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

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

data_ti4-buda
_database_code_depnum_ccdc_archive 'CCDC 1977578'
loop_
_audit_author_name
_audit_author_address
'Yifeng Wang'
;Shandong University
China
;
_audit_update_record             
;
2020-04-01 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_audit_creation_date             2020-03-25
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'O28 S4 Ti4, 2(C4 H14 N2), 2(O4 S)'
_chemical_formula_sum            'C8 H28 N4 O36 S6 Ti4'
_chemical_formula_weight         1140.30
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Ti O S N C'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           140
_space_group_name_H-M_alt        'I 4/m c m'
_space_group_name_Hall           '-I 4 2c'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x, z'
'-x, -y, z'
'y, -x, z'
'x, -y, -z+1/2'
'y, x, -z+1/2'
'-x, y, -z+1/2'
'-y, -x, -z+1/2'
'x+1/2, y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'x+1/2, -y+1/2, -z+1'
'y+1/2, x+1/2, -z+1'
'-x+1/2, y+1/2, -z+1'
'-y+1/2, -x+1/2, -z+1'
'-x, -y, -z'
'y, -x, -z'
'x, y, -z'
'-y, x, -z'
'-x, y, z-1/2'
'-y, -x, z-1/2'
'x, -y, z-1/2'
'y, x, z-1/2'
'-x+1/2, -y+1/2, -z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'x+1/2, y+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'-x+1/2, y+1/2, z'
'-y+1/2, -x+1/2, z'
'x+1/2, -y+1/2, z'
'y+1/2, x+1/2, z'

_cell_length_a                   13.8316(2)
_cell_length_b                   13.8316(2)
_cell_length_c                   20.2120(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3866.82(14)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    6134
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.1360
_cell_measurement_theta_min      4.3400
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.944
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32500
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.959
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2304
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            5413
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.268
_diffrn_reflns_theta_min         4.375
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -99.00 -57.00   1.00    0.30    --  -86.25  30.00 -74.00   42
  2  ω     85.00 165.00   1.00    0.30    --  106.49 140.00 150.00   80
  3  ω   -121.00 -36.00   1.00    0.10    --  -48.45 -38.00  60.00   85
  4  ω    -43.00 -17.00   1.00    0.30    --  -86.25  30.00 -74.00   26
  5  ω     34.00 120.00   1.00    0.30    --  106.49 -38.00  30.00   86
  6  ω     36.00 105.00   1.00    0.30    --  106.49 -99.00-180.00   69
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0878281000
_diffrn_orient_matrix_UB_12      0.0565590000
_diffrn_orient_matrix_UB_13      0.0264329000
_diffrn_orient_matrix_UB_21      -0.0536205000
_diffrn_orient_matrix_UB_22      -0.0958798000
_diffrn_orient_matrix_UB_23      0.0127107000
_diffrn_orient_matrix_UB_31      0.0427153000
_diffrn_orient_matrix_UB_32      -0.0040040000
_diffrn_orient_matrix_UB_33      0.0703165000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1019
_reflns_number_total             1080
_reflns_odcompleteness_completeness 99.19
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXL (Sheldrick, 2015)'
_refine_diff_density_max         1.345
_refine_diff_density_min         -0.768
_refine_diff_density_rms         0.177
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         1080
_refine_ls_number_restraints     187
_refine_ls_R_factor_all          0.1047
_refine_ls_R_factor_gt           0.0995
_refine_ls_restrained_S_all      1.056
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0570P)²+171.6096P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2233
_refine_ls_wR_factor_ref         0.2269
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
2. Restrained distances
 N2-C3 = C3-C4 = C4-C5 = C5-C6 = C6-N7
 1.52 with sigma of 0.02
 S2-O6 = S2-O10 = S2-O8 = S2-O9
 1.5 with sigma of 0.02
 N2-C4 = C5-N7
 2.53 with sigma of 0.04
 C3-C5 = C4-C6
 2.54 with sigma of 0.04
 S2-O6 \\sim S2-O10 \\sim S2-O8 \\sim S2-O9
 with sigma of 0.02
 O6-O8 \\sim O10-O9 \\sim O6-O9 \\sim O10-O8 \\sim O6-O10 \\sim O8-O9
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim N7: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
S2 \\sim O6 \\sim O10 \\sim O8 \\sim O9: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(N7) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N7) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 N2, C3, C4, C5, C6, N7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, N2, C3, C5, C6, N7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S2, O6, O10, O8, O9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: N2(0.25) H2A(0.25) H2B(0.25) H2C(0.25) C3(0.25) H3A(0.25)
 H3B(0.25) C4(0.25) H4A(0.25) H4B(0.25) C5(0.25) H5A(0.25) H5B(0.25) C6(0.25)
 H6A(0.25) H6B(0.25) N7(0.25) H7A(0.25) H7B(0.25) H7C(0.25) S2(0.25) O6(0.25)
 O10(0.25) O8(0.25) O9(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B)
6.b Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), N7(H7A,H7B,H7C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.0000 0.32258(15) -0.2500 0.0269(6) Uani 1 2 d S T P . .
S0AA S 0.16962(15) 0.33038(15) -0.14167(12) 0.0261(7) Uani 1 2 d S T P . .
O1 O 0.0929(4) 0.4071(4) -0.2758(4) 0.0276(18) Uani 1 2 d S T P . .
O4 O 0.1734(5) 0.3266(5) -0.0710(4) 0.033(2) Uani 1 2 d S T P . .
O5 O 0.2357(5) 0.2643(5) -0.1742(4) 0.041(2) Uani 1 2 d S T P . .
O2 O -0.0791(4) 0.2085(5) -0.2105(3) 0.0352(15) Uani 1 1 d . . . . .
O3 O 0.0686(4) 0.3081(5) -0.1630(3) 0.0330(14) Uani 1 1 d . . . . .
N2 N -0.273(3) 0.525(3) 0.008(3) 0.029(8) Uani 0.25 1 d D U . A -1
H2A H -0.3377 0.5385 0.0066 0.034 Uiso 0.25 1 calc GR . . A -1
H2B H -0.2397 0.5743 -0.0111 0.034 Uiso 0.25 1 calc GR . . A -1
H2C H -0.2544 0.5188 0.0510 0.034 Uiso 0.25 1 calc GR . . A -1
C3 C -0.254(2) 0.433(3) -0.028(2) 0.051(7) Uani 0.25 1 d D U . A -1
H3A H -0.2853 0.3793 -0.0039 0.062 Uiso 0.25 1 calc R . . A -1
H3B H -0.2852 0.4369 -0.0722 0.062 Uiso 0.25 1 calc R . . A -1
C4 C -0.152(2) 0.406(3) -0.039(2) 0.061(7) Uani 0.25 1 d D U . A -1
H4A H -0.1113 0.4471 -0.0106 0.073 Uiso 0.25 1 calc R . . A -1
H4B H -0.1353 0.4198 -0.0855 0.073 Uiso 0.25 1 calc R . . A -1
C5 C -0.127(2) 0.300(2) -0.0246(18) 0.046(7) Uani 0.25 1 d D U . A -1
H5A H -0.1823 0.2682 -0.0019 0.055 Uiso 0.25 1 calc R . . A -1
H5B H -0.1149 0.2653 -0.0666 0.055 Uiso 0.25 1 calc R . . A -1
C6 C -0.039(2) 0.298(2) 0.0184(16) 0.044(7) Uani 0.25 1 d D U . A -1
H6A H -0.0600 0.2985 0.0653 0.053 Uiso 0.25 1 calc R . . A -1
H6B H -0.0009 0.3566 0.0102 0.053 Uiso 0.25 1 calc R . . A -1
N7 N 0.024(3) 0.210(3) 0.007(4) 0.026(7) Uani 0.25 1 d D U . A -1
H7A H 0.0345 0.2020 -0.0369 0.031 Uiso 0.25 1 calc GR . . A -1
H7B H -0.0051 0.1566 0.0239 0.031 Uiso 0.25 1 calc GR . . A -1
H7C H 0.0821 0.2190 0.0280 0.031 Uiso 0.25 1 calc GR . . A -1
S2 S -0.0106(13) 0.0010(15) 0.1171(2) 0.024(2) Uani 0.25 1 d D U . B -1
O6 O -0.0477(18) 0.1014(15) 0.1123(12) 0.038(4) Uani 0.25 1 d D U . B -1
O10 O 0.0960(13) -0.001(2) 0.1074(11) 0.038(3) Uani 0.25 1 d D U . B -1
O8 O -0.0606(17) -0.0588(17) 0.0665(9) 0.040(3) Uani 0.25 1 d D U . B -1
O9 O -0.0313(19) -0.0382(19) 0.1843(7) 0.037(3) Uani 0.25 1 d D U . B -1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O1 1.814(3) 26_454 ?
Ti1 O1 1.814(3) . ?
Ti1 O2 2.079(6) 7_554 ?
Ti1 O2 2.079(6) . ?
Ti1 O3 2.009(5) . ?
Ti1 O3 2.009(5) 7_554 ?
S0AA O4 1.430(7) . ?
S0AA O5 1.450(10) . ?
S0AA O3 1.495(6) 30 ?
S0AA O3 1.495(6) . ?
O1 Ti1 1.814(3) 28_554 ?
N2 H2A 0.9100 . ?
N2 H2B 0.9100 . ?
N2 H2C 0.9100 . ?
N2 C3 1.50(2) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C3 C4 1.46(2) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C4 C5 1.527(19) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C5 C6 1.50(2) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C6 N7 1.51(2) . ?
N7 H7A 0.9100 . ?
N7 H7B 0.9100 . ?
N7 H7C 0.9100 . ?
S2 O6 1.483(13) . ?
S2 O10 1.488(13) . ?
S2 O8 1.487(13) . ?
S2 O9 1.491(12) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Ti1 O1 99.7(5) 26_454 . ?
O1 Ti1 O2 166.5(3) 26_454 7_554 ?
O1 Ti1 O2 90.3(3) . 7_554 ?
O1 Ti1 O2 90.3(3) 26_454 . ?
O1 Ti1 O2 166.5(3) . . ?
O1 Ti1 O3 98.5(3) 26_454 . ?
O1 Ti1 O3 89.0(3) 26_454 7_554 ?
O1 Ti1 O3 98.5(3) . 7_554 ?
O1 Ti1 O3 89.0(3) . . ?
O2 Ti1 O2 81.3(4) . 7_554 ?
O3 Ti1 O2 80.6(2) 7_554 7_554 ?
O3 Ti1 O2 90.7(3) 7_554 . ?
O3 Ti1 O2 90.7(3) . 7_554 ?
O3 Ti1 O2 80.6(2) . . ?
O3 Ti1 O3 168.5(4) . 7_554 ?
O4 S0AA O5 114.0(6) . . ?
O4 S0AA O3 108.3(3) . . ?
O4 S0AA O3 108.3(3) . 30 ?
O5 S0AA O3 109.2(3) . . ?
O5 S0AA O3 109.2(3) . 30 ?
O3 S0AA O3 107.7(5) 30 . ?
Ti1 O1 Ti1 146.2(5) . 28_554 ?
S0AA O3 Ti1 132.3(4) . . ?
H2A N2 H2B 109.5 . . ?
H2A N2 H2C 109.5 . . ?
H2B N2 H2C 109.5 . . ?
C3 N2 H2A 109.5 . . ?
C3 N2 H2B 109.5 . . ?
C3 N2 H2C 109.5 . . ?
N2 C3 H3A 107.9 . . ?
N2 C3 H3B 107.9 . . ?
H3A C3 H3B 107.2 . . ?
C4 C3 N2 118(3) . . ?
C4 C3 H3A 107.9 . . ?
C4 C3 H3B 107.9 . . ?
C3 C4 H4A 108.4 . . ?
C3 C4 H4B 108.4 . . ?
C3 C4 C5 115(3) . . ?
H4A C4 H4B 107.5 . . ?
C5 C4 H4A 108.4 . . ?
C5 C4 H4B 108.4 . . ?
C4 C5 H5A 110.0 . . ?
C4 C5 H5B 110.0 . . ?
H5A C5 H5B 108.4 . . ?
C6 C5 C4 108(2) . . ?
C6 C5 H5A 110.0 . . ?
C6 C5 H5B 110.0 . . ?
C5 C6 H6A 108.7 . . ?
C5 C6 H6B 108.7 . . ?
C5 C6 N7 114(2) . . ?
H6A C6 H6B 107.6 . . ?
N7 C6 H6A 108.7 . . ?
N7 C6 H6B 108.7 . . ?
C6 N7 H7A 109.5 . . ?
C6 N7 H7B 109.5 . . ?
C6 N7 H7C 109.5 . . ?
H7A N7 H7B 109.5 . . ?
H7A N7 H7C 109.5 . . ?
H7B N7 H7C 109.5 . . ?
O6 S2 O10 110.9(14) . . ?
O6 S2 O8 108.3(14) . . ?
O6 S2 O9 109.5(14) . . ?
O10 S2 O9 107.5(13) . . ?
O8 S2 O10 111.0(13) . . ?
O8 S2 O9 109.6(14) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Ti1 O1 Ti1 66.0(8) 26_454 . . 28_554 ?
O4 S0AA O3 Ti1 167.0(5) . . . . ?
O5 S0AA O3 Ti1 -68.3(6) . . . . ?
O2 Ti1 O1 Ti1 -123.0(9) 7_554 . . 28_554 ?
O2 Ti1 O1 Ti1 -71.7(18) . . . 28_554 ?
O3 Ti1 O1 Ti1 -32.4(9) . . . 28_554 ?
O3 Ti1 O1 Ti1 156.4(8) 7_554 . . 28_554 ?
O3 S0AA O3 Ti1 50.1(8) 30 . . . ?
N2 C3 C4 C5 135(5) . . . . ?
C3 C4 C5 C6 -131(3) . . . . ?
C4 C5 C6 N7 -148(4) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.123
_oxdiff_exptl_absorpt_empirical_full_min 0.745


