) 0.1880(2) 0.69500(11) 0.0724(11) Uani 0.685(4) 1 d . . P D .
C24 C 0.5437(3) 0.0806(5) 0.6456(2) 0.0415(14) Uani 1 1 d . . . . .
C25 C 0.5832(3) 0.0773(5) 0.5890(2) 0.0407(13) Uani 1 1 d . . . . .
C26 C 0.6264(3) -0.0974(5) 0.4689(2) 0.0466(14) Uani 1 1 d . . . . .
H26 H 0.6010 -0.1684 0.4801 0.056 Uiso 1 1 calc R U . . .
C27 C 0.6677(3) -0.1026(4) 0.4135(2) 0.0415(13) Uani 1 1 d . . . . .
C28 C 0.6720(3) -0.2140(5) 0.3820(2) 0.0471(14) Uani 1 1 d . . . . .
H28 H 0.6475 -0.2831 0.3967 0.057 Uiso 1 1 calc R U . . .
C29 C 0.7111(3) -0.2251(5) 0.3298(2) 0.0486(15) Uani 1 1 d . . . . .
C30 C 0.7446(3) -0.1181(5) 0.3089(2) 0.0461(14) Uani 1 1 d . . . . .
H30 H 0.7707 -0.1238 0.2732 0.055 Uiso 1 1 calc R U . . .
C31 C 0.7423(3) -0.0030(5) 0.3373(2) 0.0401(13) Uani 1 1 d . . . . .
C32 C 0.7025(3) 0.0029(5) 0.3915(2) 0.0365(13) Uani 1 1 d . . . . .
C33 C 0.7192(4) -0.3486(5) 0.2961(3) 0.0580(17) Uani 1 1 d . . . . .
C34 C 0.6534(7) -0.4411(9) 0.3105(6) 0.090(4) Uani 0.686(9) 1 d . U P E 1
H34A H 0.6524 -0.5081 0.2816 0.135 Uiso 0.686(9) 1 calc R U P E 1
H34B H 0.6059 -0.3982 0.3072 0.135 Uiso 0.686(9) 1 calc R U P E 1
H34C H 0.6619 -0.4730 0.3514 0.135 Uiso 0.686(9) 1 calc R U P E 1
C35 C 0.7926(8) -0.4062(12) 0.3104(8) 0.101(5) Uani 0.686(9) 1 d . U P E 1
C36 C 0.7076(7) -0.3305(9) 0.2258(4) 0.084(4) Uani 0.686(9) 1 d . U P E 1
H36A H 0.7468 -0.2782 0.2117 0.126 Uiso 0.686(9) 1 calc R U P E 1
H36B H 0.6593 -0.2928 0.2163 0.126 Uiso 0.686(9) 1 calc R U P E 1
H36C H 0.7095 -0.4094 0.2057 0.126 Uiso 0.686(9) 1 calc R U P E 1
C35A C 0.8011(18) -0.346(2) 0.2703(15) 0.116(9) Uani 0.316(9) 1 d . U P E 2
H35A H 0.8183 -0.4291 0.2645 0.174 Uiso 0.316(9) 1 calc R U P E 2
H35B H 0.8354 -0.3044 0.2991 0.174 Uiso 0.316(9) 1 calc R U P E 2
H35C H 0.7993 -0.3030 0.2317 0.174 Uiso 0.316(9) 1 calc R U P E 2
C34A C 0.658(2) -0.379(3) 0.2654(19) 0.146(11) Uani 0.316(9) 1 d . U P E 2
H34D H 0.6313 -0.4385 0.2883 0.219 Uiso 0.316(9) 1 calc R U P E 2
H34E H 0.6708 -0.4144 0.2269 0.219 Uiso 0.316(9) 1 calc R U P E 2
H34F H 0.6276 -0.3070 0.2581 0.219 Uiso 0.316(9) 1 calc R U P E 2
C36A C 0.7565(17) -0.4436(19) 0.3486(10) 0.083(7) Uani 0.316(9) 1 d . U P E 2
H36D H 0.7192 -0.4645 0.3771 0.125 Uiso 0.316(9) 1 calc R U P E 2
H36E H 0.7987 -0.4042 0.3701 0.125 Uiso 0.316(9) 1 calc R U P E 2
H36F H 0.7733 -0.5174 0.3290 0.125 Uiso 0.316(9) 1 calc R U P E 2
C37 C 0.7787(3) 0.1119(5) 0.3105(3) 0.0570(16) Uani 1 1 d . . . . .
C38 C 0.8183(4) 0.0827(6) 0.2512(3) 0.101(3) Uani 1 1 d . . . . .
H38A H 0.8551 0.0187 0.2592 0.151 Uiso 1 1 calc R U . . .
H38B H 0.8430 0.1557 0.2373 0.151 Uiso 1 1 calc R U . . .
H38C H 0.7816 0.0554 0.2200 0.151 Uiso 1 1 calc R U . . .
C39 C 0.7178(4) 0.2082(6) 0.2936(3) 0.090(2) Uani 1 1 d . . . . .
H39A H 0.6799 0.1723 0.2659 0.135 Uiso 1 1 calc R U . . .
H39B H 0.7404 0.2777 0.2743 0.135 Uiso 1 1 calc R U . . .
H39C H 0.6950 0.2352 0.3302 0.135 Uiso 1 1 calc R U . . .
C40 C 0.8369(4) 0.1663(7) 0.3567(3) 0.100(2) Uani 1 1 d . . . . .
H40A H 0.8122 0.1940 0.3923 0.151 Uiso 1 1 calc R U . . .
H40B H 0.8616 0.2349 0.3384 0.151 Uiso 1 1 calc R U . . .
H40C H 0.8737 0.1043 0.3686 0.151 Uiso 1 1 calc R U . . .
N1 N 0.6115(3) 0.4404(4) 0.45373(19) 0.0473(12) Uani 1 1 d . . . . .
N2 N 0.6745(3) 0.3785(4) 0.48218(18) 0.0418(11) Uani 1 1 d . . . . .
N3 N 0.6223(2) -0.0020(4) 0.50388(19) 0.0416(11) Uani 1 1 d . . . . .
N4 N 0.5805(2) -0.0222(4) 0.5559(2) 0.0483(12) Uani 1 1 d . . . . .
O1 O 0.56971(19) 0.2400(3) 0.45197(15) 0.0478(9) Uani 1 1 d . . . . .
O4 O 0.62040(19) 0.1768(3) 0.57290(14) 0.0452(9) Uani 1 1 d . . . . .
O3 O 0.69826(18) 0.1096(3) 0.42260(15) 0.0451(9) Uani 1 1 d . . . . .
O2 O 0.76026(19) 0.2035(3) 0.52838(15) 0.0474(9) Uani 1 1 d . . . . .
S1 S 0.46994(9) 0.55555(13) 0.40520(7) 0.0572(5) Uani 1 1 d . . . . .
Ti1 Ti 0.66339(5) 0.18184(8) 0.49218(4) 0.0408(4) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C4 1.380(7) . ?
C1 C2 1.423(7) . ?
C1 H1 0.9300 . ?
C2 C3 1.366(7) . ?
C2 H2 0.9300 . ?
C3 S1 1.686(6) . ?
C3 H3 0.9300 . ?
C4 C5 1.453(7) . ?
C4 S1 1.716(5) . ?
C5 N1 1.292(6) . ?
C5 O1 1.321(6) . ?
C6 N2 1.293(6) . ?
C6 C7 1.429(7) . ?
C6 H6 0.9300 . ?
C7 C12 1.400(7) . ?
C7 C8 1.412(7) . ?
C8 C9 1.370(7) . ?
C8 H8 0.9300 . ?
C9 C10 1.404(8) . ?
C9 C13 1.527(8) . ?
C10 C11 1.389(7) . ?
C10 H10 0.9300 . ?
C11 C12 1.410(7) . ?
C11 C17 1.517(8) . ?
C12 O2 1.333(6) . ?
C13 C14 1.45(2) . ?
C13 C16 1.473(11) . ?
C13 C15A 1.480(19) . ?
C13 C14A 1.65(2) . ?
C13 C15 1.660(15) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C15A H15D 0.9600 . ?
C15A H15E 0.9600 . ?
C15A H15F 0.9600 . ?
C14A H14D 0.9600 . ?
C14A H14E 0.9600 . ?
C14A H14F 0.9600 . ?
C17 C19 1.535(9) . ?
C17 C20 1.548(9) . ?
C17 C18 1.563(8) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 C22 1.329(9) . ?
C21 S2 1.522(8) . ?
C21 H21 0.9300 . ?
C22 C23 1.521(18) . ?
C22 S2A 1.540(16) . ?
C22 H22 0.9300 . ?
C23 C24 1.471(16) . ?
C23 H23 0.9300 . ?
S2A C24 1.711(15) . ?
S2 C24 1.584(6) . ?
C24 C25 1.453(7) . ?
C25 N4 1.296(6) . ?
C25 O4 1.321(6) . ?
C26 N3 1.288(6) . ?
C26 C27 1.449(7) . ?
C26 H26 0.9300 . ?
C27 C28 1.392(7) . ?
C27 C32 1.395(7) . ?
C28 C29 1.370(7) . ?
C28 H28 0.9300 . ?
C29 C30 1.390(7) . ?
C29 C33 1.535(7) . ?
C30 C31 1.391(7) . ?
C30 H30 0.9300 . ?
C31 C32 1.410(7) . ?
C31 C37 1.532(7) . ?
C32 O3 1.343(5) . ?
C33 C34A 1.28(3) . ?
C33 C35 1.460(12) . ?
C33 C36 1.548(10) . ?
C33 C34 1.582(12) . ?
C33 C35A 1.59(3) . ?
C33 C36A 1.65(2) . ?
C34 H34A 0.9600 . ?
C34 H34B 0.9600 . ?
C34 H34C 0.9600 . ?
C36 H36A 0.9600 . ?
C36 H36B 0.9600 . ?
C36 H36C 0.9600 . ?
C35A H35A 0.9600 . ?
C35A H35B 0.9600 . ?
C35A H35C 0.9600 . ?
C34A H34D 0.9600 . ?
C34A H34E 0.9600 . ?
C34A H34F 0.9600 . ?
C36A H36D 0.9600 . ?
C36A H36E 0.9600 . ?
C36A H36F 0.9600 . ?
C37 C40 1.519(8) . ?
C37 C39 1.529(8) . ?
C37 C38 1.538(8) . ?
C38 H38A 0.9600 . ?
C38 H38B 0.9600 . ?
C38 H38C 0.9600 . ?
C39 H39A 0.9600 . ?
C39 H39B 0.9600 . ?
C39 H39C 0.9600 . ?
C40 H40A 0.9600 . ?
C40 H40B 0.9600 . ?
C40 H40C 0.9600 . ?
N1 N2 1.414(5) . ?
N2 Ti1 2.149(4) . ?
N3 N4 1.407(6) . ?
N3 Ti1 2.138(4) . ?
O1 Ti1 1.937(3) . ?
O4 Ti1 1.958(3) . ?
O3 Ti1 1.844(3) . ?
O2 Ti1 1.862(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 C1 C2 110.4(5) . . ?
C4 C1 H1 124.8 . . ?
C2 C1 H1 124.8 . . ?
C3 C2 C1 113.0(5) . . ?
C3 C2 H2 123.5 . . ?
C1 C2 H2 123.5 . . ?
C2 C3 S1 112.5(4) . . ?
C2 C3 H3 123.7 . . ?
S1 C3 H3 123.7 . . ?
C1 C4 C5 128.1(5) . . ?
C1 C4 S1 112.4(4) . . ?
C5 C4 S1 119.5(4) . . ?
N1 C5 O1 122.6(5) . . ?
N1 C5 C4 118.8(5) . . ?
O1 C5 C4 118.5(5) . . ?
N2 C6 C7 125.4(5) . . ?
N2 C6 H6 117.3 . . ?
C7 C6 H6 117.3 . . ?
C12 C7 C8 120.9(5) . . ?
C12 C7 C6 121.0(5) . . ?
C8 C7 C6 118.1(5) . . ?
C9 C8 C7 121.3(5) . . ?
C9 C8 H8 119.3 . . ?
C7 C8 H8 119.3 . . ?
C8 C9 C10 116.3(5) . . ?
C8 C9 C13 121.9(6) . . ?
C10 C9 C13 121.7(6) . . ?
C11 C10 C9 125.1(5) . . ?
C11 C10 H10 117.4 . . ?
C9 C10 H10 117.4 . . ?
C10 C11 C12 117.2(5) . . ?
C10 C11 C17 122.3(5) . . ?
C12 C11 C17 120.5(5) . . ?
O2 C12 C7 119.4(5) . . ?
O2 C12 C11 121.5(5) . . ?
C7 C12 C11 119.2(5) . . ?
C14 C13 C16 118.7(12) . . ?
C14 C13 C9 115.4(9) . . ?
C16 C13 C9 111.9(6) . . ?
C15A C13 C9 109.4(8) . . ?
C15A C13 C14A 104.3(12) . . ?
C9 C13 C14A 104.5(8) . . ?
C14 C13 C15 111.0(14) . . ?
C16 C13 C15 89.3(9) . . ?
C9 C13 C15 106.9(7) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C13 C16 H16A 109.5 . . ?
C13 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C13 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C13 C15A H15D 109.5 . . ?
C13 C15A H15E 109.5 . . ?
H15D C15A H15E 109.5 . . ?
C13 C15A H15F 109.5 . . ?
H15D C15A H15F 109.5 . . ?
H15E C15A H15F 109.5 . . ?
C13 C14A H14D 109.5 . . ?
C13 C14A H14E 109.5 . . ?
H14D C14A H14E 109.5 . . ?
C13 C14A H14F 109.5 . . ?
H14D C14A H14F 109.5 . . ?
H14E C14A H14F 109.5 . . ?
C11 C17 C19 110.8(5) . . ?
C11 C17 C20 110.3(5) . . ?
C19 C17 C20 109.2(6) . . ?
C11 C17 C18 112.0(5) . . ?
C19 C17 C18 107.7(6) . . ?
C20 C17 C18 106.7(6) . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C17 C19 H19A 109.5 . . ?