# start Validation Reply Form
_vrf_PLAT430_ti4-buda            
;
PROBLEM: Short Inter D...A Contact O2 ..O6 . 2.51 Ang.
RESPONSE: This problem is caused by the disorder of the atoms.
;
_vrf_PLAT088_ti4-buda            
;
PROBLEM: Poor Data / Parameter Ratio .................... 7.25 Note
RESPONSE: This problem is caused by the poor quality of the crystals.
;
# 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_ti4-chexda
_database_code_depnum_ccdc_archive 'CCDC 1977579'
loop_
_audit_author_name
_audit_author_address
'Yifeng Wang'
;Shandong University
China
;
_audit_update_record             
;
2020-04-01 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_audit_creation_date             2020-03-25
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         '4(H16 O28 S4 Ti4), O32 S8, 8(C6 H16 N2)'
_chemical_formula_sum            'C48 H192 N16 O144 S24 Ti16'
_chemical_formula_weight         4834.00
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Ti O S'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           140
_space_group_name_H-M_alt        'I 4/m c m'
_space_group_name_Hall           '-I 4 2c'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-y, x, z'
'y, -x, z'
'-x, y, -z+1/2'
'x, -y, -z+1/2'
'y, x, -z+1/2'
'-y, -x, -z+1/2'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1'
'x+1/2, -y+1/2, -z+1'
'y+1/2, x+1/2, -z+1'
'-y+1/2, -x+1/2, -z+1'
'-x, -y, -z'
'x, y, -z'
'y, -x, -z'
'-y, x, -z'
'x, -y, z-1/2'
'-x, y, z-1/2'
'-y, -x, z-1/2'
'y, x, z-1/2'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y+1/2, -z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, z'
'-y+1/2, -x+1/2, z'
'y+1/2, x+1/2, z'

_cell_length_a                   13.7675(2)
_cell_length_b                   13.7675(2)
_cell_length_c                   20.9391(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3968.88(14)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    3451
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.0270
_cell_measurement_theta_min      6.1530
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.700
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.022
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2480
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            5055
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.289
_diffrn_reflns_theta_min         4.542
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -120.00 -55.00   1.00    0.30    --  -48.45-173.00  89.00   65
  2  ω   -154.00 -83.00   1.00    0.95    --  -86.25-114.00-130.00   71
  3  ω    111.00 177.00   1.00    0.95    --  106.49  19.00-133.00   66
  4  ω   -105.00 -70.00   1.00    0.30    --  -48.45-125.00   0.00   35
  5  ω   -112.00 -80.00   1.00    0.30    --  -48.45-125.00 -30.00   32
  6  ω     40.00  81.00   1.00    0.95    --  106.49 -94.00  30.00   41
  7  ω     94.00 158.00   1.00    0.95    --  106.49  15.00 -30.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0223046000
_diffrn_orient_matrix_UB_12      -0.1093630000
_diffrn_orient_matrix_UB_13      0.0059036000
_diffrn_orient_matrix_UB_21      -0.0173644000
_diffrn_orient_matrix_UB_22      -0.0126592000
_diffrn_orient_matrix_UB_23      -0.0721719000
_diffrn_orient_matrix_UB_31      0.1082545000
_diffrn_orient_matrix_UB_32      0.0205167000
_diffrn_orient_matrix_UB_33      -0.0127321000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1046
_reflns_number_total             1094
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXL (Sheldrick, 2015)'
_refine_diff_density_max         0.780
_refine_diff_density_min         -0.759
_refine_diff_density_rms         0.159
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.228
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     131
_refine_ls_number_reflns         1094
_refine_ls_number_restraints     108
_refine_ls_R_factor_all          0.0901
_refine_ls_R_factor_gt           0.0858
_refine_ls_restrained_S_all      1.175
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+156.6020P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1855
_refine_ls_wR_factor_ref         0.1897
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H,H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 C2B-C2B_$1
 1.5 with sigma of 0.02
 S1-O6 = S1-O7 = S1-O7 = S1-O9
 1.45 with sigma of 0.01
 C2B_$2-C2B_$3
 1.5 with sigma of 0.02
 C2B-C2B_$3
 2.3 with sigma of 0.02
 C2B_$1-C2B_$2
 2.3 with sigma of 0.02
 C2B-C1B
 1.5 with sigma of 0.02
 C2A-C2A_$1
 1.5 with sigma of 0.02
 C2A_$2-C2A_$3
 1.5 with sigma of 0.02
 C2A-C2A_$3
 2.3 with sigma of 0.02
 C2A_$2-C2A_$1
 2.3 with sigma of 0.02
 C1A-N1
 1.5 with sigma of 0.02
 C1A-C2A
 1.5 with sigma of 0.02
 S1-O7 \\sim S1-O6 \\sim S1-O8_$4 \\sim S1-O9
 with sigma of 0.02
 O6-O7 \\sim O6-O8_$4 \\sim O6-O9 \\sim O7-O8_$4 \\sim O7-O9 \\sim O8_$4-O9
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1 \\sim O6 \\sim O7 \\sim O8 \\sim O9: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(S1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C1B)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S1, O6, O7, O8, O9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: S1(0.25) O6(0.25) O7(0.25) O8(0.25) O9(0.25) H1AA(0.25) H1AC(0.25)
 H1AB(0.25) H1BE(0.25) H1BF(0.25) H1BD(0.25) C1A(0.25) H1A(0.25) C1B(0.25)
 H1B(0.25) C2A(0.5) H2AA(0.5) H2AB(0.5) C2B(0.5) H2BA(0.5) H2BB(0.5)
6.a Rotating group:
 O5(H5A,H5B)
6.b Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B)
6.c Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB)
6.d Idealised Me refined as rotating group:
 N1(H1AA,H1AC,H1AB), N1(H1BE,H1BF,H1BD)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.17835(13) 0.5000 0.2500 0.0232(5) Uani 1 2 d S T P . .
S2 S 0.17000(13) 0.67000(13) 0.35556(12) 0.0229(6) Uani 1 2 d S T P . .
O1 O 0.1713(5) 0.6713(5) 0.4239(4) 0.037(2) Uani 1 2 d S T P . .
O2 O 0.2371(4) 0.7371(4) 0.3258(4) 0.0281(17) Uani 1 2 d S T P . .
O3 O 0.1937(4) 0.5694(4) 0.3327(3) 0.0280(12) Uani 1 1 d . . . . .
O4 O 0.0934(4) 0.4066(4) 0.2754(3) 0.0212(15) Uani 1 2 d S TU P . .
O5 O 0.2935(4) 0.5781(4) 0.2107(3) 0.0283(12) Uani 1 1 d . . . . .
H5A H 0.3455 0.5744 0.2357 0.043 Uiso 1 1 d GR . . . .
H5B H 0.2799 0.6411 0.2103 0.043 Uiso 1 1 d GR . . . .
S1 S 0.5026(11) 0.5125(10) 0.6172(2) 0.018(2) Uani 0.25 1 d D U . A -1
O6 O 0.5359(18) 0.4124(10) 0.6145(8) 0.025(4) Uani 0.25 1 d D U . . .
O7 O 0.5240(12) 0.5524(12) 0.6799(5) 0.021(4) Uani 0.25 1 d D U . . .
O8 O 0.4317(13) 0.5511(14) 0.4317(7) 0.028(5) Uani 0.25 1 d D U . . .
O9 O 0.3983(11) 0.5155(19) 0.6069(9) 0.024(4) Uani 0.25 1 d D U . . .
N1 N 0.2806(8) 0.5130(8) 0.5000 0.065(4) Uani 1 2 d DS T P . .
H1AA H 0.3020 0.5205 0.5408 0.078 Uiso 0.25 1 calc GR . . B 1
H1AC H 0.2678 0.5722 0.4827 0.078 Uiso 0.25 1 calc GR . . B 1
H1AB H 0.3272 0.4826 0.4765 0.078 Uiso 0.25 1 calc GR . . B 1
H1BE H 0.2486 0.5574 0.4757 0.078 Uiso 0.25 1 calc GR . . C 2
H1BF H 0.3410 0.5030 0.4836 0.078 Uiso 0.25 1 calc GR . . C 2
H1BD H 0.2858 0.5355 0.5407 0.078 Uiso 0.25 1 calc GR . . C 2
C1A C 0.2246(16) 0.4178(16) 0.5000 0.039(6) Uani 0.5 2 d DS TU P D 2
H1A H 0.2650 0.3575 0.5000 0.047 Uiso 0.5 2 calc RS T P D 2
C1B C 0.189(2) 0.4526(16) 0.5000 0.033(5) Uani 0.5 2 d DS TU P D 1
H1B H 0.1272 0.4901 0.5000 0.040 Uiso 0.5 2 calc RS T P D 1
C2A C 0.1502(13) 0.4265(14) 0.4452(3) 0.070(7) Uani 0.5 1 d D U . D 2
H2AA H 0.1184 0.4908 0.4480 0.084 Uiso 0.5 1 calc R . . D 2
H2AB H 0.1854 0.4238 0.4041 0.084 Uiso 0.5 1 calc R . . D 2
C2B C 0.2004(13) 0.3767(13) 0.4454(3) 0.066(6) Uani 0.5 1 d D U . D 1
H2BA H 0.1987 0.4111 0.4039 0.080 Uiso 0.5 1 calc R . . D 1
H2BB H 0.2647 0.3451 0.4492 0.080 Uiso 0.5 1 calc R . . D 1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O3 1.989(5) 6_565 ?
Ti1 O3 1.989(5) . ?
Ti1 O4 1.817(2) 28 ?
Ti1 O4 1.817(2) . ?
Ti1 O5 2.084(5) . ?
Ti1 O5 2.085(5) 6_565 ?
S2 O1 1.431(8) . ?
S2 O2 1.449(8) . ?
S2 O3 1.501(5) 32_455 ?
S2 O3 1.501(5) . ?
O4 Ti1 1.817(2) 27_455 ?
O5 H5A 0.8873 . ?
O5 H5B 0.8871 . ?
S1 O6 1.453(9) . ?
S1 O7 1.454(6) . ?
S1 O9 1.452(9) . ?
O6 O7 1.643(19) 4_565 ?
O6 O7 1.67(3) 2_665 ?
O6 O8 1.56(3) 20_656 ?
O6 O8 1.18(2) 17_666 ?
O6 O9 0.750(18) 3_655 ?
O6 O9 1.35(2) 2_665 ?
O7 O6 1.67(3) 2_665 ?
O7 O6 1.643(19) 3_655 ?
O7 O7 1.59(3) 2_665 ?
O7 O7 1.12(2) 4_565 ?
O7 O7 1.12(2) 3_655 ?
O7 O9 1.678(19) 4_565 ?
O8 O6 1.56(3) 19_566 ?
O8 O6 1.18(2) 17_666 ?
O8 O8 1.66(2) 3_655 ?
O8 O8 1.66(2) 4_565 ?
O8 O9 1.05(2) 18_556 ?
O8 O9 1.57(3) 19_566 ?
O9 O6 1.35(2) 2_665 ?
O9 O6 0.750(18) 4_565 ?
O9 O7 1.678(19) 3_655 ?
O9 O8 1.57(3) 20_656 ?
O9 O8 1.05(2) 18_556 ?
N1 H1AA 0.9100 . ?
N1 H1AC 0.9100 . ?
N1 H1AB 0.9100 . ?
N1 H1BE 0.9100 . ?
N1 H1BF 0.9100 . ?
N1 H1BD 0.9100 . ?
N1 C1A 1.520(17) . ?
N1 C1B 1.51(3) . ?
C1A H1A 1.0000 . ?
C1A C2A 1.542(16) . ?
C1A C2A 1.542(16) 18_556 ?
C1B H1B 1.0000 . ?
C1B C2B 1.557(16) 18_556 ?
C1B C2B 1.557(16) . ?
C2A C2A 1.494(14) 31 ?
C2A H2AA 0.9900 . ?
C2A H2AB 0.9900 . ?
C2B C2B 1.501(14) 31 ?
C2B H2BA 0.9900 . ?
C2B H2BB 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O3 Ti1 O3 167.8(3) . 6_565 ?
O3 Ti1 O5 79.9(2) . 6_565 ?
O3 Ti1 O5 90.9(2) 6_565 6_565 ?
O3 Ti1 O5 90.9(2) . . ?
O3 Ti1 O5 79.9(2) 6_565 . ?
O4 Ti1 O3 98.8(3) . . ?
O4 Ti1 O3 89.0(3) . 6_565 ?
O4 Ti1 O3 98.8(3) 28 6_565 ?
O4 Ti1 O3 89.0(3) 28 . ?
O4 Ti1 O4 99.9(5) . 28 ?
O4 Ti1 O5 90.5(3) . 6_565 ?
O4 Ti1 O5 90.5(3) 28 . ?
O4 Ti1 O5 165.9(3) 28 6_565 ?
O4 Ti1 O5 165.9(3) . . ?
O5 Ti1 O5 81.0(3) . 6_565 ?
O1 S2 O2 114.5(5) . . ?
O1 S2 O3 109.1(3) . . ?
O1 S2 O3 109.1(3) . 32_455 ?
O2 S2 O3 108.2(3) . . ?
O2 S2 O3 108.2(3) . 32_455 ?
O3 S2 O3 107.4(5) 32_455 . ?
S2 O3 Ti1 134.2(3) . . ?
Ti1 O4 Ti1 145.6(4) . 27_455 ?
Ti1 O5 H5A 110.6 . . ?
Ti1 O5 H5B 110.3 . . ?
H5A O5 H5B 103.5 . . ?
O6 S1 O7 109.2(9) . . ?
O9 S1 O6 109.5(9) . . ?
O9 S1 O7 108.9(9) . . ?
S1 O6 O7 60.3(7) . 4_565 ?
S1 O6 O7 62.4(10) . 2_665 ?
S1 O6 O8 67.7(11) . 20_656 ?
O7 O6 O7 39.5(11) 4_565 2_665 ?
O8 O6 S1 75.4(10) 17_666 . ?
O8 O6 O7 137.4(15) 17_666 2_665 ?
O8 O6 O7 113.9(13) 17_666 4_565 ?
O8 O6 O7 94.6(14) 20_656 2_665 ?
O8 O6 O7 122.1(14) 20_656 4_565 ?
O8 O6 O8 73.2(18) 17_666 20_656 ?
O8 O6 O9 48.4(12) 17_666 2_665 ?
O9 O6 S1 87.5(17) 3_655 . ?
O9 O6 S1 61.3(14) 2_665 . ?
O9 O6 O7 78(2) 3_655 2_665 ?
O9 O6 O7 67.3(9) 2_665 4_565 ?
O9 O6 O7 116(3) 3_655 4_565 ?
O9 O6 O7 102.3(14) 2_665 2_665 ?
O9 O6 O8 107(3) 3_655 17_666 ?
O9 O6 O8 35.9(19) 3_655 20_656 ?
O9 O6 O8 108.4(17) 2_665 20_656 ?
O9 O6 O9 143(3) 3_655 2_665 ?
S1 O7 O6 45.7(8) . 3_655 ?
S1 O7 O6 43.0(11) . 2_665 ?
S1 O7 O7 64.7(7) . 2_665 ?
S1 O7 O9 46.8(8) . 4_565 ?
O6 O7 O6 67.6(10) 3_655 2_665 ?
O6 O7 O9 25.9(7) 2_665 4_565 ?
O6 O7 O9 48.1(8) 3_655 4_565 ?
O7 O7 S1 73.5(6) 4_565 . ?
O7 O7 S1 71.2(7) 3_655 . ?
O7 O7 O6 116.9(7) 3_655 3_655 ?
O7 O7 O6 71.6(15) 4_565 3_655 ?
O7 O7 O6 116.4(7) 4_565 2_665 ?
O7 O7 O6 93.4(11) 2_665 2_665 ?
O7 O7 O6 95.5(13) 2_665 3_655 ?
O7 O7 O6 68.8(13) 3_655 2_665 ?
O7 O7 O7 89.999(8) 4_565 3_655 ?
O7 O7 O7 44.999(7) 4_565 2_665 ?
O7 O7 O7 44.999(4) 3_655 2_665 ?
O7 O7 O9 94.3(13) 3_655 4_565 ?
O7 O7 O9 113.8(8) 4_565 4_565 ?
O7 O7 O9 109.8(9) 2_665 4_565 ?
O6 O8 O6 83.3(13) 17_666 19_566 ?
O6 O8 O8 42.7(10) 19_566 3_655 ?
O6 O8 O8 64.1(16) 17_666 4_565 ?
O6 O8 O8 106.1(7) 19_566 4_565 ?
O6 O8 O8 111.6(9) 17_666 3_655 ?
O6 O8 O9 27.2(11) 17_666 19_566 ?
O6 O8 O9 98.5(9) 19_566 19_566 ?
O8 O8 O8 89.998(7) 3_655 4_565 ?
O9 O8 O6 24.8(13) 18_556 19_566 ?
O9 O8 O6 74.6(13) 18_556 17_666 ?
O9 O8 O8 37.8(11) 19_566 4_565 ?
O9 O8 O8 109.5(8) 19_566 3_655 ?
O9 O8 O8 120.0(11) 18_556 4_565 ?
O9 O8 O8 66.4(18) 18_556 3_655 ?
O9 O8 O9 97.7(16) 18_556 19_566 ?
S1 O9 O7 57.7(7) . 3_655 ?
S1 O9 O8 67.5(10) . 20_656 ?
O6 O9 S1 48.8(13) 2_665 . ?
O6 O9 S1 71.7(17) 4_565 . ?
O6 O9 O6 120(3) 4_565 2_665 ?
O6 O9 O7 64.6(9) 2_665 3_655 ?
O6 O9 O7 77(2) 4_565 3_655 ?
O6 O9 O8 119(3) 4_565 18_556 ?
O6 O9 O8 46(2) 4_565 20_656 ?
O6 O9 O8 107.6(18) 2_665 20_656 ?
O8 O9 S1 72.3(11) 18_556 . ?
O8 O9 O6 56.9(12) 18_556 2_665 ?
O8 O9 O7 119.4(13) 18_556 3_655 ?
O8 O9 O7 109.9(15) 20_656 3_655 ?
O8 O9 O8 75.8(19) 18_556 20_656 ?
H1AA N1 H1AC 109.5 . . ?
H1AA N1 H1AB 109.5 . . ?
H1AC N1 H1AB 109.5 . . ?
H1BE N1 H1BF 109.5 . . ?
H1BE N1 H1BD 109.5 . . ?
H1BF N1 H1BD 109.5 . . ?
C1A N1 H1BE 109.5 . . ?
C1A N1 H1BF 109.5 . . ?
C1A N1 H1BD 109.5 . . ?
C1B N1 H1AA 109.5 . . ?
C1B N1 H1AC 109.5 . . ?
C1B N1 H1AB 109.5 . . ?
N1 C1A H1A 115.7 . . ?
N1 C1A C2A 105.7(12) . . ?
N1 C1A C2A 105.7(12) . 18_556 ?
C2A C1A H1A 115.7 . . ?
C2A C1A H1A 115.7 18_556 . ?
C2A C1A C2A 96.0(15) . 18_556 ?
N1 C1B H1B 115.4 . . ?
N1 C1B C2B 106.9(14) . 18_556 ?
N1 C1B C2B 106.9(14) . . ?
C2B C1B H1B 115.4 . . ?
C2B C1B H1B 115.4 18_556 . ?
C2B C1B C2B 94.6(14) . 18_556 ?
C1A C2A H2AA 108.6 . . ?
C1A C2A H2AB 108.6 . . ?
C2A C2A C1A 114.5(8) 31 . ?
C2A C2A H2AA 108.6 31 . ?
C2A C2A H2AB 108.6 31 . ?
H2AA C2A H2AB 107.6 . . ?
C1B C2B H2BA 108.8 . . ?
C1B C2B H2BB 108.8 . . ?
C2B C2B C1B 114.0(10) 31 . ?
C2B C2B H2BA 108.8 31 . ?
C2B C2B H2BB 108.8 31 . ?
H2BA C2B H2BB 107.7 . . ?