C17 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C17 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C17 C20 H20A 109.5 . . ?
C17 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C17 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C22 C21 S2 116.8(5) . . ?
C22 C21 H21 121.6 . . ?
S2 C21 H21 121.6 . . ?
C21 C22 C23 109.2(8) . . ?
C21 C22 S2A 118.4(7) . . ?
C21 C22 H22 125.4 . . ?
C23 C22 H22 125.4 . . ?
C24 C23 C22 105.1(11) . . ?
C24 C23 H23 127.4 . . ?
C22 C23 H23 127.4 . . ?
C22 S2A C24 93.8(7) . . ?
C21 S2 C24 98.1(4) . . ?
C25 C24 C23 124.7(8) . . ?
C25 C24 S2 124.5(4) . . ?
C23 C24 S2 110.8(8) . . ?
C25 C24 S2A 122.5(6) . . ?
S2 C24 S2A 112.9(5) . . ?
N4 C25 O4 122.1(5) . . ?
N4 C25 C24 119.3(5) . . ?
O4 C25 C24 118.6(5) . . ?
N3 C26 C27 125.0(5) . . ?
N3 C26 H26 117.5 . . ?
C27 C26 H26 117.5 . . ?
C28 C27 C32 120.1(5) . . ?
C28 C27 C26 119.3(5) . . ?
C32 C27 C26 120.6(5) . . ?
C29 C28 C27 121.9(5) . . ?
C29 C28 H28 119.0 . . ?
C27 C28 H28 119.0 . . ?
C28 C29 C30 116.4(5) . . ?
C28 C29 C33 122.6(5) . . ?
C30 C29 C33 121.0(5) . . ?
C29 C30 C31 125.2(5) . . ?
C29 C30 H30 117.4 . . ?
C31 C30 H30 117.4 . . ?
C30 C31 C32 116.2(5) . . ?
C30 C31 C37 122.2(5) . . ?
C32 C31 C37 121.6(5) . . ?
O3 C32 C27 119.3(4) . . ?
O3 C32 C31 120.5(4) . . ?
C27 C32 C31 120.2(5) . . ?
C34A C33 C29 112.0(14) . . ?
C35 C33 C29 112.1(7) . . ?
C35 C33 C36 109.4(9) . . ?
C29 C33 C36 110.7(5) . . ?
C35 C33 C34 110.2(9) . . ?
C29 C33 C34 111.4(6) . . ?
C36 C33 C34 102.6(8) . . ?
C34A C33 C35A 125(2) . . ?
C29 C33 C35A 105.5(10) . . ?
C34A C33 C36A 120(2) . . ?
C29 C33 C36A 104.8(8) . . ?
C35A C33 C36A 85.3(16) . . ?
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 . . ?
C33 C36 H36A 109.5 . . ?
C33 C36 H36B 109.5 . . ?
H36A C36 H36B 109.5 . . ?
C33 C36 H36C 109.5 . . ?
H36A C36 H36C 109.5 . . ?
H36B C36 H36C 109.5 . . ?
C33 C35A H35A 109.5 . . ?
C33 C35A H35B 109.5 . . ?
H35A C35A H35B 109.5 . . ?
C33 C35A H35C 109.5 . . ?
H35A C35A H35C 109.5 . . ?
H35B C35A H35C 109.5 . . ?
C33 C34A H34D 109.5 . . ?
C33 C34A H34E 109.5 . . ?
H34D C34A H34E 109.5 . . ?
C33 C34A H34F 109.5 . . ?
H34D C34A H34F 109.5 . . ?
H34E C34A H34F 109.5 . . ?
C33 C36A H36D 109.5 . . ?
C33 C36A H36E 109.5 . . ?
H36D C36A H36E 109.5 . . ?
C33 C36A H36F 109.5 . . ?
H36D C36A H36F 109.5 . . ?
H36E C36A H36F 109.5 . . ?
C40 C37 C39 109.7(5) . . ?
C40 C37 C31 110.2(5) . . ?
C39 C37 C31 109.8(5) . . ?
C40 C37 C38 108.1(5) . . ?
C39 C37 C38 106.8(5) . . ?
C31 C37 C38 112.1(5) . . ?
C37 C38 H38A 109.5 . . ?
C37 C38 H38B 109.5 . . ?
H38A C38 H38B 109.5 . . ?
C37 C38 H38C 109.5 . . ?
H38A C38 H38C 109.5 . . ?
H38B C38 H38C 109.5 . . ?
C37 C39 H39A 109.5 . . ?
C37 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
C37 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?
C37 C40 H40A 109.5 . . ?
C37 C40 H40B 109.5 . . ?
H40A C40 H40B 109.5 . . ?
C37 C40 H40C 109.5 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
C5 N1 N2 107.8(4) . . ?
C6 N2 N1 114.1(4) . . ?
C6 N2 Ti1 129.7(4) . . ?
N1 N2 Ti1 116.0(3) . . ?
C26 N3 N4 113.8(4) . . ?
C26 N3 Ti1 130.1(4) . . ?
N4 N3 Ti1 116.1(3) . . ?
C25 N4 N3 108.4(4) . . ?
C5 O1 Ti1 120.1(3) . . ?
C25 O4 Ti1 119.2(3) . . ?
C32 O3 Ti1 144.2(3) . . ?
C12 O2 Ti1 143.7(3) . . ?
C3 S1 C4 91.6(3) . . ?
O3 Ti1 O2 93.31(15) . . ?
O3 Ti1 O1 94.84(14) . . ?
O2 Ti1 O1 153.62(15) . . ?
O3 Ti1 O4 153.30(15) . . ?
O2 Ti1 O4 91.12(14) . . ?
O1 Ti1 O4 92.75(14) . . ?
O3 Ti1 N3 80.57(15) . . ?
O2 Ti1 N3 112.25(15) . . ?
O1 Ti1 N3 93.84(15) . . ?
O4 Ti1 N3 73.39(15) . . ?
O3 Ti1 N2 107.42(15) . . ?
O2 Ti1 N2 80.24(15) . . ?
O1 Ti1 N2 73.38(16) . . ?
O4 Ti1 N2 99.28(15) . . ?
N3 Ti1 N2 165.20(17) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 C1 C2 C3 0.2(6) . . . . ?
C1 C2 C3 S1 -0.3(6) . . . . ?
C2 C1 C4 C5 177.7(5) . . . . ?
C2 C1 C4 S1 0.0(5) . . . . ?
C1 C4 C5 N1 -178.2(5) . . . . ?
S1 C4 C5 N1 -0.6(6) . . . . ?
C1 C4 C5 O1 -1.1(7) . . . . ?
S1 C4 C5 O1 176.5(3) . . . . ?
N2 C6 C7 C12 1.5(8) . . . . ?
N2 C6 C7 C8 -176.7(5) . . . . ?
C12 C7 C8 C9 -0.1(8) . . . . ?
C6 C7 C8 C9 178.1(5) . . . . ?
C7 C8 C9 C10 1.5(8) . . . . ?
C7 C8 C9 C13 178.1(6) . . . . ?
C8 C9 C10 C11 -2.1(9) . . . . ?
C13 C9 C10 C11 -178.7(6) . . . . ?
C9 C10 C11 C12 1.2(9) . . . . ?
C9 C10 C11 C17 -179.4(6) . . . . ?
C8 C7 C12 O2 179.2(4) . . . . ?
C6 C7 C12 O2 1.0(7) . . . . ?
C8 C7 C12 C11 -0.8(8) . . . . ?
C6 C7 C12 C11 -179.0(5) . . . . ?
C10 C11 C12 O2 -179.7(5) . . . . ?
C17 C11 C12 O2 0.9(8) . . . . ?
C10 C11 C12 C7 0.3(7) . . . . ?
C17 C11 C12 C7 -179.1(5) . . . . ?
C8 C9 C13 C14 5.4(19) . . . . ?
C10 C9 C13 C14 -178.1(17) . . . . ?
C8 C9 C13 C16 145.3(8) . . . . ?
C10 C9 C13 C16 -38.3(11) . . . . ?
C8 C9 C13 C15A -55.2(15) . . . . ?
C10 C9 C13 C15A 121.3(14) . . . . ?
C8 C9 C13 C14A 56.0(11) . . . . ?
C10 C9 C13 C14A -127.6(10) . . . . ?
C8 C9 C13 C15 -118.5(9) . . . . ?
C10 C9 C13 C15 57.9(10) . . . . ?
C10 C11 C17 C19 118.8(6) . . . . ?
C12 C11 C17 C19 -61.9(7) . . . . ?
C10 C11 C17 C20 -120.2(6) . . . . ?
C12 C11 C17 C20 59.2(7) . . . . ?
C10 C11 C17 C18 -1.5(8) . . . . ?
C12 C11 C17 C18 177.8(6) . . . . ?
S2 C21 C22 C23 -0.9(10) . . . . ?
S2 C21 C22 S2A 1.3(10) . . . . ?
C21 C22 C23 C24 0.3(12) . . . . ?
C21 C22 S2A C24 -2.6(10) . . . . ?
C22 C21 S2 C24 1.0(6) . . . . ?
C22 C23 C24 C25 179.2(6) . . . . ?
C22 C23 C24 S2 0.3(11) . . . . ?
C21 S2 C24 C25 -179.6(5) . . . . ?
C21 S2 C24 C23 -0.7(8) . . . . ?
C21 S2 C24 S2A -2.7(6) . . . . ?
C22 S2A C24 C25 -179.9(5) . . . . ?
C22 S2A C24 S2 3.2(8) . . . . ?
C23 C24 C25 N4 -7.9(10) . . . . ?
S2 C24 C25 N4 170.8(4) . . . . ?
S2A C24 C25 N4 -5.8(9) . . . . ?
C23 C24 C25 O4 171.8(9) . . . . ?
S2 C24 C25 O4 -9.5(7) . . . . ?
S2A C24 C25 O4 173.8(7) . . . . ?
N3 C26 C27 C28 175.7(5) . . . . ?
N3 C26 C27 C32 -4.7(8) . . . . ?
C32 C27 C28 C29 1.3(8) . . . . ?
C26 C27 C28 C29 -179.1(5) . . . . ?
C27 C28 C29 C30 -1.8(8) . . . . ?
C27 C28 C29 C33 177.2(5) . . . . ?
C28 C29 C30 C31 1.0(8) . . . . ?
C33 C29 C30 C31 -178.0(5) . . . . ?
C29 C30 C31 C32 0.1(8) . . . . ?
C29 C30 C31 C37 -178.1(5) . . . . ?
C28 C27 C32 O3 -179.6(4) . . . . ?
C26 C27 C32 O3 0.8(7) . . . . ?
C28 C27 C32 C31 -0.1(7) . . . . ?
C26 C27 C32 C31 -179.7(4) . . . . ?
C30 C31 C32 O3 178.9(4) . . . . ?
C37 C31 C32 O3 -2.8(7) . . . . ?
C30 C31 C32 C27 -0.6(7) . . . . ?
C37 C31 C32 C27 177.6(4) . . . . ?
C28 C29 C33 C34A 75(2) . . . . ?
C30 C29 C33 C34A -106(2) . . . . ?
C28 C29 C33 C35 -100.6(10) . . . . ?
C30 C29 C33 C35 78.3(10) . . . . ?
C28 C29 C33 C36 136.9(7) . . . . ?
C30 C29 C33 C36 -44.1(9) . . . . ?
C28 C29 C33 C34 23.5(9) . . . . ?
C30 C29 C33 C34 -157.6(7) . . . . ?
C28 C29 C33 C35A -145.0(15) . . . . ?
C30 C29 C33 C35A 33.9(15) . . . . ?
C28 C29 C33 C36A -55.8(13) . . . . ?
C30 C29 C33 C36A 123.1(12) . . . . ?
C30 C31 C37 C40 -122.0(6) . . . . ?
C32 C31 C37 C40 59.9(7) . . . . ?
C30 C31 C37 C39 117.0(6) . . . . ?
C32 C31 C37 C39 -61.1(7) . . . . ?
C30 C31 C37 C38 -1.5(8) . . . . ?
C32 C31 C37 C38 -179.6(5) . . . . ?
O1 C5 N1 N2 -2.3(6) . . . . ?
C4 C5 N1 N2 174.7(4) . . . . ?
C7 C6 N2 N1 176.2(5) . . . . ?
C7 C6 N2 Ti1 1.9(7) . . . . ?
C5 N1 N2 C6 -174.2(4) . . . . ?
C5 N1 N2 Ti1 0.9(5) . . . . ?
C27 C26 N3 N4 -178.2(4) . . . . ?
C27 C26 N3 Ti1 5.6(8) . . . . ?
O4 C25 N4 N3 0.0(6) . . . . ?
C24 C25 N4 N3 179.6(4) . . . . ?
C26 N3 N4 C25 177.0(4) . . . . ?
Ti1 N3 N4 C25 -6.3(5) . . . . ?
N1 C5 O1 Ti1 2.8(6) . . . . ?
C4 C5 O1 Ti1 -174.2(3) . . . . ?
N4 C25 O4 Ti1 7.1(6) . . . . ?
C24 C25 O4 Ti1 -172.5(3) . . . . ?
C27 C32 O3 Ti1 3.0(8) . . . . ?
C31 C32 O3 Ti1 -176.5(4) . . . . ?
C7 C12 O2 Ti1 -9.8(8) . . . . ?
C11 C12 O2 Ti1 170.1(4) . . . . ?
C2 C3 S1 C4 0.3(4) . . . . ?
C1 C4 S1 C3 -0.2(4) . . . . ?
C5 C4 S1 C3 -178.1(4) . . . . ?
C32 O3 Ti1 O2 109.8(5) . . . . ?
C32 O3 Ti1 O1 -95.3(5) . . . . ?
C32 O3 Ti1 O4 10.7(7) . . . . ?
C32 O3 Ti1 N3 -2.2(5) . . . . ?
C32 O3 Ti1 N2 -169.4(5) . . . . ?
C12 O2 Ti1 O3 117.3(5) . . . . ?
C12 O2 Ti1 O1 9.4(7) . . . . ?
C12 O2 Ti1 O4 -89.0(5) . . . . ?
C12 O2 Ti1 N3 -161.5(5) . . . . ?
C12 O2 Ti1 N2 10.2(5) . . . . ?

_refine_diff_density_max         0.374
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.084

# start Validation Reply Form
_vrf_THETM01_tbu                 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Even though crystal data was collected up to 0.78 \%A 
resolution, the crystal (the largest available) still 
diffracted quite weakly at high angle. 
;
_vrf_PLAT213_tbu                 
;
PROBLEM: Atom C34A            has ADP max/min Ratio .....        5.1 oblate
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C34 and C35 carbon atoms are disordered between two orientations. 

;
_vrf_PLAT412_tbu                 
;
PROBLEM: Short Intra XH3 .. XHn     H16C   ..  H14F    ..       1.53 Ang.  
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C14 and C16 carbon atoms are disordered between two orientations.
;
# end Validation Reply Form  
####################################################################### 
# 
# 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_Complex_2
_database_code_depnum_ccdc_archive 'CCDC 1562818'
_audit_update_record             
;
2017-07-18 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C34 H36 N4 O4 S2 Ti'
_chemical_formula_sum            'C34 H36 N4 O4 S2 Ti'
_chemical_formula_weight         676.69

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      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                   13.081(4)
_cell_length_b                   23.840(8)
_cell_length_c                   15.426(5)
_cell_angle_alpha                90
_cell_angle_beta                 101.148(12)
_cell_angle_gamma                90
_cell_volume                     4720(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    7301
_cell_measurement_theta_min      2.17
_cell_measurement_theta_max      21.08

_exptl_crystal_description       Block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.952
_exptl_crystal_F_000             1416
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.160
_exptl_absorpt_coefficient_mu    0.301
_shelx_estimated_absorpt_T_min   0.929
_shelx_estimated_absorpt_T_max   0.953
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.929
_exptl_absorpt_correction_T_max  0.953
_exptl_absorpt_process_details   'SADABS V2014/5(Bruker AXS.Inc)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            13883
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         1.594
_diffrn_reflns_theta_max         21.139
_diffrn_reflns_theta_full        21.139
_diffrn_measured_fraction_theta_max 0.894
_diffrn_measured_fraction_theta_full 0.894
_diffrn_reflns_Laue_measured_fraction_max 0.894
_diffrn_reflns_Laue_measured_fraction_full 0.894
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_point_group_measured_fraction_full 0.894
_reflns_number_total             4625
_reflns_number_gt                3395
_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. 