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 S2 O3 Ti1 163.6(5) . . . . ?
O2 S2 O3 Ti1 -71.2(6) . . . . ?
O3 Ti1 O4 Ti1 -32.8(7) 6_565 . . 27_455 ?
O3 Ti1 O4 Ti1 156.5(7) . . . 27_455 ?
O3 S2 O3 Ti1 45.5(7) 32_455 . . . ?
O4 Ti1 O4 Ti1 66.0(7) 28 . . 27_455 ?
O5 Ti1 O4 Ti1 -70.8(15) . . . 27_455 ?
O5 Ti1 O4 Ti1 -123.7(7) 6_565 . . 27_455 ?
O6 S1 O7 O6 -173.4(16) . . . 2_665 ?
O6 S1 O7 O6 81.3(11) . . . 3_655 ?
O6 S1 O7 O7 -46.3(16) . . . 2_665 ?
O6 S1 O7 O7 -94.6(17) . . . 3_655 ?
O6 S1 O7 O7 1.2(16) . . . 4_565 ?
O6 S1 O7 O9 150.0(15) . . . 4_565 ?
O6 S1 O9 O6 -176.0(18) . . . 2_665 ?
O6 S1 O9 O6 15.6(18) . . . 4_565 ?
O6 S1 O9 O7 101.0(13) . . . 3_655 ?
O6 S1 O9 O8 -114.8(17) . . . 18_556 ?
O6 S1 O9 O8 -33.2(12) . . . 20_656 ?
O7 S1 O6 O7 -0.9(12) . . . 4_565 ?
O7 S1 O6 O7 44.4(14) . . . 2_665 ?
O7 S1 O6 O8 152.5(14) . . . 20_656 ?
O7 S1 O6 O8 -130.0(16) . . . 17_666 ?
O7 S1 O6 O9 -79.7(16) . . . 2_665 ?
O7 S1 O6 O9 122(2) . . . 3_655 ?
O7 S1 O9 O6 64.6(16) . . . 2_665 ?
O7 S1 O9 O6 -104(2) . . . 4_565 ?
O7 S1 O9 O7 -18.4(12) . . . 3_655 ?
O7 S1 O9 O8 -152.6(14) . . . 20_656 ?
O7 S1 O9 O8 125.8(17) . . . 18_556 ?
O9 S1 O6 O7 -120.0(14) . . . 4_565 ?
O9 S1 O6 O7 -74.8(14) . . . 2_665 ?
O9 S1 O6 O8 110.9(15) . . . 17_666 ?
O9 S1 O6 O8 33.3(12) . . . 20_656 ?
O9 S1 O6 O9 2.5(19) . . . 3_655 ?
O9 S1 O6 O9 161.2(17) . . . 2_665 ?
O9 S1 O7 O6 -159.2(14) . . . 3_655 ?
O9 S1 O7 O6 -53.8(12) . . . 2_665 ?
O9 S1 O7 O7 73.2(18) . . . 2_665 ?
O9 S1 O7 O7 24.9(17) . . . 3_655 ?
O9 S1 O7 O7 120.7(18) . . . 4_565 ?
O9 S1 O7 O9 -90.5(11) . . . 4_565 ?
N1 C1A C2A C2A -167.7(8) . . . 31 ?
N1 C1B C2B C2B 170.4(8) . . . 31 ?
C2A C1A C2A C2A -59.5(15) 18_556 . . 31 ?
C2B C1B C2B C2B 61.2(16) 18_556 . . 31 ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.778

# start Validation Reply Form
_vrf_PLAT417_ti4-chexda          
;
PROBLEM: Short Inter D-H..H-D H5A ..H5A . 1.67 Ang.
RESPONSE: This problem is caused by the disorder of the atoms.
;
# 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_ti4-hmta
_database_code_depnum_ccdc_archive 'CCDC 1977581'
loop_
_audit_author_name
_audit_author_address
'Yifeng Wang'
;Shandong University
China
;
_audit_update_record             
;
2020-04-01 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_audit_creation_date             2020-03-09
_audit_creation_method           
;
Olex2 1.3-dev
(compiled 2020.03.04 svn.rc2590c38 for OlexSys, GUI svn.r5830)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'H8 O40 S8 Ti4, 10[H2O]'
_chemical_formula_sum            'H28 O50 S8 Ti4'
_chemical_formula_weight         1276.30
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           122
_space_group_name_H-M_alt        'I -4 2 d'
_space_group_name_Hall           'I -4 2bw'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'y, -x, -z'
'-y, x, -z'
'-x+1/2, y, -z+3/4'
'x+1/2, -y, -z+3/4'
'-y+1/2, -x, z+3/4'
'y+1/2, x, z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'-x+1, y+1/2, -z+5/4'
'x+1, -y+1/2, -z+5/4'
'-y+1, -x+1/2, z+5/4'
'y+1, x+1/2, z+5/4'