A small region of electron density well removed from the main 
molecule was removed with the SQUEEZE procedure in PLATON 
[Spek (2009). Acta Cryst. D65, 148-155] following unsuccessful 
attempts to model it as a plausible solvent molecule. 
The unit-cell characteristics do not take into account 
this feature of the structure.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0843P)²+2.5851P] 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         4625
_refine_ls_number_parameters     424
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0585
_refine_ls_wR_factor_ref         0.1676
_refine_ls_wR_factor_gt          0.1552
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_restrained_S_all      1.111
_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
C1 C 0.8282(4) 0.5132(2) 0.2790(3) 0.0725(15) Uani 1 1 d . . . . .
H1 H 0.8600 0.4871 0.3202 0.087 Uiso 1 1 calc R U . . .
C2 C 0.8681(6) 0.5677(3) 0.2659(5) 0.110(2) Uani 1 1 d . . . . .
H2 H 0.9303 0.5812 0.2988 0.131 Uiso 1 1 calc R U . . .
C3 C 0.8081(6) 0.5974(3) 0.2019(5) 0.100(2) Uani 1 1 d . . . . .
H3 H 0.8250 0.6332 0.1854 0.120 Uiso 1 1 calc R U . . .
C4 C 0.7336(4) 0.5056(2) 0.2200(3) 0.0597(13) Uani 1 1 d . . . . .
C5 C 0.6620(4) 0.45615(19) 0.2157(3) 0.0515(12) Uani 1 1 d . . . . .
C6 C 0.4325(4) 0.4011(2) 0.1150(3) 0.0617(13) Uani 1 1 d . . . . .
H6 H 0.4146 0.4284 0.0716 0.074 Uiso 1 1 calc R U . . .
C7 C 0.3580(4) 0.3562(2) 0.1166(3) 0.0548(13) Uani 1 1 d . . . . .
C8 C 0.2615(4) 0.3588(3) 0.0589(3) 0.0753(16) Uani 1 1 d . . . . .
H8 H 0.2471 0.3884 0.0192 0.090 Uiso 1 1 calc R U . . .
C9 C 0.1871(4) 0.3175(3) 0.0604(3) 0.0755(16) Uani 1 1 d . . . . .
C10 C 0.2123(4) 0.2729(2) 0.1203(3) 0.0689(15) Uani 1 1 d . . . . .
H10 H 0.1621 0.2454 0.1209 0.083 Uiso 1 1 calc R U . . .
C11 C 0.3078(4) 0.2670(2) 0.1793(3) 0.0558(13) Uani 1 1 d . . . . .
C12 C 0.3815(4) 0.3105(2) 0.1772(3) 0.0500(12) Uani 1 1 d . . . . .
C13 C 0.3309(4) 0.2174(2) 0.2433(3) 0.0647(14) Uani 1 1 d . . . . .
C14 C 0.2416(5) 0.1741(3) 0.2303(4) 0.099(2) Uani 1 1 d . . . . .
H14A H 0.1792 0.1917 0.2410 0.148 Uiso 1 1 calc R U . . .
H14B H 0.2601 0.1436 0.2709 0.148 Uiso 1 1 calc R U . . .
H14C H 0.2300 0.1601 0.1709 0.148 Uiso 1 1 calc R U . . .
C15 C 0.4305(5) 0.1857(2) 0.2307(4) 0.0936(19) Uani 1 1 d . . . . .
H15A H 0.4388 0.1525 0.2666 0.140 Uiso 1 1 calc R U . . .
H15B H 0.4901 0.2095 0.2479 0.140 Uiso 1 1 calc R U . . .
H15C H 0.4242 0.1754 0.1697 0.140 Uiso 1 1 calc R U . . .
C16 C 0.3444(5) 0.2396(3) 0.3397(3) 0.0858(18) Uani 1 1 d . . . . .
H16A H 0.2806 0.2566 0.3483 0.129 Uiso 1 1 calc R U . . .
H16B H 0.3993 0.2670 0.3501 0.129 Uiso 1 1 calc R U . . .
H16C H 0.3618 0.2090 0.3803 0.129 Uiso 1 1 calc R U . . .
C17 C 0.0826(5) 0.3193(3) -0.0020(4) 0.117(2) Uani 1 1 d . . . . .
H17A H 0.0303 0.3321 0.0293 0.176 Uiso 1 1 calc R U . . .
H17B H 0.0649 0.2825 -0.0252 0.176 Uiso 1 1 calc R U . . .
H17C H 0.0862 0.3446 -0.0498 0.176 Uiso 1 1 calc R U . . .
C18 C 0.4002(9) 0.4450(5) 0.4902(6) 0.063(4) Uani 1 1 d . U . A 1
H18 H 0.3589 0.4479 0.4341 0.076 Uiso 1 1 calc R U . A 1
S2A S 0.3738(12) 0.4479(9) 0.4611(9) 0.051(4) Uani 0.177(4) 1 d . U P A 2
C19 C 0.4470(5) 0.4572(3) 0.6380(4) 0.0891(19) Uani 1 1 d . . . . .
H19 H 0.4432 0.4694 0.6945 0.107 Uiso 1 1 calc R U . . .
C20 C 0.3744(5) 0.4694(2) 0.5682(4) 0.0813(17) Uani 1 1 d . . . . .
H20 H 0.3151 0.4907 0.5695 0.098 Uiso 1 1 calc R U . A 1
C21 C 0.4959(4) 0.41609(19) 0.5089(3) 0.0524(12) Uani 1 1 d . . . . .
C22 C 0.5515(4) 0.38526(18) 0.4478(3) 0.0506(12) Uani 1 1 d . . . . .
C23 C 0.7491(4) 0.2978(2) 0.4324(3) 0.0530(12) Uani 1 1 d . . . . .
H23 H 0.7767 0.2949 0.4925 0.064 Uiso 1 1 calc R U . . .
C24 C 0.7994(3) 0.2660(2) 0.3730(3) 0.0515(12) Uani 1 1 d . . . . .
C25 C 0.8849(4) 0.2318(2) 0.4083(3) 0.0641(14) Uani 1 1 d . . . . .
H25 H 0.9070 0.2300 0.4693 0.077 Uiso 1 1 calc R U . . .
C26 C 0.9370(4) 0.2007(2) 0.3547(3) 0.0650(14) Uani 1 1 d . . . . .
C27 C 0.8994(4) 0.2043(2) 0.2641(3) 0.0632(13) Uani 1 1 d . . . . .
H27 H 0.9334 0.1831 0.2277 0.076 Uiso 1 1 calc R U . . .
C28 C 0.8155(4) 0.23681(19) 0.2233(3) 0.0531(12) Uani 1 1 d . . . . .
C29 C 0.7637(3) 0.26838(19) 0.2803(3) 0.0469(11) Uani 1 1 d . . . . .
C30 C 0.7784(4) 0.2395(2) 0.1215(3) 0.0687(14) Uani 1 1 d . . . . .
C31 C 0.6644(5) 0.2202(3) 0.0955(3) 0.0923(19) Uani 1 1 d . . . . .
H31A H 0.6438 0.2200 0.0323 0.138 Uiso 1 1 calc R U . . .
H31B H 0.6205 0.2455 0.1201 0.138 Uiso 1 1 calc R U . . .
H31C H 0.6576 0.1831 0.1179 0.138 Uiso 1 1 calc R U . . .
C32 C 0.7881(5) 0.3004(3) 0.0894(3) 0.0909(18) Uani 1 1 d . . . . .
H32A H 0.8598 0.3118 0.1030 0.136 Uiso 1 1 calc R U . . .
H32B H 0.7473 0.3249 0.1186 0.136 Uiso 1 1 calc R U . . .
H32C H 0.7633 0.3023 0.0267 0.136 Uiso 1 1 calc R U . . .
C33 C 0.8441(6) 0.2017(3) 0.0743(4) 0.114(2) Uani 1 1 d . . . . .
H33A H 0.9163 0.2113 0.0925 0.171 Uiso 1 1 calc R U . . .
H33B H 0.8236 0.2067 0.0116 0.171 Uiso 1 1 calc R U . . .
H33C H 0.8337 0.1632 0.0890 0.171 Uiso 1 1 calc R U . . .
C34 C 1.0288(4) 0.1628(3) 0.3936(4) 0.0931(19) Uani 1 1 d . . . . .
H34A H 1.0355 0.1336 0.3523 0.140 Uiso 1 1 calc R U . . .
H34B H 1.0170 0.1465 0.4477 0.140 Uiso 1 1 calc R U . . .
H34C H 1.0917 0.1846 0.4052 0.140 Uiso 1 1 calc R U . . .
N1 N 0.5777(3) 0.45488(17) 0.1545(3) 0.0611(11) Uani 1 1 d . . . . .
N2 N 0.5216(3) 0.40678(16) 0.1681(2) 0.0562(10) Uani 1 1 d . . . . .
N3 N 0.6325(3) 0.35581(16) 0.4796(2) 0.0558(10) Uani 1 1 d . . . . .
N4 N 0.6681(3) 0.33016(16) 0.4089(2) 0.0498(10) Uani 1 1 d . . . . .
O1 O 0.6876(2) 0.41609(13) 0.27495(19) 0.0584(8) Uani 1 1 d . . . . .
O2 O 0.4742(2) 0.30907(12) 0.23232(19) 0.0556(8) Uani 1 1 d . . . . .
O3 O 0.5137(2) 0.38954(13) 0.36085(19) 0.0557(8) Uani 1 1 d . . . . .
O4 O 0.6814(2) 0.30072(13) 0.24835(16) 0.0507(8) Uani 1 1 d . . . . .
S1 S 0.69884(15) 0.56321(7) 0.15432(11) 0.1034(6) Uani 1 1 d . . . . .
S2 S 0.54521(15) 0.41872(8) 0.61764(11) 0.0839(8) Uani 0.823(4) 1 d . . P A .
Ti1 Ti 0.58936(6) 0.35379(3) 0.27822(5) 0.0487(3) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C4 1.399(7) . ?
C1 C2 1.428(8) . ?
C1 H1 0.9300 . ?
C2 C3 1.340(9) . ?
C2 H2 0.9300 . ?
C3 S1 1.686(7) . ?
C3 H3 0.9300 . ?
C4 C5 1.498(7) . ?
C4 S1 1.716(5) . ?
C5 N1 1.306(6) . ?
C5 O1 1.320(5) . ?
C6 N2 1.296(6) . ?
C6 C7 1.451(7) . ?
C6 H6 0.9300 . ?
C7 C8 1.397(6) . ?
C7 C12 1.429(6) . ?
C8 C9 1.387(7) . ?
C8 H8 0.9300 . ?
C9 C10 1.406(7) . ?
C9 C17 1.513(7) . ?
C10 C11 1.403(6) . ?
C10 H10 0.9300 . ?
C11 C12 1.421(6) . ?
C11 C13 1.533(7) . ?
C12 O2 1.340(5) . ?
C13 C14 1.542(7) . ?
C13 C15 1.552(7) . ?
C13 C16 1.556(6) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 C21 1.408(11) . ?
C18 C20 1.434(11) . ?
C18 H18 0.9300 . ?
S2A C20 1.728(15) . ?
S2A C21 1.792(14) . ?
C19 C20 1.323(8) . ?
C19 S2 1.657(6) . ?
C19 H19 0.9300 . ?
C20 H20 0.9300 . ?
C21 C22 1.491(6) . ?
C21 S2 1.678(5) . ?
C22 N3 1.287(5) . ?
C22 O3 1.341(5) . ?
C23 N4 1.305(5) . ?
C23 C24 1.441(6) . ?
C23 H23 0.9300 . ?
C24 C25 1.407(6) . ?
C24 C29 1.416(6) . ?
C25 C26 1.384(6) . ?
C25 H25 0.9300 . ?
C26 C27 1.392(6) . ?
C26 C34 1.530(7) . ?
C27 C28 1.391(6) . ?
C27 H27 0.9300 . ?
C28 C29 1.425(6) . ?
C28 C30 1.552(6) . ?
C29 O4 1.339(5) . ?
C30 C33 1.524(7) . ?
C30 C31 1.538(7) . ?
C30 C32 1.547(8) . ?
C31 H31A 0.9600 . ?
C31 H31B 0.9600 . ?
C31 H31C 0.9600 . ?
C32 H32A 0.9600 . ?
C32 H32B 0.9600 . ?
C32 H32C 0.9600 . ?
C33 H33A 0.9600 . ?
C33 H33B 0.9600 . ?
C33 H33C 0.9600 . ?
C34 H34A 0.9600 . ?
C34 H34B 0.9600 . ?
C34 H34C 0.9600 . ?
N1 N2 1.400(5) . ?
N2 Ti1 2.164(4) . ?
N3 N4 1.406(5) . ?
N4 Ti1 2.154(4) . ?
O1 Ti1 1.971(3) . ?
O2 Ti1 1.870(3) . ?
O3 Ti1 1.954(3) . ?
O4 Ti1 1.865(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 C1 C2 109.2(5) . . ?
C4 C1 H1 125.4 . . ?
C2 C1 H1 125.4 . . ?
C3 C2 C1 114.1(6) . . ?
C3 C2 H2 123.0 . . ?
C1 C2 H2 123.0 . . ?
C2 C3 S1 113.0(5) . . ?
C2 C3 H3 123.5 . . ?
S1 C3 H3 123.5 . . ?
C1 C4 C5 126.8(5) . . ?
C1 C4 S1 112.3(4) . . ?
C5 C4 S1 120.7(4) . . ?
N1 C5 O1 123.4(4) . . ?
N1 C5 C4 118.9(4) . . ?
O1 C5 C4 117.7(5) . . ?
N2 C6 C7 126.3(4) . . ?
N2 C6 H6 116.9 . . ?
C7 C6 H6 116.9 . . ?
C8 C7 C12 120.2(5) . . ?
C8 C7 C6 118.9(5) . . ?
C12 C7 C6 120.8(4) . . ?
C9 C8 C7 120.6(5) . . ?
C9 C8 H8 119.7 . . ?
C7 C8 H8 119.7 . . ?
C8 C9 C10 118.1(5) . . ?
C8 C9 C17 121.4(6) . . ?
C10 C9 C17 120.5(5) . . ?
C11 C10 C9 124.6(5) . . ?
C11 C10 H10 117.7 . . ?
C9 C10 H10 117.7 . . ?
C10 C11 C12 115.8(5) . . ?
C10 C11 C13 122.3(4) . . ?
C12 C11 C13 121.8(4) . . ?
O2 C12 C11 120.1(4) . . ?
O2 C12 C7 119.3(4) . . ?
C11 C12 C7 120.6(4) . . ?
C11 C13 C14 112.5(4) . . ?
C11 C13 C15 111.2(4) . . ?
C14 C13 C15 106.9(5) . . ?
C11 C13 C16 109.0(4) . . ?
C14 C13 C16 107.2(4) . . ?
C15 C13 C16 110.1(4) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C13 C16 H16A 109.5 . . ?
C13 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C13 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C9 C17 H17A 109.5 . . ?
C9 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C9 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C21 C18 C20 111.8(6) . . ?
C21 C18 H18 124.1 . . ?
C20 C18 H18 124.1 . . ?
C20 S2A C21 83.9(7) . . ?
C20 C19 S2 115.4(4) . . ?
C20 C19 H19 122.3 . . ?
S2 C19 H19 122.3 . . ?
C19 C20 C18 110.2(6) . . ?
C19 C20 S2A 125.6(6) . . ?
C19 C20 H20 124.9 . . ?
C18 C20 H20 124.9 . . ?
C18 C21 C22 129.4(5) . . ?
C18 C21 S2 109.9(5) . . ?
C22 C21 S2 120.6(4) . . ?
C22 C21 S2A 117.0(5) . . ?
S2 C21 S2A 122.4(5) . . ?
N3 C22 O3 122.7(4) . . ?
N3 C22 C21 119.7(4) . . ?
O3 C22 C21 117.7(4) . . ?
N4 C23 C24 125.4(4) . . ?
N4 C23 H23 117.3 . . ?
C24 C23 H23 117.3 . . ?
C25 C24 C29 119.7(4) . . ?
C25 C24 C23 119.0(4) . . ?
C29 C24 C23 121.3(4) . . ?
C26 C25 C24 121.7(4) . . ?
C26 C25 H25 119.1 . . ?
C24 C25 H25 119.1 . . ?
C25 C26 C27 116.7(4) . . ?
C25 C26 C34 121.5(4) . . ?
C27 C26 C34 121.8(5) . . ?
C28 C27 C26 125.7(4) . . ?
C28 C27 H27 117.2 . . ?
C26 C27 H27 117.2 . . ?
C27 C28 C29 116.3(4) . . ?
C27 C28 C30 123.1(4) . . ?
C29 C28 C30 120.7(4) . . ?
O4 C29 C24 118.6(4) . . ?
O4 C29 C28 121.4(4) . . ?
C24 C29 C28 120.0(4) . . ?
C33 C30 C31 107.9(5) . . ?
C33 C30 C32 108.3(4) . . ?
C31 C30 C32 109.4(5) . . ?
C33 C30 C28 111.4(4) . . ?
C31 C30 C28 110.4(4) . . ?
C32 C30 C28 109.5(4) . . ?
C30 C31 H31A 109.5 . . ?
C30 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
C30 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
C30 C32 H32A 109.5 . . ?
C30 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
C30 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
C30 C33 H33A 109.5 . . ?
C30 C33 H33B 109.5 . . ?
H33A C33 H33B 109.5 . . ?
C30 C33 H33C 109.5 . . ?
H33A C33 H33C 109.5 . . ?
H33B C33 H33C 109.5 . . ?
C26 C34 H34A 109.5 . . ?
C26 C34 H34B 109.5 . . ?
H34A C34 H34B 109.5 . . ?
C26 C34 H34C 109.5 . . ?
H34A C34 H34C 109.5 . . ?
H34B C34 H34C 109.5 . . ?
C5 N1 N2 107.7(4) . . ?
C6 N2 N1 115.1(4) . . ?
C6 N2 Ti1 128.1(3) . . ?
N1 N2 Ti1 116.7(3) . . ?
C22 N3 N4 108.3(3) . . ?
C23 N4 N3 114.5(3) . . ?
C23 N4 Ti1 129.1(3) . . ?
N3 N4 Ti1 116.2(3) . . ?
C5 O1 Ti1 118.9(3) . . ?
C12 O2 Ti1 142.1(3) . . ?
C22 O3 Ti1 119.0(3) . . ?
C29 O4 Ti1 144.2(2) . . ?
C3 S1 C4 91.4(3) . . ?
C19 S2 C21 92.7(3) . . ?
O4 Ti1 O2 91.76(13) . . ?
O4 Ti1 O3 152.84(13) . . ?
O2 Ti1 O3 91.33(13) . . ?
O4 Ti1 O1 92.85(13) . . ?
O2 Ti1 O1 154.38(13) . . ?
O3 Ti1 O1 95.91(13) . . ?
O4 Ti1 N4 80.73(13) . . ?
O2 Ti1 N4 114.20(13) . . ?
O3 Ti1 N4 73.42(13) . . ?
O1 Ti1 N4 91.42(13) . . ?
O4 Ti1 N2 112.84(13) . . ?
O2 Ti1 N2 81.83(15) . . ?
O3 Ti1 N2 94.30(13) . . ?
O1 Ti1 N2 73.16(14) . . ?
N4 Ti1 N2 159.45(15) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 C1 C2 C3 -0.5(8) . . . . ?
C1 C2 C3 S1 1.2(8) . . . . ?
C2 C1 C4 C5 -175.4(5) . . . . ?
C2 C1 C4 S1 -0.4(6) . . . . ?
C1 C4 C5 N1 -178.0(4) . . . . ?
S1 C4 C5 N1 7.4(5) . . . . ?
C1 C4 C5 O1 2.5(6) . . . . ?
S1 C4 C5 O1 -172.2(3) . . . . ?
N2 C6 C7 C8 174.9(4) . . . . ?
N2 C6 C7 C12 -4.0(7) . . . . ?
C12 C7 C8 C9 0.8(7) . . . . ?
C6 C7 C8 C9 -178.1(5) . . . . ?
C7 C8 C9 C10 -1.0(8) . . . . ?
C7 C8 C9 C17 -179.6(5) . . . . ?
C8 C9 C10 C11 0.1(8) . . . . ?
C17 C9 C10 C11 178.7(5) . . . . ?
C9 C10 C11 C12 1.0(7) . . . . ?
C9 C10 C11 C13 179.9(5) . . . . ?
C10 C11 C12 O2 178.7(4) . . . . ?
C13 C11 C12 O2 -0.2(6) . . . . ?
C10 C11 C12 C7 -1.2(6) . . . . ?
C13 C11 C12 C7 179.9(4) . . . . ?
C8 C7 C12 O2 -179.6(4) . . . . ?
C6 C7 C12 O2 -0.7(6) . . . . ?
C8 C7 C12 C11 0.3(6) . . . . ?
C6 C7 C12 C11 179.2(4) . . . . ?
C10 C11 C13 C14 4.0(6) . . . . ?
C12 C11 C13 C14 -177.1(4) . . . . ?
C10 C11 C13 C15 123.8(5) . . . . ?
C12 C11 C13 C15 -57.3(6) . . . . ?
C10 C11 C13 C16 -114.7(5) . . . . ?
C12 C11 C13 C16 64.1(5) . . . . ?
S2 C19 C20 C18 0.2(8) . . . . ?
S2 C19 C20 S2A 0.9(12) . . . . ?
C21 C18 C20 C19 -1.2(11) . . . . ?
C21 S2A C20 C19 -1.7(13) . . . . ?
C20 C18 C21 C22 -179.7(5) . . . . ?
C20 C18 C21 S2 1.6(10) . . . . ?
C20 S2A C21 C22 -179.6(5) . . . . ?
C20 S2A C21 S2 2.1(11) . . . . ?
C18 C21 C22 N3 -171.7(7) . . . . ?
S2 C21 C22 N3 6.9(6) . . . . ?
S2A C21 C22 N3 -171.4(8) . . . . ?
C18 C21 C22 O3 8.1(9) . . . . ?
S2 C21 C22 O3 -173.3(3) . . . . ?
S2A C21 C22 O3 8.4(9) . . . . ?
N4 C23 C24 C25 -178.6(4) . . . . ?
N4 C23 C24 C29 0.8(7) . . . . ?
C29 C24 C25 C26 1.1(7) . . . . ?
C23 C24 C25 C26 -179.5(5) . . . . ?
C24 C25 C26 C27 -1.0(8) . . . . ?
C24 C25 C26 C34 -179.0(5) . . . . ?
C25 C26 C27 C28 0.9(8) . . . . ?
C34 C26 C27 C28 178.9(5) . . . . ?
C26 C27 C28 C29 -0.8(7) . . . . ?
C26 C27 C28 C30 179.2(5) . . . . ?
C25 C24 C29 O4 179.2(4) . . . . ?
C23 C24 C29 O4 -0.2(6) . . . . ?
C25 C24 C29 C28 -1.0(7) . . . . ?
C23 C24 C29 C28 179.6(4) . . . . ?
C27 C28 C29 O4 -179.3(4) . . . . ?
C30 C28 C29 O4 0.7(7) . . . . ?
C27 C28 C29 C24 0.8(6) . . . . ?
C30 C28 C29 C24 -179.2(4) . . . . ?
C27 C28 C30 C33 1.0(7) . . . . ?
C29 C28 C30 C33 -179.0(5) . . . . ?
C27 C28 C30 C31 120.8(5) . . . . ?
C29 C28 C30 C31 -59.2(6) . . . . ?
C27 C28 C30 C32 -118.7(5) . . . . ?
C29 C28 C30 C32 61.3(6) . . . . ?
O1 C5 N1 N2 3.3(5) . . . . ?
C4 C5 N1 N2 -176.2(3) . . . . ?
C7 C6 N2 N1 -178.0(4) . . . . ?
C7 C6 N2 Ti1 -1.4(7) . . . . ?
C5 N1 N2 C6 176.5(4) . . . . ?
C5 N1 N2 Ti1 -0.4(4) . . . . ?
O3 C22 N3 N4 -1.3(6) . . . . ?
C21 C22 N3 N4 178.5(3) . . . . ?
C24 C23 N4 N3 178.9(4) . . . . ?
C24 C23 N4 Ti1 -5.7(7) . . . . ?
C22 N3 N4 C23 -178.4(4) . . . . ?
C22 N3 N4 Ti1 5.6(4) . . . . ?
N1 C5 O1 Ti1 -5.0(5) . . . . ?
C4 C5 O1 Ti1 174.5(3) . . . . ?
C11 C12 O2 Ti1 -164.8(3) . . . . ?
C7 C12 O2 Ti1 15.1(6) . . . . ?
N3 C22 O3 Ti1 -4.1(5) . . . . ?
C21 C22 O3 Ti1 176.1(3) . . . . ?
C24 C29 O4 Ti1 7.0(7) . . . . ?
C28 C29 O4 Ti1 -172.8(3) . . . . ?
C2 C3 S1 C4 -1.2(6) . . . . ?
C1 C4 S1 C3 0.9(4) . . . . ?
C5 C4 S1 C3 176.2(4) . . . . ?
C20 C19 S2 C21 0.6(5) . . . . ?
C18 C21 S2 C19 -1.3(6) . . . . ?
C22 C21 S2 C19 179.9(4) . . . . ?
S2A C21 S2 C19 -1.9(9) . . . . ?
C29 O4 Ti1 O2 -123.0(5) . . . . ?
C29 O4 Ti1 O3 -26.6(6) . . . . ?
C29 O4 Ti1 O1 82.2(5) . . . . ?
C29 O4 Ti1 N4 -8.8(5) . . . . ?
C29 O4 Ti1 N2 155.1(5) . . . . ?
C12 O2 Ti1 O4 -128.8(4) . . . . ?
C12 O2 Ti1 O3 78.2(4) . . . . ?
C12 O2 Ti1 O1 -28.5(6) . . . . ?
C12 O2 Ti1 N4 150.6(4) . . . . ?
C12 O2 Ti1 N2 -16.0(4) . . . . ?