_cell_length_a                   24.0919(2)
_cell_length_b                   24.0919(2)
_cell_length_c                   23.1592(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     13442.1(3)
_cell_formula_units_Z            12
_cell_measurement_reflns_used    11452
_cell_measurement_temperature    173
_cell_measurement_theta_max      76.4890
_cell_measurement_theta_min      2.5990
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.586
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.53281
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.892
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             7728
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            17257
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.480
_diffrn_reflns_theta_min         2.647
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       ?
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   ?
_reflns_Friedel_coverage         0.810
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.927
_reflns_number_gt                6032
_reflns_number_total             6388
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_refine_diff_density_max         0.537
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details 
;
 Flack x determined using 2505 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.019(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         6388
_refine_ls_number_restraints     359
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0439
_refine_ls_restrained_S_all      1.091
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0396P)²+117.7442P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1065
_refine_ls_wR_factor_ref         0.1175
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 O17-O1A \\sim O17-O1B \\sim O1A-O1B \\sim O1B-O1C
 with sigma of 0.002
 S1-O17 \\sim S1-O1A \\sim S1-O1B \\sim S1-O1C
 with sigma of 0.001
 O17-O1A \\sim O17A-O31
 with sigma of 0.04
 Ti1-O17 \\sim Ti1-O17A
 with sigma of 0.02
 S1-O17 \\sim S1A-O17A
 with sigma of 0.02
 S1-O1A \\sim S1A-O31
 with sigma of 0.02
 S1-O1B \\sim S1A-O1D
 with sigma of 0.02
 O1A-O1C \\sim O31-O1E
 with sigma of 0.04
 S1-O1C \\sim S1A-O1E
 with sigma of 0.02
 O17-O1C \\sim O17A-O1E
 with sigma of 0.04
 O17-O1B \\sim O17A-O1D
 with sigma of 0.04
 O1A-O1B \\sim O31-O1D
 with sigma of 0.04
 O1B-O1C \\sim O1D-O1E
 with sigma of 0.04
 Ti1-S1 \\sim Ti1-S1A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(S1A)=Sof(O17A)=Sof(O31)=Sof(O1D)=Sof(O1E)=1-FVAR(1)
 Sof(S1)=Sof(O17)=Sof(O1A)=Sof(O1B)=Sof(O1C)=FVAR(1)
5.a Rotating group:
 O24(H24A,H24B), O9(H9A,H9B), O4(H4A,H4B)
;
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
Ti3 Ti 0.50393(5) 0.60242(5) 0.49664(5) 0.0161(3) Uani 1 1 d . . . . .
Ti1 Ti 0.61455(5) 0.76895(5) 0.22808(5) 0.0170(3) Uani 1 1 d D . . . .
Ti2 Ti 0.62134(5) 0.64919(5) 0.14661(5) 0.0184(3) Uani 1 1 d . . . . .
S5 S 0.50992(7) 0.68088(7) 0.21886(8) 0.0212(4) Uani 1 1 d . . . . .
S10 S 0.59494(7) 0.69196(8) 0.44470(8) 0.0218(4) Uani 1 1 d . . . . .
S15 S 0.57799(8) 0.58140(8) 0.61256(8) 0.0250(4) Uani 1 1 d . . . . .
S20 S 0.68409(9) 0.57615(9) 0.24516(8) 0.0315(5) Uani 1 1 d . . . . .
S25 S 0.54891(10) 0.86488(8) 0.30195(11) 0.0362(5) Uani 1 1 d . . . . .
O2 O 0.5961(2) 0.8075(2) 0.1688(2) 0.0198(9) Uani 1 1 d . . . . .
O22 O 0.5412(2) 0.6702(2) 0.4680(3) 0.0329(12) Uani 1 1 d . . . . .
O5 O 0.5920(2) 0.8211(2) 0.2898(2) 0.0269(10) Uani 1 1 d . . . . .
O24 O 0.4476(2) 0.6642(2) 0.5293(3) 0.0280(12) Uani 1 1 d . . . . .
H24A H 0.418935 0.648553 0.545060 0.042 Uiso 1 1 d R U . . .
H24B H 0.433549 0.683190 0.501106 0.042 Uiso 1 1 d R U . . .
O23 O 0.5525(2) 0.5533(2) 0.4759(2) 0.0217(10) Uani 1 1 d . . . . .
O13 O 0.5460(2) 0.6466(2) 0.1810(2) 0.0257(10) Uani 1 1 d . . . . .
O14 O 0.6452(2) 0.5858(2) 0.1957(2) 0.0298(11) Uani 1 1 d . . . . .
O9 O 0.6441(2) 0.7250(2) 0.3034(2) 0.0274(11) Uani 1 1 d . . . . .
H9A H 0.629773 0.739435 0.334164 0.041 Uiso 1 1 d R U . . .
H9B H 0.631714 0.691394 0.303537 0.041 Uiso 1 1 d R U . . .
O3 O 0.6420(2) 0.7040(2) 0.1901(2) 0.0181(9) Uani 1 1 d . . . . .
O4 O 0.5899(3) 0.5810(2) 0.0971(3) 0.0333(13) Uani 1 1 d . . . . .
H4A H 0.616807 0.563662 0.080451 0.050 Uiso 1 1 d R U . . .
H4B H 0.570195 0.593298 0.068677 0.050 Uiso 1 1 d R U . . .
O25 O 0.5376(2) 0.6110(2) 0.5739(2) 0.0280(11) Uani 1 1 d . . . . .
O20 O 0.5813(3) 0.7302(3) 0.3981(3) 0.0371(14) Uani 1 1 d . . . . .
O15 O 0.7405(3) 0.5813(3) 0.2231(3) 0.0424(14) Uani 1 1 d . . . . .
O27 O 0.6189(3) 0.6193(3) 0.6315(4) 0.060(2) Uani 1 1 d . . . . .
O18 O 0.6702(4) 0.6155(4) 0.2905(3) 0.063(2) Uani 1 1 d . . . . .
O19 O 0.6280(3) 0.6458(3) 0.4229(3) 0.0451(15) Uani 1 1 d . . . . .
O8 O 0.5013(3) 0.8385(3) 0.3277(4) 0.058(2) Uani 1 1 d . . . . .
O11 O 0.4951(4) 0.6488(3) 0.2681(3) 0.0570(19) Uani 1 1 d . . . . .
O28 O 0.5467(3) 0.5574(4) 0.6599(3) 0.062(2) Uani 1 1 d . . . . .
O21 O 0.6228(3) 0.7218(4) 0.4902(3) 0.0598(19) Uani 1 1 d . . . . .
O6 O 0.5318(4) 0.8889(4) 0.2471(4) 0.073(2) Uani 1 1 d . . . . .
O12 O 0.4622(3) 0.6984(4) 0.1858(4) 0.069(2) Uani 1 1 d . . . . .
O16 O 0.6733(3) 0.5199(3) 0.2658(4) 0.0589(19) Uani 1 1 d . . . . .
O7 O 0.5715(4) 0.9055(4) 0.3379(4) 0.078(3) Uani 1 1 d . . . . .
O10 O 0.5415(2) 0.7309(2) 0.2385(2) 0.0274(11) Uani 1 1 d . . . . .
O26 O 0.6044(2) 0.5357(2) 0.5798(2) 0.0294(12) Uani 1 1 d . . . . .
S1 S 0.7230(3) 0.8416(3) 0.1998(4) 0.0183(19) Uani 0.495(17) 1 d D . P A 1
O17 O 0.6928(6) 0.7966(5) 0.2288(7) 0.022(2) Uani 0.495(17) 1 d D . P A 1
O1A O 0.6991(8) 0.8521(6) 0.1425(5) 0.027(4) Uani 0.495(17) 1 d D . P A 1
O1B O 0.7213(7) 0.8923(4) 0.2349(5) 0.045(4) Uani 0.495(17) 1 d D . P A 1
O1C O 0.7807(4) 0.8238(6) 0.1908(6) 0.042(4) Uani 0.495(17) 1 d D . P A 1
S1A S 0.7266(4) 0.8359(4) 0.1892(5) 0.0245(18) Uani 0.505(17) 1 d D . P A 2
O17A O 0.6885(6) 0.8064(6) 0.2317(7) 0.020(2) Uani 0.505(17) 1 d D . P A 2
O31 O 0.6904(7) 0.8658(8) 0.1465(6) 0.020(3) Uani 0.505(17) 1 d D . P A 2
O1D O 0.7574(6) 0.8762(5) 0.2208(5) 0.036(4) Uani 0.505(17) 1 d D . P A 2
O1E O 0.7597(6) 0.7954(6) 0.1584(6) 0.045(4) Uani 0.505(17) 1 d D . P A 2


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti3 O22 1.978(6) . ?
Ti3 O24 2.152(5) . ?
Ti3 O23 1.732(5) . ?
Ti3 O23 1.937(5) 4_656 ?
Ti3 O25 1.976(5) . ?
Ti3 O26 2.013(6) 4_656 ?
Ti1 O2 1.715(5) . ?
Ti1 O5 1.978(5) . ?
Ti1 O9 2.162(5) . ?
Ti1 O3 1.914(5) . ?
Ti1 O10 1.999(5) . ?
Ti1 O17 1.998(12) . ?
Ti1 O17A 1.999(12) . ?
Ti2 O2 1.938(5) 14_464 ?
Ti2 O13 1.984(5) . ?
Ti2 O14 1.988(5) . ?
Ti2 O3 1.733(5) . ?
Ti2 O4 2.142(6) . ?
Ti2 O1A 2.080(17) 14_464 ?
Ti2 O31 1.973(14) 14_464 ?
S5 O13 1.486(5) . ?
S5 O11 1.422(7) . ?
S5 O12 1.444(7) . ?
S5 O10 1.495(6) . ?
S10 O22 1.498(6) . ?
S10 O20 1.456(6) . ?
S10 O19 1.459(7) . ?
S10 O21 1.442(7) . ?
S15 O25 1.502(6) . ?
S15 O27 1.414(7) . ?
S15 O28 1.451(8) . ?
S15 O26 1.480(6) . ?
S20 O14 1.499(6) . ?
S20 O15 1.457(7) . ?
S20 O18 1.454(7) . ?
S20 O16 1.461(8) . ?
S25 O5 1.507(6) . ?
S25 O8 1.440(7) . ?
S25 O6 1.456(9) . ?
S25 O7 1.396(8) . ?
O24 H24A 0.8678 . ?
O24 H24B 0.8669 . ?
O9 H9A 0.8636 . ?
O9 H9B 0.8631 . ?
O4 H4A 0.8629 . ?
O4 H4B 0.8631 . ?
S1 O17 1.469(6) . ?
S1 O1A 1.469(6) . ?
S1 O1B 1.469(6) . ?
S1 O1C 1.469(6) . ?
S1A O17A 1.522(12) . ?
S1A O31 1.502(12) . ?
S1A O1D 1.422(13) . ?
S1A O1E 1.449(14) . ?