_refine_diff_density_max         0.269
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.048


# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.001 0.500 0.001 836 177 ' '
2 0.499 0.000 0.446 836 177 ' '
_platon_squeeze_details          
;
;

# start Validation Reply Form
_vrf_THETM01_sag                 
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Even though crystal data was collected up to 0.78 \%A 
resolution, the crystal (the largest available) still 
diffracted quite weakly at high angle.  
;
_vrf_PLAT029_sag                 
;
PROBLEM: _diffrn_measured_fraction_theta_full Low .......      0.894 Note  
RESPONSE:  Even though crystal data was collected up to 0.78 \%A 
resolution, the crystal (the largest available) still 
diffracted quite weakly at high angle. 
;
# end Validation Reply Form
####################################################################### 
# 
# 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_Complex_4
_database_code_depnum_ccdc_archive 'CCDC 1562819'
_audit_update_record             
;
2017-07-18 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C40 H48 N4 O4 S2 Zr'
_chemical_formula_sum            'C40 H48 N4 O4 S2 Zr'
_chemical_formula_weight         804.16

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -2.9673 0.5597 '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/c'
_space_group_name_Hall           '-P 2ybc'

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

_cell_length_a                   17.8233(9)
_cell_length_b                   10.9084(6)
_cell_length_c                   21.6049(11)
_cell_angle_alpha                90
_cell_angle_beta                 94.0606(18)
_cell_angle_gamma                90
_cell_volume                     4190.0(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    7991
_cell_measurement_theta_min      2.28
_cell_measurement_theta_max      26.93