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
O22 Ti3 O24 80.4(2) . . ?
O22 Ti3 O26 84.3(2) . 4_656 ?
O23 Ti3 O22 99.5(2) . . ?
O23 Ti3 O22 161.0(2) 4_656 . ?
O23 Ti3 O24 82.3(2) 4_656 . ?
O23 Ti3 O24 174.9(2) . . ?
O23 Ti3 O23 98.5(3) . 4_656 ?
O23 Ti3 O25 92.6(2) . . ?
O23 Ti3 O25 93.4(2) 4_656 . ?
O23 Ti3 O26 95.4(3) . 4_656 ?
O23 Ti3 O26 88.0(2) 4_656 4_656 ?
O25 Ti3 O22 91.8(3) . . ?
O25 Ti3 O24 82.4(2) . . ?
O25 Ti3 O26 171.6(2) . 4_656 ?
O26 Ti3 O24 89.7(2) 4_656 . ?
O2 Ti1 O5 99.4(2) . . ?
O2 Ti1 O9 175.0(2) . . ?
O2 Ti1 O3 99.5(2) . . ?
O2 Ti1 O10 96.7(2) . . ?
O2 Ti1 O17 94.1(5) . . ?
O2 Ti1 O17A 91.1(5) . . ?
O5 Ti1 O9 79.5(2) . . ?
O5 Ti1 O10 87.8(2) . . ?
O5 Ti1 O17 92.4(5) . . ?
O5 Ti1 O17A 85.9(5) . . ?
O3 Ti1 O5 161.1(2) . . ?
O3 Ti1 O9 81.8(2) . . ?
O3 Ti1 O10 89.1(2) . . ?
O3 Ti1 O17 87.2(4) . . ?
O3 Ti1 O17A 94.6(5) . . ?
O10 Ti1 O9 88.2(2) . . ?
O10 Ti1 O17A 170.7(5) . . ?
O17 Ti1 O9 81.1(5) . . ?
O17 Ti1 O10 169.1(5) . . ?
O17A Ti1 O9 83.9(5) . . ?
O2 Ti2 O13 92.5(2) 14_464 . ?
O2 Ti2 O14 162.0(2) 14_464 . ?
O2 Ti2 O4 83.3(2) 14_464 . ?
O2 Ti2 O1A 87.1(5) 14_464 14_464 ?
O2 Ti2 O31 88.1(5) 14_464 14_464 ?
O13 Ti2 O14 90.6(2) . . ?
O13 Ti2 O4 82.3(2) . . ?
O13 Ti2 O1A 176.6(4) . 14_464 ?
O14 Ti2 O4 79.6(2) . . ?
O14 Ti2 O1A 88.7(5) . 14_464 ?
O3 Ti2 O2 97.7(2) . 14_464 ?
O3 Ti2 O13 93.1(2) . . ?
O3 Ti2 O14 99.8(2) . . ?
O3 Ti2 O4 175.4(2) . . ?
O3 Ti2 O1A 90.3(4) . 14_464 ?
O3 Ti2 O31 101.0(5) . 14_464 ?
O1A Ti2 O4 94.3(4) 14_464 . ?
O31 Ti2 O13 165.6(5) 14_464 . ?
O31 Ti2 O14 84.6(5) 14_464 . ?
O31 Ti2 O4 83.5(5) 14_464 . ?
O13 S5 O10 109.3(3) . . ?
O11 S5 O13 108.5(4) . . ?
O11 S5 O12 112.6(6) . . ?
O11 S5 O10 108.7(4) . . ?
O12 S5 O13 108.4(4) . . ?
O12 S5 O10 109.3(4) . . ?
O20 S10 O22 107.0(4) . . ?
O20 S10 O19 110.5(4) . . ?
O19 S10 O22 109.3(4) . . ?
O21 S10 O22 108.3(4) . . ?
O21 S10 O20 109.3(5) . . ?
O21 S10 O19 112.3(5) . . ?
O27 S15 O25 109.3(4) . . ?
O27 S15 O28 112.7(6) . . ?
O27 S15 O26 109.8(4) . . ?
O28 S15 O25 107.6(4) . . ?
O28 S15 O26 108.3(4) . . ?
O26 S15 O25 109.1(3) . . ?
O15 S20 O14 107.6(3) . . ?
O15 S20 O16 111.1(5) . . ?
O18 S20 O14 107.9(4) . . ?
O18 S20 O15 114.3(5) . . ?
O18 S20 O16 109.1(5) . . ?
O16 S20 O14 106.5(4) . . ?
O8 S25 O5 108.5(4) . . ?
O8 S25 O6 108.1(6) . . ?
O6 S25 O5 108.1(4) . . ?
O7 S25 O5 109.5(5) . . ?
O7 S25 O8 111.9(5) . . ?
O7 S25 O6 110.7(6) . . ?
Ti1 O2 Ti2 146.7(3) . 14_464 ?
S10 O22 Ti3 143.3(4) . . ?
S25 O5 Ti1 140.3(4) . . ?
Ti3 O24 H24A 110.4 . . ?
Ti3 O24 H24B 110.2 . . ?
H24A O24 H24B 103.5 . . ?
Ti3 O23 Ti3 144.6(3) . 3_566 ?
S5 O13 Ti2 139.0(3) . . ?
S20 O14 Ti2 137.5(4) . . ?
Ti1 O9 H9A 109.7 . . ?
Ti1 O9 H9B 110.4 . . ?
H9A O9 H9B 103.7 . . ?
Ti2 O3 Ti1 142.3(3) . . ?
Ti2 O4 H4A 110.2 . . ?
Ti2 O4 H4B 109.9 . . ?
H4A O4 H4B 103.8 . . ?
S15 O25 Ti3 139.1(3) . . ?
S5 O10 Ti1 141.3(3) . . ?
S15 O26 Ti3 142.5(3) . 3_566 ?
O17 S1 O1A 110.3(4) . . ?
O1B S1 O17 110.2(4) . . ?
O1B S1 O1A 110.3(4) . . ?
O1C S1 O17 108.6(9) . . ?
O1C S1 O1A 107.1(10) . . ?
O1C S1 O1B 110.3(4) . . ?
S1 O17 Ti1 135.2(11) . . ?
S1 O1A Ti2 138.0(13) . 14_464 ?
O31 S1A O17A 107.4(9) . . ?
O1D S1A O17A 107.5(9) . . ?
O1D S1A O31 108.4(10) . . ?
O1D S1A O1E 115.2(11) . . ?
O1E S1A O17A 109.5(10) . . ?
O1E S1A O31 108.5(10) . . ?
S1A O17A Ti1 136.2(11) . . ?

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
O2 Ti2 O3 Ti1 60.8(5) 14_464 . . . ?
O22 Ti3 O23 Ti3 119.6(5) . . . 3_566 ?
O5 Ti1 O2 Ti2 108.7(5) . . . 14_464 ?
O23 Ti3 O23 Ti3 -66.5(5) 4_656 . . 3_566 ?
O13 Ti2 O3 Ti1 -32.1(5) . . . . ?
O13 S5 O10 Ti1 3.9(7) . . . . ?
O14 Ti2 O3 Ti1 -123.3(5) . . . . ?
O3 Ti1 O2 Ti2 -72.2(6) . . . 14_464 ?
O25 Ti3 O23 Ti3 27.3(6) . . . 3_566 ?
O25 S15 O26 Ti3 -5.1(8) . . . 3_566 ?
O20 S10 O22 Ti3 139.3(7) . . . . ?
O15 S20 O14 Ti2 -70.3(6) . . . . ?
O27 S15 O25 Ti3 128.6(6) . . . . ?
O27 S15 O26 Ti3 -124.8(7) . . . 3_566 ?
O18 S20 O14 Ti2 53.6(7) . . . . ?
O19 S10 O22 Ti3 19.6(8) . . . . ?
O8 S25 O5 Ti1 89.4(7) . . . . ?
O11 S5 O13 Ti2 -121.8(6) . . . . ?
O11 S5 O10 Ti1 122.2(7) . . . . ?
O28 S15 O25 Ti3 -108.8(7) . . . . ?
O28 S15 O26 Ti3 111.7(7) . . . 3_566 ?
O21 S10 O22 Ti3 -103.0(7) . . . . ?
O6 S25 O5 Ti1 -27.5(7) . . . . ?
O12 S5 O13 Ti2 115.6(7) . . . . ?
O12 S5 O10 Ti1 -114.6(7) . . . . ?
O16 S20 O14 Ti2 170.6(5) . . . . ?
O7 S25 O5 Ti1 -148.2(6) . . . . ?
O10 Ti1 O2 Ti2 -162.4(5) . . . 14_464 ?
O10 S5 O13 Ti2 -3.4(7) . . . . ?
O26 Ti3 O23 Ti3 -155.3(5) 4_656 . . 3_566 ?
O26 S15 O25 Ti3 8.5(7) . . . . ?
O17 Ti1 O2 Ti2 15.6(7) . . . 14_464 ?
O17 S1 O1A Ti2 34.7(17) . . . 14_464 ?
O1A Ti2 O3 Ti1 148.0(6) 14_464 . . . ?
O1A S1 O17 Ti1 -31.1(18) . . . . ?
O1B S1 O17 Ti1 90.9(13) . . . . ?
O1B S1 O1A Ti2 -87.3(13) . . . 14_464 ?
O1C S1 O17 Ti1 -148.1(13) . . . . ?
O1C S1 O1A Ti2 152.7(13) . . . 14_464 ?
O17A Ti1 O2 Ti2 22.6(7) . . . 14_464 ?
O17A S1A O31 Ti2 -41(2) . . . 14_464 ?
O31 Ti2 O3 Ti1 150.4(7) 14_464 . . . ?
O31 S1A O17A Ti1 34(2) . . . . ?
O1D S1A O17A Ti1 150.8(14) . . . . ?
O1D S1A O31 Ti2 -157.1(15) . . . 14_464 ?
O1E S1A O17A Ti1 -83.4(18) . . . . ?
O1E S1A O31 Ti2 77.1(18) . . . 14_464 ?

_smtbx_masks_special_details     
;
A solvent mask was calculated and 1249 electrons were
found in a volume of 2687Å^3 in 1 void per unit cell.
This is consistent with the presence of 10[H2O] per Formula Unit 
which account for 1200 electrons per unit cell.
;
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.009 -0.340 0.423 2686.8 1248.6 '120 water'
2 -0.037 0.222 0.864 8.0 8.8 '0.75 water'
3 -0.037 0.278 0.386 8.0 8.8 '0.75 water'
4 0.037 0.722 0.386 8.0 9.0 '0.75 water'
5 0.037 0.778 0.864 8.0 9.1 '0.75 water'
6 0.222 0.037 0.136 8.0 9.0 '0.75 water'
7 0.222 0.463 0.114 8.0 8.9 '0.75 water'
8 0.278 0.037 0.614 8.0 8.9 '0.75 water'
9 0.278 0.463 0.636 8.0 8.9 '0.75 water'
10 0.463 0.722 0.364 8.0 8.8 '0.75 water'
11 0.463 0.778 0.886 8.0 8.8 '0.75 water'
12 0.537 0.222 0.886 8.0 9.0 '0.75 water'
13 0.537 0.278 0.364 8.0 9.1 '0.75 water'
14 0.722 0.537 0.636 8.0 9.0 '0.75 water'
15 0.722 0.963 0.614 8.0 8.9 '0.75 water'
16 0.778 0.537 0.114 8.0 8.9 '0.75 water'
17 0.778 0.963 0.136 8.0 8.9 '0.75 water'

_smtbx_masks_void_probe_radius   1.1
_smtbx_masks_void_truncation_radius 0.8
_olex2_submission_special_instructions 'No special instructions were received'


# start Validation Reply Form
_vrf_PLAT987_ti4-hmta            
;
PROBLEM: The Flack x is >> 0 - Do a BASF/TWIN Refinement Please Check
RESPONSE: We did not make the BASF/TWIN refinement. This is
because the contribution of TWIN is small.
;
# 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_ti4-ocda
_database_code_depnum_ccdc_archive 'CCDC 1977580'
loop_
_audit_author_name
_audit_author_address
'Yifeng Wang'
;Shandong University
China
;
_audit_update_record             
;
2020-03-28 deposited with the CCDC.	2020-04-06 downloaded from the CCDC.
;
_audit_creation_date             2020-03-25
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         
'2(H8 O40 S8 Ti4), 7(C8 H22 N2), 2(C8 H21 N2), 6(H2 O), 3(Cl), O4 S'
_chemical_formula_sum            'C72 H224 Cl3 N18 O90 S17 Ti8'
_chemical_formula_weight         3817.25
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Ti O C SN'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   15.4295(4)
_cell_length_b                   17.3585(5)
_cell_length_c                   18.1126(4)
_cell_angle_alpha                109.769(2)
_cell_angle_beta                 90.193(2)
_cell_angle_gamma                109.105(2)
_cell_volume                     4278.1(2)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    14657
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      75.7490
_cell_measurement_theta_min      2.5590
_shelx_estimated_absorpt_T_max   0.788
_shelx_estimated_absorpt_T_min   0.521
_exptl_absorpt_coefficient_mu    6.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2001
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1331
_diffrn_reflns_av_unetI/netI     0.1130
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42809
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.628
_diffrn_reflns_theta_min         2.614
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.941
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -80.00  22.00   1.00    0.20    --  -48.45  98.00-139.00  102
  2  ω     -8.00  78.00   1.00    0.20    --   48.45 -98.00 113.00   86
  3  ω    -71.00 -13.00   1.00    2.00    --  -86.25  98.00-139.00   58
  4  ω   -122.00 -82.00   1.00    2.00    --  -86.25 -98.00 113.00   40
  5  ω    103.00 147.00   1.00    2.00    --  106.49  98.00-139.00   44
  6  ω     42.00 109.00   1.00    2.00    --  106.49 -98.00 113.00   67
  7  ω    -63.00 -10.00   1.00    0.20    --  -48.45  57.00  60.00   53
  8  ω     -6.00  23.00   1.00    0.20    --  -48.45  57.00  60.00   29
  9  ω    -71.00  23.00   1.00    0.20    --  -48.45  77.00-180.00   94
 10  ω    -61.00  25.00   1.00    0.20    --  -48.45  37.00 150.00   86
 11  ω     36.00 116.00   1.00    2.00    --  106.49-125.00 120.00   80
 12  ω     86.00 178.00   1.00    2.00    --  106.49  77.00 -90.00   92
 13  ω     94.00 178.00   1.00    2.00    --  106.49  61.00-180.00   84
 14  ω     35.00 118.00   1.00    2.00    --  106.49 -45.00 -60.00   83
 15  ω     93.00 178.00   1.00    2.00    --  106.49  15.00-150.00   85
 16  ω     38.00 108.00   1.00    2.00    --  106.49 -94.00-180.00   70
 17  ω     42.00 123.00   1.00    2.00    --  106.49 -61.00-180.00   81
 18  ω     90.00 178.00   1.00    2.00    --  106.49  61.00 -60.00   88
 19  ω     34.00  60.00   1.00    2.00    --  106.49-125.00 -30.00   26
 20  ω     76.00 117.00   1.00    2.00    --  106.49-125.00 -30.00   41
 21  ω     35.00 119.00   1.00    2.00    --  106.49 -61.00 -90.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0062193000
_diffrn_orient_matrix_UB_12      -0.0660323000
_diffrn_orient_matrix_UB_13      -0.0837102000
_diffrn_orient_matrix_UB_21      -0.0773304000
_diffrn_orient_matrix_UB_22      -0.0702734000
_diffrn_orient_matrix_UB_23      0.0193353000
_diffrn_orient_matrix_UB_31      -0.0730295000
_diffrn_orient_matrix_UB_32      0.0287923000
_diffrn_orient_matrix_UB_33      -0.0304010000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                12571
_reflns_number_total             16946
_reflns_odcompleteness_completeness 98.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXL (Sheldrick, 2015)'
_refine_diff_density_max         1.653
_refine_diff_density_min         -1.256
_refine_diff_density_rms         0.209
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     987
_refine_ls_number_reflns         16946
_refine_ls_number_restraints     303
_refine_ls_R_factor_all          0.1876
_refine_ls_R_factor_gt           0.1504
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0820P)²+182.8221P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3949
_refine_ls_wR_factor_ref         0.4155
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 S1_1-O1_1 = S1_1-O2_1 = S1_1-O3_1 = S1_1-O4_1
 1.5 with sigma of 0.02
 C22-C21 = C23-C22 = C24-C23 = C25-C24 = C26-C25 = C27-C26 = C28-C27
 1.45 with sigma of 0.01
 C11-C10 = C9-C10 = C9-C8 = C5-C37 = N6-C5 = C7-C37
 1.45 with sigma of 0.01
 N5-C36 = C36-C35 = C35-C34 = C34-C33 = C33-C32 = C32-C31 = C31-C30 = C30-C29 =
  N4-C29
 1.45 with sigma of 0.01
 C2-C1 = C4-C3
 1.45 with sigma of 0.02
 C16-C15 = C19-C18
 1.45 with sigma of 0.02
 O1_1-O3_1 \\sim O2_1-O4_1 \\sim O1_1-O4_1 \\sim O2_1-O3_1 \\sim O1_1-O2_1
\\sim O3_1-O4_1
 with sigma of 0.04
 O1_1-O2_1 \\sim O3_1-O4_1
 Cl1_2-Cl1_2 \\sim Cl1_2-Cl1_2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C21 \\sim N2 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim
C28 \\sim N3: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C11 \\sim C10 \\sim C9 \\sim C8 \\sim C7 \\sim C37 \\sim C5 \\sim N6 \\sim C12
\\sim N7: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C36 \\sim C35 \\sim C34 \\sim C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim
N4: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O33) \\sim Ueq, Uanis(O30) \\sim Ueq, Uanis(O13) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(O28) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S1_1, O1_1, O2_1, O3_1, O4_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl3(0.5) Cl1(0.5) S1(0.5) O1(0.5) O2(0.5) O3(0.5) O4(0.5) Cl1(0.5)
6.a Riding coordinates:
 N6(H6A,H6B), O39(H39A,H39B), O38(H38A,H38B), O37(H37C,H37D)
6.b Free rotating group:
 O5(H5A,H5B)
6.c Rotating group:
 O25(H25A,H25B), O15(H15A,H15B), O32(H32A,H32B)
6.d Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C13(H13A,H13B), C19(H19A,H19B), C36(H36A,
 H36B), C12(H12A,H12B), C18(H18A,H18B), C28(H28A,H28B), C17(H17A,H17B),
 C16(H16A,H16B), C15(H15C,H15D), C14(H14A,H14B), C11(H11A,H11B), C37(H37A,H37B),
  C22(H22A,H22B), C9(H9D,H9E), C7(H7D,H7E), C24(H24A,H24B), C25(H25C,H25D),
 C35(H35A,H35B), C8(H8D,H8E), C29(H29A,H29B), C27(H27A,H27B), C30(H30A,H30B),
 C32(H32C,H32D), C31(H31A,H31B), C10(H10A,H10B), C23(H23A,H23B), C26(H26A,H26B),
  C33(H33A,H33B), C1(H1D,H1E), C2(H2D,H2E), C3(H3D,H3E), C4(H4D,H4E), C34(H34A,
 H34B), C5(H5F,H5G)
6.e Idealised Me refined as rotating group:
 N8(H8A,H8B,H8C), N7(H7A,H7B,H7C), N9(H9A,H9B,H9C), N3(H3A,H3B,H3C), N2(H2A,
 H2B,H2C), N5(H5C,H5D,H5E), N4(H4A,H4B,H4C), N1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.13101(13) 0.53142(15) 0.85712(13) 0.0259(5) Uani 1 1 d . . . . .
Ti2 Ti 0.35752(13) 0.52764(15) 0.85905(12) 0.0255(5) Uani 1 1 d . . . . .
Ti4 Ti 0.11971(14) 0.49216(17) 0.65372(13) 0.0294(5) Uani 1 1 d . . . . .
Ti3 Ti 0.34763(14) 0.49730(17) 0.65795(13) 0.0314(5) Uani 1 1 d . . . . .
S6 S 0.50623(19) 0.4289(2) 0.85658(17) 0.0286(6) Uani 1 1 d . . . . .
S4 S 0.17566(19) 0.3619(2) 0.85342(17) 0.0280(6) Uani 1 1 d . . . . .
S3 S 0.1724(2) 0.6347(2) 1.04737(19) 0.0342(7) Uani 1 1 d . . . . .
S8 S 0.3631(2) 0.5330(3) 0.49177(19) 0.0370(8) Uani 1 1 d . . . . .
S7 S 0.1763(2) 0.3172(2) 0.56189(19) 0.0366(7) Uani 1 1 d . . . . .
S5 S 0.4875(2) 0.6757(2) 0.7944(2) 0.0359(7) Uani 1 1 d . . . . .
S2 S 0.1407(3) 0.6816(3) 0.7840(2) 0.0428(8) Uani 1 1 d . . . . .
S1 S -0.1064(2) 0.4311(3) 0.6432(3) 0.0488(10) Uani 1 1 d . . . . .
O33 O 0.2508(6) 0.5268(5) 0.6565(5) 0.0281(17) Uani 1 1 d . U . . .
O20 O 0.1167(6) 0.4184(6) 0.8710(5) 0.0327(19) Uani 1 1 d . . . . .
O17 O 0.2510(5) 0.5649(6) 0.8698(5) 0.0281(18) Uani 1 1 d . . . . .
O16 O 0.2756(5) 0.4201(6) 0.8771(5) 0.0285(18) Uani 1 1 d . . . . .
O25 O -0.0178(5) 0.4826(6) 0.8482(5) 0.034(2) Uani 1 1 d . . . . .
H25A H -0.0374 0.4361 0.8622 0.052 Uiso 1 1 d GR . . . .
H25B H -0.0425 0.4621 0.7980 0.052 Uiso 1 1 d GR . . . .
O19 O 0.1549(6) 0.3106(6) 0.9039(6) 0.036(2) Uani 1 1 d . . . . .
O15 O 0.3802(6) 0.6014(6) 0.9862(5) 0.0303(19) Uani 1 1 d . . . . .
H15A H 0.3307 0.5804 1.0106 0.045 Uiso 1 1 d GR . . . .
H15B H 0.4269 0.5941 1.0113 0.045 Uiso 1 1 d GR . . . .
O10 O 0.4637(6) 0.4999(6) 0.8884(5) 0.034(2) Uani 1 1 d . . . . .