_exptl_crystal_description       Rectangular
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_F_000             1680
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.160
_exptl_absorpt_coefficient_mu    0.404
_shelx_estimated_absorpt_T_min   0.906
_shelx_estimated_absorpt_T_max   0.938
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_T_max  0.938
_exptl_absorpt_process_details   'SADABS V2014/5(Bruker AXS.Inc)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            31084
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         1.145
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_full        24.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             7376
_reflns_number_gt                5723
_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0564P)²+1.6152P] 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         7376
_refine_ls_number_parameters     514
_refine_ls_number_restraints     50
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0374
_refine_ls_wR_factor_ref         0.1113
_refine_ls_wR_factor_gt          0.0951
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.091
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.29728(16) 0.5045(2) 0.11276(12) 0.0318(6) Uani 1 1 d . . . . .
C2 C 0.25714(16) 0.5112(3) 0.16623(13) 0.0346(7) Uani 1 1 d . . . . .
C3 C 0.25412(17) 0.6245(3) 0.19478(13) 0.0395(7) Uani 1 1 d . . . . .
H3 H 0.2267 0.6304 0.2297 0.047 Uiso 1 1 calc R U . . .
C4 C 0.28916(17) 0.7307(3) 0.17510(13) 0.0383(7) Uani 1 1 d . . . . .
C5 C 0.32854(17) 0.7206(3) 0.12276(13) 0.0387(7) Uani 1 1 d . . . . .
H5 H 0.3527 0.7893 0.1082 0.046 Uiso 1 1 calc R U . . .
C6 C 0.33306(16) 0.6096(3) 0.09103(13) 0.0337(7) Uani 1 1 d . . . . .
C7 C 0.37368(17) 0.6083(3) 0.03578(13) 0.0390(7) Uani 1 1 d . . . . .
H7 H 0.3979 0.6804 0.0257 0.047 Uiso 1 1 calc R U . . .
C8 C 0.42010(16) 0.4454(3) -0.08846(12) 0.0319(6) Uani 1 1 d . . . . .
C9 C 0.46105(16) 0.4496(3) -0.14477(12) 0.0356(7) Uani 1 1 d D . . . .
C10 C 0.5075(4) 0.5429(5) -0.1633(4) 0.048(2) Uani 1 1 d D U . A 1
H10 H 0.5178 0.6159 -0.1421 0.058 Uiso 1 1 calc R U . A 1
S1A S 0.5160(4) 0.5679(6) -0.1651(3) 0.0318(12) Uani 0.254(3) 1 d . U P A 2
S1 S 0.45708(8) 0.33540(11) -0.19447(5) 0.0586(5) Uani 0.746(3) 1 d . . P A .
C11 C 0.5383(2) 0.5057(4) -0.22341(17) 0.0655(11) Uani 1 1 d . . . . .
H11 H 0.5709 0.5524 -0.2455 0.079 Uiso 1 1 calc R U . A 1
C12 C 0.5121(2) 0.3970(4) -0.24004(16) 0.0698(12) Uani 1 1 d . . . . .
H12 H 0.5251 0.3587 -0.2762 0.084 Uiso 1 1 calc R U . A .
C13 C 0.21778(19) 0.3987(3) 0.19137(15) 0.0495(9) Uani 1 1 d . . . . .
C14 C 0.2752(3) 0.2986(3) 0.20951(19) 0.0729(12) Uani 1 1 d . . . . .
H14A H 0.3005 0.2744 0.1737 0.109 Uiso 1 1 calc R U . . .
H14B H 0.2498 0.2290 0.2255 0.109 Uiso 1 1 calc R U . . .
H14C H 0.3113 0.3294 0.2407 0.109 Uiso 1 1 calc R U . . .
C15 C 0.1595(2) 0.3503(4) 0.1419(2) 0.0832(14) Uani 1 1 d . . . . .
H15A H 0.1241 0.4140 0.1303 0.125 Uiso 1 1 calc R U . . .
H15B H 0.1335 0.2818 0.1583 0.125 Uiso 1 1 calc R U . . .
H15C H 0.1844 0.3247 0.1061 0.125 Uiso 1 1 calc R U . . .
C16 C 0.1761(3) 0.4291(4) 0.24914(19) 0.0853(15) Uani 1 1 d . . . . .
H16A H 0.2115 0.4571 0.2816 0.128 Uiso 1 1 calc R U . . .
H16B H 0.1511 0.3569 0.2627 0.128 Uiso 1 1 calc R U . . .
H16C H 0.1397 0.4922 0.2393 0.128 Uiso 1 1 calc R U . . .
C17 C 0.2806(2) 0.8531(3) 0.20931(15) 0.0486(8) Uani 1 1 d . . . . .
C18 C 0.2933(3) 0.8370(4) 0.27892(19) 0.1061(19) Uani 1 1 d . . . . .
H18A H 0.2927 0.9157 0.2987 0.159 Uiso 1 1 calc R U . . .
H18B H 0.3412 0.7985 0.2885 0.159 Uiso 1 1 calc R U . . .
H18C H 0.2542 0.7865 0.2936 0.159 Uiso 1 1 calc R U . . .
C19 C 0.3381(3) 0.9460(4) 0.1928(3) 0.122(2) Uani 1 1 d . . . . .
H19A H 0.3304 0.9664 0.1496 0.183 Uiso 1 1 calc R U . . .
H19B H 0.3876 0.9124 0.2009 0.183 Uiso 1 1 calc R U . . .
H19C H 0.3331 1.0185 0.2173 0.183 Uiso 1 1 calc R U . . .
C20 C 0.2033(3) 0.9005(5) 0.1947(3) 0.166(3) Uani 1 1 d . . . . .
H20A H 0.1948 0.9697 0.2208 0.249 Uiso 1 1 calc R U . . .
H20B H 0.1675 0.8374 0.2020 0.249 Uiso 1 1 calc R U . . .
H20C H 0.1977 0.9252 0.1520 0.249 Uiso 1 1 calc R U . . .
C21 C 0.18654(17) 0.1963(3) -0.05033(13) 0.0356(7) Uani 1 1 d . . . . .
C22 C 0.11898(18) 0.2269(3) -0.08411(14) 0.0441(8) Uani 1 1 d . . . . .
C23 C 0.07154(19) 0.1305(3) -0.10278(15) 0.0515(9) Uani 1 1 d . . . . .
H23 H 0.0268 0.1495 -0.1255 0.062 Uiso 1 1 calc R U . . .
C24 C 0.0864(2) 0.0068(3) -0.08969(16) 0.0517(9) Uani 1 1 d . . . . .
C25 C 0.15205(18) -0.0189(3) -0.05561(15) 0.0472(8) Uani 1 1 d . . . . .
H25 H 0.1635 -0.1000 -0.0455 0.057 Uiso 1 1 calc R U . . .
C26 C 0.20287(17) 0.0740(3) -0.03536(13) 0.0377(7) Uani 1 1 d . . . . .
C27 C 0.27132(17) 0.0367(3) -0.00153(14) 0.0397(7) Uani 1 1 d . . . . .
H27 H 0.2770 -0.0466 0.0067 0.048 Uiso 1 1 calc R U . . .
C28 C 0.44204(17) 0.1224(3) 0.05968(12) 0.0345(7) Uani 1 1 d . . . . .
C29 C 0.51465(17) 0.0777(3) 0.08493(12) 0.0363(7) Uani 1 1 d . . . . .
C30 C 0.57886(17) 0.1459(3) 0.10030(13) 0.0396(7) Uani 1 1 d . . . . .
H30 H 0.5823 0.2306 0.0966 0.048 Uiso 1 1 calc R U . . .
C31 C 0.63852(19) 0.0680(3) 0.12250(14) 0.0468(8) Uani 1 1 d . . . . .
H31 H 0.6863 0.0967 0.1352 0.056 Uiso 1 1 calc R U . . .
C32 C 0.61949(19) -0.0514(3) 0.12347(14) 0.0464(8) Uani 1 1 d . . . . .
H32 H 0.6525 -0.1135 0.1370 0.056 Uiso 1 1 calc R U . . .
C33 C 0.0297(2) -0.0935(4) -0.1109(2) 0.0697(11) Uani 1 1 d . . . . .
C34 C 0.0531(6) -0.2173(8) -0.0925(7) 0.125(5) Uani 0.583(9) 1 d . U P B 1
H34A H 0.0159 -0.2750 -0.1085 0.187 Uiso 0.583(9) 1 calc R U P B 1
H34B H 0.0583 -0.2227 -0.0481 0.187 Uiso 0.583(9) 1 calc R U P B 1
H34C H 0.1004 -0.2356 -0.1090 0.187 Uiso 0.583(9) 1 calc R U P B 1
C35 C -0.0485(4) -0.0636(9) -0.0786(4) 0.080(3) Uani 0.583(9) 1 d . U P B 1
H35A H -0.0845 -0.1272 -0.0889 0.120 Uiso 0.583(9) 1 calc R U P B 1
H35B H -0.0682 0.0136 -0.0936 0.120 Uiso 0.583(9) 1 calc R U P B 1
H35C H -0.0387 -0.0596 -0.0344 0.120 Uiso 0.583(9) 1 calc R U P B 1
C36 C 0.0073(9) -0.0798(18) -0.1782(7) 0.125(7) Uani 0.583(9) 1 d . U P B 1
H36A H 0.0502 -0.0939 -0.2017 0.188 Uiso 0.583(9) 1 calc R U P B 1
H36B H -0.0114 0.0017 -0.1861 0.188 Uiso 0.583(9) 1 calc R U P B 1
H36C H -0.0313 -0.1382 -0.1901 0.188 Uiso 0.583(9) 1 calc R U P B 1
C34A C 0.0044(9) -0.1616(14) -0.0597(6) 0.105(6) Uani 0.418(9) 1 d . U P B 2
H34D H -0.0240 -0.1088 -0.0346 0.158 Uiso 0.418(9) 1 calc R U P B 2
H34E H 0.0470 -0.1936 -0.0353 0.158 Uiso 0.418(9) 1 calc R U P B 2
H34F H -0.0269 -0.2281 -0.0751 0.158 Uiso 0.418(9) 1 calc R U P B 2
C35A C 0.0807(8) -0.1928(12) -0.1507(7) 0.099(5) Uani 0.418(9) 1 d . U P B 2
H35D H 0.1197 -0.2278 -0.1232 0.148 Uiso 0.418(9) 1 calc R U P B 2
H35E H 0.1030 -0.1502 -0.1837 0.148 Uiso 0.418(9) 1 calc R U P B 2
H35F H 0.0486 -0.2567 -0.1677 0.148 Uiso 0.418(9) 1 calc R U P B 2
C36A C -0.0232(12) -0.059(2) -0.1637(11) 0.126(8) Uani 0.418(9) 1 d . U P B 2
H36D H -0.0411 -0.1312 -0.1851 0.190 Uiso 0.418(9) 1 calc R U P B 2
H36E H 0.0020 -0.0072 -0.1916 0.190 Uiso 0.418(9) 1 calc R U P B 2
H36F H -0.0650 -0.0151 -0.1486 0.190 Uiso 0.418(9) 1 calc R U P B 2
C37 C 0.0984(2) 0.3605(3) -0.10022(17) 0.0566(9) Uani 1 1 d . . . . .
C38 C 0.0213(3) 0.3717(4) -0.1362(3) 0.1053(18) Uani 1 1 d . . . . .
H38A H 0.0220 0.3278 -0.1746 0.158 Uiso 1 1 calc R U . . .
H38B H 0.0104 0.4565 -0.1445 0.158 Uiso 1 1 calc R U . . .
H38C H -0.0167 0.3377 -0.1119 0.158 Uiso 1 1 calc R U . . .
C39 C 0.0951(3) 0.4351(4) -0.0398(2) 0.0788(12) Uani 1 1 d . . . . .
H39A H 0.0815 0.5183 -0.0497 0.118 Uiso 1 1 calc R U . . .
H39B H 0.1435 0.4336 -0.0173 0.118 Uiso 1 1 calc R U . . .
H39C H 0.0583 0.3998 -0.0148 0.118 Uiso 1 1 calc R U . . .
C40 C 0.1569(3) 0.4160(4) -0.1404(2) 0.0824(13) Uani 1 1 d . . . . .
H40A H 0.1577 0.3705 -0.1784 0.124 Uiso 1 1 calc R U . . .
H40B H 0.2056 0.4126 -0.1184 0.124 Uiso 1 1 calc R U . . .
H40C H 0.1440 0.4998 -0.1496 0.124 Uiso 1 1 calc R U . . .
N1 N 0.37956(13) 0.5156(2) -0.00123(10) 0.0345(6) Uani 1 1 d . . . . .
N2 N 0.32582(13) 0.1075(2) 0.01852(10) 0.0337(6) Uani 1 1 d . . . . .
N3 N 0.38835(14) 0.0447(2) 0.04628(11) 0.0378(6) Uani 1 1 d . . . . .
N4 N 0.42051(14) 0.5416(2) -0.05331(11) 0.0401(6) Uani 1 1 d . . . . .
O1 O 0.30257(11) 0.39888(17) 0.08194(9) 0.0399(5) Uani 1 1 d . . . . .
O2 O 0.38464(12) 0.34310(17) -0.07635(9) 0.0418(5) Uani 1 1 d . . . . .
O3 O 0.23673(12) 0.28315(17) -0.03177(9) 0.0408(5) Uani 1 1 d . . . . .
O4 O 0.43473(11) 0.24068(18) 0.05046(9) 0.0412(5) Uani 1 1 d . . . . .
S2 S 0.52864(5) -0.07638(7) 0.09732(4) 0.0473(2) Uani 1 1 d . . . . .
Zr1 Zr 0.33880(2) 0.31693(2) 0.00798(2) 0.03246(11) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 O1 1.337(3) . ?
C1 C2 1.403(4) . ?
C1 C6 1.409(4) . ?
C2 C3 1.384(4) . ?
C2 C13 1.532(4) . ?
C3 C4 1.397(4) . ?
C3 H3 0.9300 . ?
C4 C5 1.377(4) . ?
C4 C17 1.539(4) . ?
C5 C6 1.397(4) . ?
C5 H5 0.9300 . ?
C6 C7 1.439(4) . ?
C7 N1 1.298(3) . ?
C7 H7 0.9300 . ?
C8 N4 1.295(3) . ?
C8 O2 1.317(3) . ?
C8 C9 1.463(4) . ?
C9 C10 1.388(2) . ?
C9 S1 1.643(3) . ?
C9 S1A 1.697(7) . ?
C10 C11 1.502(8) . ?
C10 H10 0.9300 . ?
S1A C11 1.509(8) . ?
S1 C12 1.588(4) . ?
C11 C12 1.314(5) . ?
C11 H11 0.9300 . ?
C12 H12 0.9300 . ?
C13 C14 1.529(5) . ?
C13 C15 1.530(5) . ?
C13 C16 1.533(4) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 C20 1.484(6) . ?
C17 C19 1.503(5) . ?
C17 C18 1.515(5) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 O3 1.344(3) . ?
C21 C26 1.399(4) . ?
C21 C22 1.403(4) . ?
C22 C23 1.391(5) . ?
C22 C37 1.537(5) . ?
C23 C24 1.400(5) . ?
C23 H23 0.9300 . ?
C24 C25 1.367(5) . ?
C24 C33 1.536(5) . ?
C25 C26 1.408(4) . ?
C25 H25 0.9300 . ?
C26 C27 1.436(4) . ?
C27 N2 1.292(4) . ?
C27 H27 0.9300 . ?
C28 N3 1.295(4) . ?
C28 O4 1.311(3) . ?
C28 C29 1.453(4) . ?
C29 C30 1.385(4) . ?
C29 S2 1.717(3) . ?
C30 C31 1.418(4) . ?
C30 H30 0.9300 . ?
C31 C32 1.347(5) . ?
C31 H31 0.9300 . ?
C32 S2 1.699(3) . ?
C32 H32 0.9300 . ?
C33 C34A 1.431(11) . ?
C33 C34 1.460(10) . ?
C33 C36A 1.48(2) . ?
C33 C36 1.488(16) . ?