O11 O 0.4740(7) 0.3688(7) 0.8992(5) 0.039(2) Uani 1 1 d . . . . .
O9 O 0.4396(6) 0.6413(6) 0.8561(5) 0.034(2) Uani 1 1 d . . . . .
O13 O 0.6068(6) 0.4719(6) 0.8740(5) 0.0330(19) Uani 1 1 d . U . . .
O14 O 0.3442(5) 0.4801(6) 0.7589(5) 0.0278(18) Uani 1 1 d . . . . .
O26 O 0.1206(6) 0.6353(6) 0.8423(5) 0.0318(19) Uani 1 1 d . . . . .
O41 O -0.0141(6) 0.4490(7) 0.6153(6) 0.041(2) Uani 1 1 d . . . . .
O30 O 0.1246(6) 0.6145(6) 0.7028(5) 0.035(2) Uani 1 1 d . U . . .
O4 O 0.3911(6) 0.5080(8) 0.5575(5) 0.043(2) Uani 1 1 d . . . . .
O12 O 0.4784(6) 0.3858(7) 0.7722(5) 0.035(2) Uani 1 1 d . . . . .
O6 O 0.4322(6) 0.6192(7) 0.7167(5) 0.041(2) Uani 1 1 d . . . . .
O34 O 0.2722(6) 0.3717(7) 0.6023(5) 0.039(2) Uani 1 1 d . . . . .
O27 O 0.1095(5) 0.4760(6) 0.7427(5) 0.0318(19) Uani 1 1 d . . . . .
O18 O 0.1600(6) 0.3114(7) 0.7705(6) 0.041(2) Uani 1 1 d . . . . .
O21 O 0.1109(6) 0.5829(6) 0.9680(5) 0.0320(19) Uani 1 1 d . . . . .
O24 O 0.1084(6) 0.6472(7) 1.1059(6) 0.041(2) Uani 1 1 d . . . . .
O31 O 0.1163(6) 0.3718(7) 0.5865(6) 0.041(2) Uani 1 1 d . . . . .
O36 O 0.1782(7) 0.2919(8) 0.4778(6) 0.047(3) Uani 1 1 d . . . . .
O42 O -0.1092(7) 0.3862(8) 0.6976(6) 0.049(3) Uani 1 1 d . . . . .
O22 O 0.2314(7) 0.7177(7) 1.0446(6) 0.049(3) Uani 1 1 d . . . . .
O32 O 0.1260(6) 0.5209(7) 0.5445(6) 0.041(2) Uani 1 1 d . . . . .
H32A H 0.1837 0.5317 0.5300 0.062 Uiso 1 1 d GR . . . .
H32B H 0.1166 0.5718 0.5522 0.062 Uiso 1 1 d GR . . . .
O3 O 0.4466(7) 0.5829(8) 0.4695(6) 0.047(3) Uani 1 1 d . . . . .
O5 O 0.4617(7) 0.4520(9) 0.6567(6) 0.051(3) Uani 1 1 d . . . . .
H5A H 0.5103 0.4767 0.6376 0.076 Uiso 1 1 d G . . . .
H5B H 0.4814 0.4274 0.6844 0.076 Uiso 1 1 d G . . . .
O35 O 0.1435(8) 0.2441(7) 0.5875(7) 0.053(3) Uani 1 1 d . . . . .
N8 N 0.3332(8) 1.3704(9) 1.0006(7) 0.044(3) Uani 1 1 d . . . . .
H8A H 0.3501 1.4261 1.0360 0.053 Uiso 1 1 calc GR . . . .
H8B H 0.2759 1.3548 0.9747 0.053 Uiso 1 1 calc GR . . . .
H8C H 0.3746 1.3672 0.9650 0.053 Uiso 1 1 calc GR . . . .
O23 O 0.2245(7) 0.5829(8) 1.0594(6) 0.047(3) Uani 1 1 d . . . . .
O2 O 0.3129(8) 0.4527(8) 0.4253(6) 0.057(3) Uani 1 1 d . . . . .
O7 O 0.5779(7) 0.6703(10) 0.7934(7) 0.065(4) Uani 1 1 d . . . . .
O8 O 0.4877(10) 0.7636(8) 0.8136(7) 0.064(3) Uani 1 1 d . . . . .
O1 O 0.3066(7) 0.5854(8) 0.5205(7) 0.053(3) Uani 1 1 d . . . . .
N7 N -0.3055(9) -0.2583(9) 0.3068(8) 0.046(3) Uani 1 1 d . U . . .
H7A H -0.3580 -0.3061 0.2877 0.056 Uiso 1 1 calc GR . . . .
H7B H -0.3070 -0.2289 0.3587 0.056 Uiso 1 1 calc GR . . . .
H7C H -0.2554 -0.2755 0.3019 0.056 Uiso 1 1 calc GR . . . .
O29 O 0.2420(9) 0.7303(10) 0.7981(8) 0.080(4) Uani 1 1 d . . . . .
N9 N 0.3456(9) 0.7572(8) 0.9381(8) 0.046(3) Uani 1 1 d . . . . .
H9A H 0.2999 0.7389 0.9665 0.055 Uiso 1 1 calc GR . . . .
H9B H 0.3709 0.7152 0.9178 0.055 Uiso 1 1 calc GR . . . .
H9C H 0.3215 0.7675 0.8980 0.055 Uiso 1 1 calc GR . . . .
N3 N -0.0170(8) 0.2621(9) 0.6759(8) 0.048(3) Uani 1 1 d . U . . .
H3A H -0.0224 0.2265 0.6247 0.057 Uiso 1 1 calc GR . . . .
H3B H 0.0414 0.2780 0.6997 0.057 Uiso 1 1 calc GR . . . .
H3C H -0.0288 0.3106 0.6774 0.057 Uiso 1 1 calc GR . . . .
O28 O 0.0901(11) 0.7346(10) 0.7907(8) 0.081(4) Uani 1 1 d . U . . .
O44 O -0.1754(9) 0.3705(12) 0.5724(9) 0.088(5) Uani 1 1 d . . . . .
N2 N -0.3745(11) -0.3154(10) 0.5517(9) 0.063(4) Uani 1 1 d . U . . .
H2A H -0.4293 -0.3464 0.5197 0.076 Uiso 1 1 calc GR . . . .
H2B H -0.3487 -0.3529 0.5591 0.076 Uiso 1 1 calc GR . . . .
H2C H -0.3356 -0.2808 0.5288 0.076 Uiso 1 1 calc GR . . . .
C20 C 0.3316(13) 1.3118(11) 1.0419(11) 0.057(4) Uani 1 1 d . . . . .
H20A H 0.2825 1.3111 1.0770 0.069 Uiso 1 1 calc R . . . .
H20B H 0.3915 1.3330 1.0753 0.069 Uiso 1 1 calc R . . . .
N5 N -0.6893(12) -0.2685(11) 0.6555(11) 0.079(5) Uani 1 1 d D . . . .
H5C H -0.6810 -0.3078 0.6105 0.095 Uiso 1 1 calc GR . . . .
H5D H -0.7441 -0.2613 0.6481 0.095 Uiso 1 1 calc GR . . . .
H5E H -0.6897 -0.2884 0.6960 0.095 Uiso 1 1 calc GR . . . .
N4 N -0.2829(11) 0.3940(13) 0.7748(11) 0.079(5) Uani 1 1 d D U . . .
H4A H -0.2772 0.4172 0.8285 0.095 Uiso 1 1 calc GR . . . .
H4B H -0.3014 0.4278 0.7539 0.095 Uiso 1 1 calc GR . . . .
H4C H -0.2274 0.3919 0.7593 0.095 Uiso 1 1 calc GR . . . .
C21 C -0.3901(14) -0.2622(14) 0.6265(13) 0.077(6) Uani 1 1 d D U . . .
H21A H -0.4165 -0.2995 0.6576 0.093 Uiso 1 1 calc R . . . .
H21B H -0.4364 -0.2370 0.6174 0.093 Uiso 1 1 calc R . . . .
C13 C 0.4174(13) 0.8382(13) 0.9902(12) 0.067(5) Uani 1 1 d . . . . .
H13A H 0.4487 0.8252 1.0298 0.080 Uiso 1 1 calc R . . . .
H13B H 0.4643 0.8606 0.9582 0.080 Uiso 1 1 calc R . . . .
C19 C 0.3139(15) 1.2204(14) 0.9842(12) 0.074(6) Uani 1 1 d D . . . .
H19A H 0.2549 1.1997 0.9497 0.089 Uiso 1 1 calc R . . . .
H19B H 0.3641 1.2206 0.9504 0.089 Uiso 1 1 calc R . . . .
C36 C -0.6145(17) -0.1856(12) 0.6745(18) 0.117(7) Uani 1 1 d D U . . .
H36A H -0.5988 -0.1762 0.6245 0.141 Uiso 1 1 calc R . . . .
H36B H -0.5594 -0.1895 0.6992 0.141 Uiso 1 1 calc R . . . .
C12 C -0.2994(15) -0.2009(13) 0.2616(12) 0.068(4) Uani 1 1 d . U . . .
H12A H -0.3551 -0.1841 0.2652 0.082 Uiso 1 1 calc R . . . .
H12B H -0.2974 -0.2329 0.2052 0.082 Uiso 1 1 calc R . . . .
C18 C 0.3093(16) 1.1607(12) 1.0268(14) 0.081(7) Uani 1 1 d D . . . .
H18A H 0.3629 1.1883 1.0688 0.097 Uiso 1 1 calc R . . . .
H18B H 0.2526 1.1535 1.0532 0.097 Uiso 1 1 calc R . . . .
C28 C -0.0832(15) 0.2159(14) 0.7174(13) 0.075(5) Uani 1 1 d D U . . .
H28A H -0.0830 0.2579 0.7704 0.090 Uiso 1 1 calc R . . . .
H28B H -0.1458 0.1948 0.6882 0.090 Uiso 1 1 calc R . . . .
C17 C 0.3089(18) 1.0737(14) 0.9775(15) 0.087(7) Uani 1 1 d . . . . .
H17A H 0.3581 1.0806 0.9427 0.104 Uiso 1 1 calc R . . . .
H17B H 0.2489 1.0409 0.9431 0.104 Uiso 1 1 calc R . . . .
C16 C 0.3238(17) 1.0211(13) 1.0238(14) 0.086(7) Uani 1 1 d D . . . .
H16A H 0.3740 1.0598 1.0679 0.103 Uiso 1 1 calc R . . . .
H16B H 0.2668 1.0011 1.0474 0.103 Uiso 1 1 calc R . . . .
C15 C 0.3477(16) 0.9442(12) 0.9783(13) 0.078(6) Uani 1 1 d D . . . .
H15C H 0.3976 0.9615 0.9466 0.094 Uiso 1 1 calc R . . . .
H15D H 0.2930 0.8994 0.9412 0.094 Uiso 1 1 calc R . . . .
C14 C 0.3788(15) 0.9059(13) 1.0312(12) 0.074(6) Uani 1 1 d . . . . .
H14A H 0.4262 0.9533 1.0738 0.089 Uiso 1 1 calc R . . . .
H14B H 0.3256 0.8803 1.0563 0.089 Uiso 1 1 calc R . . . .
C11 C -0.2145(18) -0.1200(14) 0.2927(13) 0.086(5) Uani 1 1 d D U . . .
H11A H -0.2241 -0.0825 0.3446 0.103 Uiso 1 1 calc R . . . .
H11B H -0.1617 -0.1376 0.3019 0.103 Uiso 1 1 calc R . . . .
C37 C 0.0251(19) 0.1974(14) 0.3072(13) 0.108(6) Uani 1 1 d D U . . .
H37A H 0.0449 0.1853 0.3529 0.129 Uiso 1 1 calc R . . . .
H37B H -0.0364 0.2032 0.3146 0.129 Uiso 1 1 calc R . . . .
C22 C -0.3075(16) -0.1917(17) 0.6724(17) 0.118(9) Uani 1 1 d D U . . .
H22A H -0.2665 -0.1711 0.6359 0.142 Uiso 1 1 calc R . . . .
H22B H -0.2741 -0.2143 0.7020 0.142 Uiso 1 1 calc R . . . .
C9 C -0.1025(19) 0.0062(17) 0.2686(15) 0.118(6) Uani 1 1 d D U . . .
H9D H -0.1078 0.0478 0.3201 0.142 Uiso 1 1 calc R . . . .
H9E H -0.0526 -0.0150 0.2776 0.142 Uiso 1 1 calc R . . . .
C7 C 0.014(2) 0.1224(17) 0.2362(14) 0.116(6) Uani 1 1 d D U . . .
H7D H 0.0276 0.1432 0.1914 0.139 Uiso 1 1 calc R . . . .
H7E H 0.0619 0.0974 0.2427 0.139 Uiso 1 1 calc R . . . .
C24 C -0.253(2) -0.036(2) 0.769(2) 0.142(10) Uani 1 1 d D U . . .
H24A H -0.2134 -0.0482 0.8038 0.170 Uiso 1 1 calc R . . . .
H24B H -0.2819 0.0030 0.8044 0.170 Uiso 1 1 calc R . . . .
C25 C -0.191(2) 0.014(2) 0.7289(19) 0.139(10) Uani 1 1 d D U . . .
H25C H -0.2296 0.0189 0.6879 0.167 Uiso 1 1 calc R . . . .
H25D H -0.1532 -0.0201 0.7009 0.167 Uiso 1 1 calc R . . . .
C35 C -0.632(2) -0.1094(16) 0.7270(19) 0.136(7) Uani 1 1 d D U . . .
H35A H -0.6723 -0.0948 0.6950 0.164 Uiso 1 1 calc R . . . .
H35B H -0.6693 -0.1276 0.7666 0.164 Uiso 1 1 calc R . . . .
C8 C -0.075(2) 0.0532(19) 0.2152(16) 0.126(6) Uani 1 1 d D U . . .
H8D H -0.1224 0.0787 0.2101 0.151 Uiso 1 1 calc R . . . .
H8E H -0.0757 0.0104 0.1624 0.151 Uiso 1 1 calc R . . . .
C29 C -0.351(2) 0.3064(15) 0.747(2) 0.150(8) Uani 1 1 d D U . . .
H29A H -0.3993 0.3064 0.7828 0.180 Uiso 1 1 calc R . . . .
H29B H -0.3807 0.2959 0.6943 0.180 Uiso 1 1 calc R . . . .
C27 C -0.066(2) 0.1424(18) 0.727(2) 0.131(10) Uani 1 1 d D U . . .
H27A H -0.0019 0.1622 0.7520 0.157 Uiso 1 1 calc R . . . .
H27B H -0.0721 0.0979 0.6739 0.157 Uiso 1 1 calc R . . . .
C30 C -0.325(2) 0.2321(19) 0.740(3) 0.157(8) Uani 1 1 d D U . . .
H30A H -0.2916 0.2413 0.7908 0.188 Uiso 1 1 calc R . . . .
H30B H -0.2825 0.2250 0.6990 0.188 Uiso 1 1 calc R . . . .
C32 C -0.463(3) 0.116(2) 0.770(2) 0.157(8) Uani 1 1 d D U . . .
H32C H -0.4981 0.1533 0.7969 0.188 Uiso 1 1 calc R . . . .