C33 C35 1.634(8) . ?
C33 C35A 1.688(14) . ?
C34 H34A 0.9600 . ?
C34 H34B 0.9600 . ?
C34 H34C 0.9600 . ?
C35 H35A 0.9600 . ?
C35 H35B 0.9600 . ?
C35 H35C 0.9600 . ?
C36 H36A 0.9600 . ?
C36 H36B 0.9600 . ?
C36 H36C 0.9600 . ?
C34A H34D 0.9600 . ?
C34A H34E 0.9600 . ?
C34A H34F 0.9600 . ?
C35A H35D 0.9600 . ?
C35A H35E 0.9600 . ?
C35A H35F 0.9600 . ?
C36A H36D 0.9600 . ?
C36A H36E 0.9600 . ?
C36A H36F 0.9600 . ?
C37 C40 1.528(5) . ?
C37 C38 1.534(5) . ?
C37 C39 1.543(5) . ?
C38 H38A 0.9600 . ?
C38 H38B 0.9600 . ?
C38 H38C 0.9600 . ?
C39 H39A 0.9600 . ?
C39 H39B 0.9600 . ?
C39 H39C 0.9600 . ?
C40 H40A 0.9600 . ?
C40 H40B 0.9600 . ?
C40 H40C 0.9600 . ?
N1 N4 1.413(3) . ?
N1 Zr1 2.299(2) . ?
N2 N3 1.406(3) . ?
N2 Zr1 2.309(2) . ?
O1 Zr1 1.9789(18) . ?
O2 Zr1 2.0684(19) . ?
O3 Zr1 1.990(2) . ?
O4 Zr1 2.058(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 C2 120.9(2) . . ?
O1 C1 C6 119.1(2) . . ?
C2 C1 C6 120.1(2) . . ?
C3 C2 C1 116.9(3) . . ?
C3 C2 C13 121.6(2) . . ?
C1 C2 C13 121.5(3) . . ?
C2 C3 C4 124.9(3) . . ?
C2 C3 H3 117.5 . . ?
C4 C3 H3 117.5 . . ?
C5 C4 C3 116.7(3) . . ?
C5 C4 C17 122.5(3) . . ?
C3 C4 C17 120.8(3) . . ?
C4 C5 C6 121.5(3) . . ?
C4 C5 H5 119.2 . . ?
C6 C5 H5 119.2 . . ?
C5 C6 C1 119.9(2) . . ?
C5 C6 C7 117.7(3) . . ?
C1 C6 C7 122.3(2) . . ?
N1 C7 C6 125.9(3) . . ?
N1 C7 H7 117.1 . . ?
C6 C7 H7 117.1 . . ?
N4 C8 O2 123.5(2) . . ?
N4 C8 C9 118.6(3) . . ?
O2 C8 C9 117.8(2) . . ?
C10 C9 C8 127.2(4) . . ?
C10 C9 S1 111.5(4) . . ?
C8 C9 S1 121.2(2) . . ?
C8 C9 S1A 124.8(3) . . ?
S1 C9 S1A 114.0(3) . . ?
C9 C10 C11 108.2(5) . . ?
C9 C10 H10 125.9 . . ?
C11 C10 H10 125.9 . . ?
C11 S1A C9 93.7(4) . . ?
C12 S1 C9 94.83(19) . . ?
C12 C11 C10 109.6(3) . . ?
C12 C11 S1A 121.7(4) . . ?
C12 C11 H11 125.2 . . ?
C10 C11 H11 125.2 . . ?
C11 C12 S1 115.8(3) . . ?
C11 C12 H12 122.1 . . ?
S1 C12 H12 122.1 . . ?
C14 C13 C15 109.9(3) . . ?
C14 C13 C2 110.4(3) . . ?
C15 C13 C2 109.5(3) . . ?
C14 C13 C16 107.4(3) . . ?
C15 C13 C16 107.4(3) . . ?
C2 C13 C16 112.1(3) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C13 C16 H16A 109.5 . . ?
C13 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C13 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C20 C17 C19 110.7(4) . . ?
C20 C17 C18 108.8(4) . . ?
C19 C17 C18 104.9(4) . . ?
C20 C17 C4 108.8(3) . . ?
C19 C17 C4 112.2(3) . . ?
C18 C17 C4 111.3(3) . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C17 C19 H19A 109.5 . . ?
C17 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C17 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C17 C20 H20A 109.5 . . ?
C17 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C17 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
O3 C21 C26 118.7(3) . . ?
O3 C21 C22 121.1(3) . . ?
C26 C21 C22 120.2(3) . . ?
C23 C22 C21 116.9(3) . . ?
C23 C22 C37 121.4(3) . . ?
C21 C22 C37 121.7(3) . . ?
C22 C23 C24 124.6(3) . . ?
C22 C23 H23 117.7 . . ?
C24 C23 H23 117.7 . . ?
C25 C24 C23 116.7(3) . . ?
C25 C24 C33 122.3(3) . . ?
C23 C24 C33 121.0(3) . . ?
C24 C25 C26 121.8(3) . . ?
C24 C25 H25 119.1 . . ?
C26 C25 H25 119.1 . . ?
C21 C26 C25 119.7(3) . . ?
C21 C26 C27 122.9(3) . . ?
C25 C26 C27 117.3(3) . . ?
N2 C27 C26 126.3(3) . . ?
N2 C27 H27 116.8 . . ?
C26 C27 H27 116.8 . . ?
N3 C28 O4 123.1(3) . . ?
N3 C28 C29 119.3(3) . . ?
O4 C28 C29 117.6(3) . . ?
C30 C29 C28 127.5(3) . . ?
C30 C29 S2 112.3(2) . . ?
C28 C29 S2 120.2(2) . . ?
C29 C30 C31 110.3(3) . . ?
C29 C30 H30 124.9 . . ?
C31 C30 H30 124.9 . . ?
C32 C31 C30 113.7(3) . . ?
C32 C31 H31 123.2 . . ?
C30 C31 H31 123.2 . . ?
C31 C32 S2 112.6(3) . . ?
C31 C32 H32 123.7 . . ?
S2 C32 H32 123.7 . . ?
C34A C33 C36A 120.6(11) . . ?
C34 C33 C36 114.2(10) . . ?
C34A C33 C24 112.1(5) . . ?
C34 C33 C24 114.1(5) . . ?
C36A C33 C24 114.7(9) . . ?
C36 C33 C24 110.2(7) . . ?
C34 C33 C35 107.7(7) . . ?
C36 C33 C35 102.6(7) . . ?
C24 C33 C35 107.1(4) . . ?
C34A C33 C35A 105.7(9) . . ?
C36A C33 C35A 96.3(11) . . ?
C24 C33 C35A 104.0(5) . . ?
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 . . ?
C33 C35 H35A 109.5 . . ?
C33 C35 H35B 109.5 . . ?
H35A C35 H35B 109.5 . . ?
C33 C35 H35C 109.5 . . ?
H35A C35 H35C 109.5 . . ?
H35B C35 H35C 109.5 . . ?
C33 C36 H36A 109.5 . . ?
C33 C36 H36B 109.5 . . ?
H36A C36 H36B 109.5 . . ?
C33 C36 H36C 109.5 . . ?
H36A C36 H36C 109.5 . . ?
H36B C36 H36C 109.5 . . ?
C33 C34A H34D 109.5 . . ?
C33 C34A H34E 109.5 . . ?
H34D C34A H34E 109.5 . . ?
C33 C34A H34F 109.5 . . ?
H34D C34A H34F 109.5 . . ?
H34E C34A H34F 109.5 . . ?
C33 C35A H35D 109.5 . . ?
C33 C35A H35E 109.5 . . ?
H35D C35A H35E 109.5 . . ?
C33 C35A H35F 109.5 . . ?
H35D C35A H35F 109.5 . . ?
H35E C35A H35F 109.5 . . ?
C33 C36A H36D 109.5 . . ?
C33 C36A H36E 109.5 . . ?
H36D C36A H36E 109.5 . . ?
C33 C36A H36F 109.5 . . ?
H36D C36A H36F 109.5 . . ?
H36E C36A H36F 109.5 . . ?
C40 C37 C38 107.7(3) . . ?
C40 C37 C22 110.0(3) . . ?
C38 C37 C22 112.4(3) . . ?
C40 C37 C39 109.9(3) . . ?
C38 C37 C39 107.5(4) . . ?
C22 C37 C39 109.3(3) . . ?
C37 C38 H38A 109.5 . . ?
C37 C38 H38B 109.5 . . ?
H38A C38 H38B 109.5 . . ?
C37 C38 H38C 109.5 . . ?
H38A C38 H38C 109.5 . . ?
H38B C38 H38C 109.5 . . ?
C37 C39 H39A 109.5 . . ?
C37 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
C37 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?
C37 C40 H40A 109.5 . . ?
C37 C40 H40B 109.5 . . ?
H40A C40 H40B 109.5 . . ?
C37 C40 H40C 109.5 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
C7 N1 N4 113.8(2) . . ?
C7 N1 Zr1 129.90(18) . . ?
N4 N1 Zr1 116.26(16) . . ?
C27 N2 N3 114.0(2) . . ?
C27 N2 Zr1 129.6(2) . . ?
N3 N2 Zr1 116.25(17) . . ?
C28 N3 N2 109.1(2) . . ?
C8 N4 N1 108.8(2) . . ?
C1 O1 Zr1 146.08(17) . . ?
C8 O2 Zr1 121.12(16) . . ?
C21 O3 Zr1 145.87(19) . . ?
C28 O4 Zr1 122.42(18) . . ?
C32 S2 C29 91.12(16) . . ?
O1 Zr1 O3 95.24(8) . . ?
O1 Zr1 O4 97.51(8) . . ?
O3 Zr1 O4 145.36(8) . . ?
O1 Zr1 O2 145.15(8) . . ?
O3 Zr1 O2 92.96(8) . . ?
O4 Zr1 O2 94.65(8) . . ?
O1 Zr1 N1 76.54(8) . . ?
O3 Zr1 N1 114.96(8) . . ?
O4 Zr1 N1 99.32(8) . . ?
O2 Zr1 N1 69.32(7) . . ?
O1 Zr1 N2 109.06(8) . . ?
O3 Zr1 N2 76.38(8) . . ?
O4 Zr1 N2 69.03(8) . . ?
O2 Zr1 N2 105.78(8) . . ?
N1 Zr1 N2 167.35(8) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C1 C2 C3 -179.5(3) . . . . ?
C6 C1 C2 C3 0.9(4) . . . . ?
O1 C1 C2 C13 -0.1(4) . . . . ?
C6 C1 C2 C13 -179.8(3) . . . . ?
C1 C2 C3 C4 -1.4(5) . . . . ?
C13 C2 C3 C4 179.2(3) . . . . ?
C2 C3 C4 C5 1.0(5) . . . . ?
C2 C3 C4 C17 178.5(3) . . . . ?
C3 C4 C5 C6 0.0(5) . . . . ?
C17 C4 C5 C6 -177.4(3) . . . . ?
C4 C5 C6 C1 -0.5(5) . . . . ?
C4 C5 C6 C7 178.3(3) . . . . ?
O1 C1 C6 C5 -179.7(3) . . . . ?
C2 C1 C6 C5 0.0(4) . . . . ?
O1 C1 C6 C7 1.6(4) . . . . ?
C2 C1 C6 C7 -178.7(3) . . . . ?
C5 C6 C7 N1 -175.6(3) . . . . ?
C1 C6 C7 N1 3.2(5) . . . . ?
N4 C8 C9 C10 6.4(6) . . . . ?
O2 C8 C9 C10 -173.6(5) . . . . ?
N4 C8 C9 S1 -174.8(2) . . . . ?
O2 C8 C9 S1 5.2(4) . . . . ?
N4 C8 C9 S1A 5.5(5) . . . . ?
O2 C8 C9 S1A -174.5(3) . . . . ?
C8 C9 C10 C11 178.9(3) . . . . ?
S1 C9 C10 C11 0.0(6) . . . . ?
C8 C9 S1A C11 178.6(3) . . . . ?
S1 C9 S1A C11 -1.2(4) . . . . ?
C10 C9 S1 C12 0.0(4) . . . . ?
C8 C9 S1 C12 -179.0(3) . . . . ?
S1A C9 S1 C12 0.8(3) . . . . ?
C9 C10 C11 C12 -0.1(6) . . . . ?
C9 S1A C11 C12 1.2(6) . . . . ?
C10 C11 C12 S1 0.1(5) . . . . ?
S1A C11 C12 S1 -0.9(6) . . . . ?
C9 S1 C12 C11 0.0(4) . . . . ?
C3 C2 C13 C14 -119.1(3) . . . . ?
C1 C2 C13 C14 61.6(4) . . . . ?
C3 C2 C13 C15 119.8(3) . . . . ?
C1 C2 C13 C15 -59.5(4) . . . . ?
C3 C2 C13 C16 0.6(5) . . . . ?
C1 C2 C13 C16 -178.7(3) . . . . ?
C5 C4 C17 C20 104.5(5) . . . . ?
C3 C4 C17 C20 -72.9(5) . . . . ?
C5 C4 C17 C19 -18.4(5) . . . . ?
C3 C4 C17 C19 164.3(4) . . . . ?
C5 C4 C17 C18 -135.6(4) . . . . ?
C3 C4 C17 C18 47.1(5) . . . . ?
O3 C21 C22 C23 178.2(3) . . . . ?
C26 C21 C22 C23 -1.7(4) . . . . ?
O3 C21 C22 C37 -1.4(4) . . . . ?
C26 C21 C22 C37 178.7(3) . . . . ?
C21 C22 C23 C24 0.6(5) . . . . ?
C37 C22 C23 C24 -179.8(3) . . . . ?
C22 C23 C24 C25 0.7(5) . . . . ?
C22 C23 C24 C33 178.5(3) . . . . ?
C23 C24 C25 C26 -0.9(5) . . . . ?
C33 C24 C25 C26 -178.7(3) . . . . ?
O3 C21 C26 C25 -178.4(3) . . . . ?
C22 C21 C26 C25 1.5(4) . . . . ?
O3 C21 C26 C27 -0.7(4) . . . . ?
C22 C21 C26 C27 179.3(3) . . . . ?
C24 C25 C26 C21 -0.2(5) . . . . ?
C24 C25 C26 C27 -178.1(3) . . . . ?
C21 C26 C27 N2 -0.8(5) . . . . ?
C25 C26 C27 N2 177.0(3) . . . . ?
N3 C28 C29 C30 178.0(3) . . . . ?
O4 C28 C29 C30 -0.7(4) . . . . ?
N3 C28 C29 S2 -0.5(3) . . . . ?
O4 C28 C29 S2 -179.20(18) . . . . ?
C28 C29 C30 C31 -178.9(3) . . . . ?
S2 C29 C30 C31 -0.3(3) . . . . ?
C29 C30 C31 C32 0.0(4) . . . . ?
C30 C31 C32 S2 0.3(3) . . . . ?
C25 C24 C33 C34A 57.7(10) . . . . ?
C23 C24 C33 C34A -120.0(10) . . . . ?
C25 C24 C33 C34 -1.3(9) . . . . ?
C23 C24 C33 C34 -178.9(8) . . . . ?
C25 C24 C33 C36A -159.9(12) . . . . ?
C23 C24 C33 C36A 22.5(13) . . . . ?
C25 C24 C33 C36 -131.2(8) . . . . ?
C23 C24 C33 C36 51.1(9) . . . . ?
C25 C24 C33 C35 117.9(5) . . . . ?
C23 C24 C33 C35 -59.8(6) . . . . ?
C25 C24 C33 C35A -56.1(7) . . . . ?
C23 C24 C33 C35A 126.3(7) . . . . ?
C23 C22 C37 C40 -118.4(4) . . . . ?
C21 C22 C37 C40 61.2(4) . . . . ?
C23 C22 C37 C38 1.6(5) . . . . ?
C21 C22 C37 C38 -178.9(3) . . . . ?
C23 C22 C37 C39 120.8(4) . . . . ?
C21 C22 C37 C39 -59.6(4) . . . . ?
C6 C7 N1 N4 177.7(3) . . . . ?
C6 C7 N1 Zr1 -5.5(5) . . . . ?
C26 C27 N2 N3 -175.6(2) . . . . ?
C26 C27 N2 Zr1 -1.3(4) . . . . ?
O4 C28 N3 N2 3.0(3) . . . . ?
C29 C28 N3 N2 -175.7(2) . . . . ?
C27 N2 N3 C28 174.3(2) . . . . ?
Zr1 N2 N3 C28 -0.7(3) . . . . ?
O2 C8 N4 N1 1.7(4) . . . . ?
C9 C8 N4 N1 -178.4(2) . . . . ?
C7 N1 N4 C8 -177.1(3) . . . . ?
Zr1 N1 N4 C8 5.7(3) . . . . ?
C2 C1 O1 Zr1 175.2(2) . . . . ?
C6 C1 O1 Zr1 -5.2(5) . . . . ?
N4 C8 O2 Zr1 -9.5(4) . . . . ?
C9 C8 O2 Zr1 170.57(18) . . . . ?
C26 C21 O3 Zr1 6.4(5) . . . . ?
C22 C21 O3 Zr1 -173.6(2) . . . . ?
N3 C28 O4 Zr1 -4.2(3) . . . . ?
C29 C28 O4 Zr1 174.50(17) . . . . ?
C31 C32 S2 C29 -0.4(2) . . . . ?
C30 C29 S2 C32 0.4(2) . . . . ?
C28 C29 S2 C32 179.1(2) . . . . ?

_refine_diff_density_max         0.558
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.214

####################################################################### 
# 
# 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_Ligand_2
_database_code_depnum_ccdc_archive 'CCDC 1562816'
_audit_update_record             
;
2017-07-18 deposited with the CCDC.	2021-06-28 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H26 N2 O3 S2'
_chemical_formula_weight         394.54

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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                   9.8710(3)
_cell_length_b                   9.8841(3)
_cell_length_c                   10.9592(3)
_cell_angle_alpha                98.4485(11)
_cell_angle_beta                 94.8760(11)
_cell_angle_gamma                94.1161(12)
_cell_volume                     1049.95(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    8999
_cell_measurement_theta_min      2.59
_cell_measurement_theta_max      27.08

_exptl_crystal_description       BLock
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_F_000             420
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.260
_exptl_crystal_size_min          0.130
_exptl_absorpt_coefficient_mu    0.273
_shelx_estimated_absorpt_T_min   0.910
_shelx_estimated_absorpt_T_max   0.965
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.910
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_process_details   'SADABS V2014/5(Bruker AXS.Inc)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            15632
_diffrn_reflns_av_unetI/netI     0.0135
_diffrn_reflns_av_R_equivalents  0.0169
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         1.887
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_full        24.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3699
_reflns_number_gt                3160
_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1191P)²+1.3564P] 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         3699
_refine_ls_number_parameters     249
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0743
_refine_ls_wR_factor_ref         0.2207
_refine_ls_wR_factor_gt          0.2076
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.001

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C -0.3350(3) 0.4601(4) 0.5850(3) 0.0457(7) Uani 1 1 d . . . . .
H1 H -0.3060 0.3779 0.5476 0.055 Uiso 1 1 calc R U . . .
C2 C -0.4325(4) 0.4702(5) 0.6720(4) 0.0636(10) Uani 1 1 d . . . . .
H2 H -0.4750 0.3943 0.6988 0.076 Uiso 1 1 calc R U . . .
C3 C -0.4577(5) 0.5970(6) 0.7117(4) 0.0806(13) Uani 1 1 d . . . . .
H3 H -0.5205 0.6197 0.7683 0.097 Uiso 1 1 calc R U . . .
C4 C -0.2884(3) 0.5886(3) 0.5626(3) 0.0405(7) Uani 1 1 d . . . . .
C5 C -0.1903(3) 0.6332(3) 0.4795(3) 0.0429(7) Uani 1 1 d . . . . .
C6 C -0.0025(3) 0.4760(3) 0.2511(3) 0.0407(7) Uani 1 1 d . . . . .
H6 H -0.0310 0.3843 0.2515 0.049 Uiso 1 1 calc R U . . .
C7 C 0.0922(3) 0.5113(3) 0.1644(3) 0.0367(6) Uani 1 1 d . . . . .
C8 C 0.1369(3) 0.6490(3) 0.1584(3) 0.0364(6) Uani 1 1 d . . . . .
C9 C 0.2247(3) 0.6806(3) 0.0710(3) 0.0360(6) Uani 1 1 d . . . . .
C10 C 0.2671(3) 0.5711(3) -0.0074(3) 0.0405(7) Uani 1 1 d . . . . .
H10 H 0.3253 0.5907 -0.0661 0.049 Uiso 1 1 calc R U . . .
C11 C 0.2275(3) 0.4343(3) -0.0029(3) 0.0417(7) Uani 1 1 d . . . . .
C12 C 0.1392(3) 0.4068(3) 0.0826(3) 0.0399(7) Uani 1 1 d . . . . .
H12 H 0.1100 0.3160 0.0861 0.048 Uiso 1 1 calc R U . . .
C13 C 0.2713(3) 0.8306(3) 0.0621(3) 0.0441(7) Uani 1 1 d . . . . .
C14 C 0.1477(4) 0.9113(4) 0.0367(4) 0.0633(10) Uani 1 1 d . . . . .
H14A H 0.1778 1.0062 0.0386 0.095 Uiso 1 1 calc R U . . .
H14B H 0.0861 0.9033 0.0990 0.095 Uiso 1 1 calc R U . . .
H14C H 0.1018 0.8748 -0.0434 0.095 Uiso 1 1 calc R U . . .
C15 C 0.3562(5) 0.8974(4) 0.1828(4) 0.0681(11) Uani 1 1 d . . . . .
H15A H 0.4331 0.8458 0.1973 0.102 Uiso 1 1 calc R U . . .
H15B H 0.3008 0.8985 0.2507 0.102 Uiso 1 1 calc R U . . .
H15C H 0.3878 0.9898 0.1756 0.102 Uiso 1 1 calc R U . . .
C16 C 0.3611(4) 0.8412(4) -0.0439(4) 0.0582(9) Uani 1 1 d . . . . .
H16A H 0.4430 0.7970 -0.0288 0.087 Uiso 1 1 calc R U . . .
H16B H 0.3842 0.9362 -0.0488 0.087 Uiso 1 1 calc R U . . .
H16C H 0.3123 0.7972 -0.1206 0.087 Uiso 1 1 calc R U . . .
C17 C 0.2768(4) 0.3204(4) -0.0922(4) 0.0629(10) Uani 1 1 d . . . . .
H17A H 0.2767 0.2379 -0.0555 0.094 Uiso 1 1 calc R U . . .
H17B H 0.3678 0.3467 -0.1099 0.094 Uiso 1 1 calc R U . . .
H17C H 0.2172 0.3043 -0.1677 0.094 Uiso 1 1 calc R U . . .
C18 C 0.3237(6) 0.9763(6) 0.5929(8) 0.121(3) Uani 1 1 d . . . . .
H18A H 0.3544 0.9945 0.6797 0.181 Uiso 1 1 calc R U . . .
H18B H 0.3113 1.0614 0.5627 0.181 Uiso 1 1 calc R U . . .
H18C H 0.3905 0.9289 0.5487 0.181 Uiso 1 1 calc R U . . .
C19 C 0.0724(5) 0.9771(4) 0.6682(4) 0.0743(12) Uani 1 1 d . . . . .
H19A H -0.0194 0.9358 0.6623 0.111 Uiso 1 1 calc R U . . .
H19B H 0.0716 1.0664 0.6437 0.111 Uiso 1 1 calc R U . . .
H19C H 0.1126 0.9856 0.7522 0.111 Uiso 1 1 calc R U . . .
N1 N -0.1386(3) 0.5324(3) 0.4059(3) 0.0428(6) Uani 1 1 d . . . . .
N2 N -0.0474(3) 0.5690(3) 0.3268(2) 0.0421(6) Uani 1 1 d . . . . .
O1 O -0.1605(3) 0.7549(2) 0.4771(3) 0.0682(8) Uani 1 1 d . . . . .
O2 O 0.0958(3) 0.7529(3) 0.2377(2) 0.0540(7) Uani 1 1 d . . . . .
O3 O 0.1975(4) 0.7523(3) 0.6355(3) 0.0766(9) Uani 1 1 d . . . . .
S1 S -0.36471(14) 0.71435(12) 0.64961(12) 0.0804(4) Uani 1 1 d . . . . .
S2 S 0.16814(11) 0.87402(9) 0.57041(9) 0.0596(3) Uani 1 1 d . . . . .
H1N H -0.156(4) 0.463(4) 0.405(3) 0.036(10) Uiso 1 1 d . . . . .
H2O H 0.053(4) 0.725(4) 0.270(4) 0.046(12) Uiso 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C4 1.383(5) . ?
C1 C2 1.410(5) . ?
C1 H1 0.9300 . ?
C2 C3 1.313(7) . ?
C2 H2 0.9300 . ?
C3 S1 1.684(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.472(4) . ?
C4 S1 1.712(3) . ?
C5 O1 1.223(4) . ?
C5 N1 1.345(4) . ?
C6 N2 1.275(4) . ?
C6 C7 1.449(4) . ?
C6 H6 0.9300 . ?
C7 C12 1.398(4) . ?
C7 C8 1.413(4) . ?
C8 O2 1.354(4) . ?
C8 C9 1.399(4) . ?
C9 C10 1.391(4) . ?
C9 C13 1.540(4) . ?
C10 C11 1.389(4) . ?
C10 H10 0.9300 . ?
C11 C12 1.375(4) . ?
C11 C17 1.516(5) . ?
C12 H12 0.9300 . ?
C13 C16 1.531(4) . ?
C13 C14 1.532(5) . ?
C13 C15 1.537(5) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 S2 1.755(5) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 S2 1.752(4) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
N1 N2 1.368(4) . ?
N1 H1N 0.69(4) . ?
O2 H2O 0.65(4) . ?
O3 S2 1.519(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C4 C1 C2 111.0(3) . . ?
C4 C1 H1 124.5 . . ?
C2 C1 H1 124.5 . . ?
C3 C2 C1 113.6(4) . . ?
C3 C2 H2 123.2 . . ?
C1 C2 H2 123.2 . . ?
C2 C3 S1 113.2(3) . . ?
C2 C3 H3 123.4 . . ?
S1 C3 H3 123.4 . . ?
C1 C4 C5 132.2(3) . . ?
C1 C4 S1 110.8(2) . . ?
C5 C4 S1 117.0(2) . . ?
O1 C5 N1 122.8(3) . . ?
O1 C5 C4 121.2(3) . . ?
N1 C5 C4 116.0(3) . . ?
N2 C6 C7 120.9(3) . . ?
N2 C6 H6 119.6 . . ?
C7 C6 H6 119.6 . . ?
C12 C7 C8 118.8(3) . . ?
C12 C7 C6 119.4(3) . . ?
C8 C7 C6 121.9(3) . . ?
O2 C8 C9 118.7(3) . . ?
O2 C8 C7 120.5(3) . . ?
C9 C8 C7 120.8(3) . . ?
C10 C9 C8 117.2(3) . . ?
C10 C9 C13 121.8(3) . . ?
C8 C9 C13 121.0(3) . . ?
C11 C10 C9 123.8(3) . . ?
C11 C10 H10 118.1 . . ?
C9 C10 H10 118.1 . . ?
C12 C11 C10 117.6(3) . . ?
C12 C11 C17 121.5(3) . . ?
C10 C11 C17 120.8(3) . . ?
C11 C12 C7 121.9(3) . . ?
C11 C12 H12 119.1 . . ?
C7 C12 H12 119.1 . . ?
C16 C13 C14 106.7(3) . . ?
C16 C13 C15 107.2(3) . . ?
C14 C13 C15 110.5(3) . . ?
C16 C13 C9 112.1(3) . . ?
C14 C13 C9 110.5(3) . . ?
C15 C13 C9 109.8(3) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C13 C16 H16A 109.5 . . ?
C13 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C13 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C11 C17 H17A 109.5 . . ?
C11 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C11 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
S2 C18 H18A 109.5 . . ?
S2 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
S2 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
S2 C19 H19A 109.5 . . ?
S2 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
S2 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C5 N1 N2 118.1(3) . . ?
C5 N1 H1N 124(3) . . ?
N2 N1 H1N 118(3) . . ?
C6 N2 N1 119.4(3) . . ?
C8 O2 H2O 106(4) . . ?
C3 S1 C4 91.5(2) . . ?
O3 S2 C19 105.79(19) . . ?
O3 S2 C18 104.0(2) . . ?
C19 S2 C18 99.7(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 C1 C2 C3 0.3(5) . . . . ?
C1 C2 C3 S1 -0.9(5) . . . . ?
C2 C1 C4 C5 -178.6(3) . . . . ?
C2 C1 C4 S1 0.5(4) . . . . ?
C1 C4 C5 O1 -177.8(3) . . . . ?
S1 C4 C5 O1 3.1(4) . . . . ?
C1 C4 C5 N1 3.5(5) . . . . ?
S1 C4 C5 N1 -175.6(2) . . . . ?
N2 C6 C7 C12 -180.0(3) . . . . ?
N2 C6 C7 C8 -1.0(5) . . . . ?
C12 C7 C8 O2 -178.6(3) . . . . ?
C6 C7 C8 O2 2.4(4) . . . . ?
C12 C7 C8 C9 1.2(4) . . . . ?
C6 C7 C8 C9 -177.8(3) . . . . ?
O2 C8 C9 C10 178.7(3) . . . . ?
C7 C8 C9 C10 -1.1(4) . . . . ?
O2 C8 C9 C13 -1.6(4) . . . . ?
C7 C8 C9 C13 178.6(3) . . . . ?
C8 C9 C10 C11 -0.2(4) . . . . ?
C13 C9 C10 C11 -179.8(3) . . . . ?
C9 C10 C11 C12 1.3(5) . . . . ?
C9 C10 C11 C17 179.5(3) . . . . ?
C10 C11 C12 C7 -1.2(5) . . . . ?
C17 C11 C12 C7 -179.3(3) . . . . ?
C8 C7 C12 C11 0.0(4) . . . . ?
C6 C7 C12 C11 179.0(3) . . . . ?
C10 C9 C13 C16 2.5(4) . . . . ?
C8 C9 C13 C16 -177.2(3) . . . . ?
C10 C9 C13 C14 121.3(3) . . . . ?
C8 C9 C13 C14 -58.3(4) . . . . ?
C10 C9 C13 C15 -116.6(3) . . . . ?
C8 C9 C13 C15 63.8(4) . . . . ?
O1 C5 N1 N2 1.1(5) . . . . ?
C4 C5 N1 N2 179.8(3) . . . . ?
C7 C6 N2 N1 178.8(3) . . . . ?
C5 N1 N2 C6 -176.1(3) . . . . ?
C2 C3 S1 C4 1.0(4) . . . . ?
C1 C4 S1 C3 -0.8(3) . . . . ?
C5 C4 S1 C3 178.4(3) . . . . ?

_refine_diff_density_max         2.190
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.069