H32D H -0.4216 0.1138 0.8104 0.188 Uiso 1 1 calc R . . . .
C31 C -0.407(2) 0.154(2) 0.718(2) 0.160(8) Uani 1 1 d D U . . .
H31A H -0.4506 0.1642 0.6853 0.192 Uiso 1 1 calc R . . . .
H31B H -0.3883 0.1069 0.6817 0.192 Uiso 1 1 calc R . . . .
C10 C -0.1890(18) -0.0679(15) 0.2426(14) 0.110(6) Uani 1 1 d D U . . .
H10A H -0.2395 -0.0458 0.2376 0.132 Uiso 1 1 calc R . . . .
H10B H -0.1855 -0.1069 0.1892 0.132 Uiso 1 1 calc R . . . .
C23 C -0.327(2) -0.1181(18) 0.728(2) 0.151(11) Uani 1 1 d D U . . .
H23A H -0.3714 -0.1052 0.6991 0.181 Uiso 1 1 calc R . . . .
H23B H -0.3589 -0.1381 0.7690 0.181 Uiso 1 1 calc R . . . .
C26 C -0.128(2) 0.102(2) 0.774(2) 0.155(11) Uani 1 1 d D U . . .
H26A H -0.0909 0.0991 0.8170 0.186 Uiso 1 1 calc R . . . .
H26B H -0.1650 0.1387 0.7987 0.186 Uiso 1 1 calc R . . . .
C33 C -0.526(3) 0.028(2) 0.726(2) 0.159(7) Uani 1 1 d D U . . .
H33A H -0.5817 0.0331 0.7024 0.191 Uiso 1 1 calc R . . . .
H33B H -0.4964 0.0004 0.6813 0.191 Uiso 1 1 calc R . . . .
O43 O -0.1260(13) 0.5076(13) 0.6739(13) 0.120(7) Uani 1 1 d . . . . .
N1 N -0.0356(9) 0.6563(9) 0.9755(8) 0.048(3) Uani 1 1 d . . . . .
H1A H -0.0664 0.6558 1.0182 0.057 Uiso 1 1 calc GR . . . .
H1B H 0.0014 0.6238 0.9707 0.057 Uiso 1 1 calc GR . . . .
H1C H -0.0771 0.6332 0.9311 0.057 Uiso 1 1 calc GR . . . .
C1 C 0.0222(11) 0.7480(10) 0.9863(10) 0.047(4) Uani 1 1 d D . . . .
H1D H 0.0635 0.7742 1.0370 0.057 Uiso 1 1 calc R . . . .
H1E H 0.0617 0.7473 0.9433 0.057 Uiso 1 1 calc R . . . .
C2 C -0.0329(12) 0.8036(11) 0.9863(11) 0.053(4) Uani 1 1 d D . . . .
H2D H -0.0713 0.8054 1.0302 0.064 Uiso 1 1 calc R . . . .
H2E H -0.0752 0.7766 0.9362 0.064 Uiso 1 1 calc R . . . .
C3 C 0.0244(12) 0.8949(11) 0.9953(11) 0.055(4) Uani 1 1 d D . . . .
H3D H 0.0662 0.9214 1.0458 0.066 Uiso 1 1 calc R . . . .
H3E H 0.0637 0.8923 0.9520 0.066 Uiso 1 1 calc R . . . .
C4 C -0.0268(13) 0.9533(11) 0.9945(11) 0.056(4) Uani 1 1 d D . . . .
H4D H -0.0677 0.9535 1.0365 0.067 Uiso 1 1 calc R . . . .
H4E H -0.0673 0.9269 0.9433 0.067 Uiso 1 1 calc R . . . .
C34 C -0.557(2) -0.029(2) 0.770(2) 0.152(7) Uani 1 1 d D U . . .
H34A H -0.5768 0.0027 0.8197 0.182 Uiso 1 1 calc R . . . .
H34B H -0.5038 -0.0433 0.7849 0.182 Uiso 1 1 calc R . . . .
N6 N 0.0973(19) 0.3547(14) 0.3806(13) 0.122(7) Uani 1 1 d D U . . .
H6A H 0.0417 0.3623 0.3819 0.147 Uiso 1 1 d R . . . .
H6B H 0.1424 0.4046 0.3819 0.147 Uiso 1 1 d R . . . .
C5 C 0.0900(19) 0.2811(14) 0.3094(13) 0.109(6) Uani 1 1 d D U . . .
H5F H 0.1520 0.2762 0.3035 0.130 Uiso 1 1 calc R . . . .
H5G H 0.0711 0.2931 0.2634 0.130 Uiso 1 1 calc R . . . .
O39 O -0.1551(11) 0.5968(11) 0.8321(9) 0.087(5) Uani 1 1 d . . . . .
H39A H -0.2051 0.5549 0.8321 0.131 Uiso 1 1 d R . . . .
H39B H -0.1295 0.5724 0.7925 0.131 Uiso 1 1 d R . . . .
O38 O -0.3150(9) 0.5578(14) 0.7354(8) 0.105(6) Uani 1 1 d . . . . .
H38A H -0.2642 0.5707 0.7653 0.157 Uiso 1 1 d R . . . .
H38B H -0.3378 0.5977 0.7602 0.157 Uiso 1 1 d R . . . .
Cl3 Cl -0.1157(13) 0.1277(14) 0.4963(10) 0.137(8) Uani 0.5 1 d . . P A 2
O37 O -0.043(2) 0.3564(16) 0.4456(13) 0.169(12) Uani 1 1 d . . . . .
H37C H -0.0287 0.3619 0.4942 0.254 Uiso 1 1 d R . . . .
H37D H -0.0848 0.3046 0.4250 0.254 Uiso 1 1 d R . . . .
Cl1 Cl -0.3356(12) -0.1668(9) 0.4789(8) 0.095(4) Uani 0.5 1 d . . P B 2
S1_1 S -0.1896(15) 0.1581(11) 0.4775(9) 0.143(6) Uani 0.5 1 d D U P C 1
O1_1 O -0.181(3) 0.205(2) 0.4214(17) 0.133(10) Uani 0.5 1 d D U P C 1
O2_1 O -0.093(2) 0.174(3) 0.512(3) 0.158(12) Uani 0.5 1 d D U P C 1
O3_1 O -0.239(3) 0.0629(14) 0.444(2) 0.157(11) Uani 0.5 1 d D U P C 1
O4_1 O -0.236(3) 0.198(2) 0.5460(17) 0.151(11) Uani 0.5 1 d D U P C 1
Cl1_2 Cl -0.3998(12) -0.1807(12) 0.4594(8) 0.116(6) Uani 0.5 1 d D . P D 1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 O20 2.004(9) . ?
Ti1 O17 1.738(8) . ?
Ti1 O25 2.155(8) . ?
Ti1 O26 1.966(9) . ?
Ti1 O27 1.941(9) . ?
Ti1 O21 1.974(8) . ?
Ti2 O17 1.942(8) . ?
Ti2 O16 2.016(9) . ?
Ti2 O15 2.185(9) . ?
Ti2 O10 1.970(9) . ?
Ti2 O9 1.984(9) . ?
Ti2 O14 1.699(8) . ?
Ti4 O33 1.908(8) . ?
Ti4 O41 1.984(9) . ?
Ti4 O30 1.980(9) . ?
Ti4 O27 1.726(9) . ?
Ti4 O31 2.014(10) . ?
Ti4 O32 2.193(9) . ?
Ti3 O33 1.733(8) . ?
Ti3 O14 1.947(8) . ?
Ti3 O4 1.988(9) . ?
Ti3 O6 1.993(11) . ?
Ti3 O34 1.993(11) . ?
Ti3 O5 2.147(10) . ?
S6 O10 1.528(10) . ?
S6 O11 1.463(9) . ?
S6 O13 1.464(9) . ?
S6 O12 1.446(9) . ?
S4 O20 1.505(9) . ?
S4 O16 1.505(9) . ?
S4 O19 1.448(9) . ?
S4 O18 1.433(10) . ?
S3 O21 1.528(9) . ?
S3 O24 1.463(9) . ?
S3 O22 1.448(11) . ?
S3 O23 1.451(11) . ?
S8 O4 1.503(9) . ?
S8 O3 1.443(10) . ?
S8 O2 1.465(12) . ?
S8 O1 1.436(11) . ?
S7 O34 1.493(10) . ?
S7 O31 1.499(10) . ?
S7 O36 1.438(10) . ?
S7 O35 1.436(11) . ?
S5 O9 1.522(8) . ?
S5 O6 1.476(10) . ?
S5 O7 1.429(11) . ?
S5 O8 1.446(13) . ?
S2 O26 1.506(9) . ?
S2 O30 1.493(10) . ?
S2 O29 1.486(13) . ?
S2 O28 1.366(11) . ?
S1 O41 1.483(8) . ?
S1 O42 1.441(11) . ?
S1 O44 1.493(14) . ?
S1 O43 1.389(16) . ?
O25 H25A 0.8883 . ?
O25 H25B 0.8878 . ?
O15 H15A 0.9157 . ?
O15 H15B 0.9156 . ?
O32 H32A 0.9065 . ?
O32 H32B 0.9072 . ?
O5 H5A 0.8704 . ?
O5 H5B 0.8687 . ?
N8 H8A 0.9100 . ?
N8 H8B 0.9100 . ?
N8 H8C 0.9100 . ?
N8 C20 1.45(2) . ?
N7 H7A 0.9100 . ?
N7 H7B 0.9100 . ?
N7 H7C 0.9100 . ?
N7 C12 1.47(2) . ?
N9 H9A 0.9100 . ?
N9 H9B 0.9100 . ?
N9 H9C 0.9100 . ?
N9 C13 1.47(2) . ?
N3 H3A 0.9100 . ?
N3 H3B 0.9100 . ?
N3 H3C 0.9100 . ?
N3 C28 1.46(2) . ?
N2 H2A 0.9100 . ?
N2 H2B 0.9100 . ?
N2 H2C 0.9100 . ?
N2 C21 1.43(2) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C20 C19 1.51(3) . ?
N5 H5C 0.9100 . ?
N5 H5D 0.9100 . ?
N5 H5E 0.9100 . ?
N5 C36 1.448(10) . ?
N4 H4A 0.9100 . ?
N4 H4B 0.9100 . ?
N4 H4C 0.9100 . ?
N4 C29 1.449(10) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C21 C22 1.448(10) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C13 C14 1.47(3) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C19 C18 1.471(17) . ?
C36 H36A 0.9900 . ?
C36 H36B 0.9900 . ?
C36 C35 1.455(10) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C12 C11 1.50(3) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C18 C17 1.47(3) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C28 C27 1.447(10) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C17 C16 1.50(3) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C16 C15 1.477(17) . ?
C15 H15C 0.9900 . ?
C15 H15D 0.9900 . ?
C15 C14 1.49(3) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C11 C10 1.456(10) . ?
C37 H37A 0.9900 . ?
C37 H37B 0.9900 . ?
C37 C7 1.450(10) . ?
C37 C5 1.457(10) . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C22 C23 1.454(10) . ?
C9 H9D 0.9900 . ?
C9 H9E 0.9900 . ?
C9 C8 1.445(10) . ?
C9 C10 1.456(10) . ?
C7 H7D 0.9900 . ?
C7 H7E 0.9900 . ?
C7 C8 1.45(4) . ?
C24 H24A 0.9900 . ?
C24 H24B 0.9900 . ?
C24 C25 1.448(10) . ?
C24 C23 1.445(10) . ?
C25 H25C 0.9900 . ?
C25 H25D 0.9900 . ?
C25 C26 1.449(10) . ?
C35 H35A 0.9900 . ?
C35 H35B 0.9900 . ?
C35 C34 1.454(10) . ?
C8 H8D 0.9900 . ?
C8 H8E 0.9900 . ?
C29 H29A 0.9900 . ?
C29 H29B 0.9900 . ?
C29 C30 1.441(10) . ?
C27 H27A 0.9900 . ?
C27 H27B 0.9900 . ?
C27 C26 1.453(10) . ?
C30 H30A 0.9900 . ?
C30 H30B 0.9900 . ?
C30 C31 1.452(10) . ?
C32 H32C 0.9900 . ?
C32 H32D 0.9900 . ?
C32 C31 1.449(10) . ?
C32 C33 1.453(10) . ?
C31 H31A 0.9900 . ?
C31 H31B 0.9900 . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C26 H26A 0.9900 . ?
C26 H26B 0.9900 . ?
C33 H33A 0.9900 . ?
C33 H33B 0.9900 . ?
C33 C34 1.446(10) . ?
N1 H1A 0.9100 . ?
N1 H1B 0.9100 . ?
N1 H1C 0.9100 . ?
N1 C1 1.49(2) . ?
C1 H1D 0.9900 . ?
C1 H1E 0.9900 . ?
C1 C2 1.480(15) . ?
C2 H2D 0.9900 . ?
C2 H2E 0.9900 . ?
C2 C3 1.49(2) . ?
C3 H3D 0.9900 . ?
C3 H3E 0.9900 . ?
C3 C4 1.481(15) . ?
C4 C4 1.50(4) 2_577 ?
C4 H4D 0.9900 . ?
C4 H4E 0.9900 . ?
C34 H34A 0.9900 . ?
C34 H34B 0.9900 . ?
N6 H6A 0.9099 . ?
N6 H6B 0.9098 . ?
N6 C5 1.449(10) . ?
C5 H5F 0.9900 . ?
C5 H5G 0.9900 . ?
O39 H39A 0.8700 . ?
O39 H39B 0.8696 . ?
O38 H38A 0.8703 . ?
O38 H38B 0.8701 . ?
O37 H37C 0.8707 . ?
O37 H37D 0.8701 . ?
S1_1 O1_1 1.479(18) . ?
S1_1 O2_1 1.519(19) . ?
S1_1 O3_1 1.476(18) . ?
S1_1 O4_1 1.509(18) . ?

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
O20 Ti1 O25 82.6(3) . . ?
O17 Ti1 O20 92.6(4) . . ?
O17 Ti1 O25 174.6(4) . . ?
O17 Ti1 O26 97.7(4) . . ?
O17 Ti1 O27 98.6(4) . . ?
O17 Ti1 O21 99.3(4) . . ?
O26 Ti1 O20 169.7(3) . . ?
O26 Ti1 O25 87.1(4) . . ?
O26 Ti1 O21 86.9(4) . . ?
O27 Ti1 O20 92.0(4) . . ?
O27 Ti1 O25 84.0(3) . . ?
O27 Ti1 O26 87.0(4) . . ?
O27 Ti1 O21 161.7(3) . . ?
O21 Ti1 O20 90.8(4) . . ?
O21 Ti1 O25 78.4(4) . . ?
O17 Ti2 O16 86.3(3) . . ?
O17 Ti2 O15 79.9(3) . . ?
O17 Ti2 O10 159.7(4) . . ?
O17 Ti2 O9 92.1(4) . . ?
O16 Ti2 O15 90.1(3) . . ?
O10 Ti2 O16 87.2(4) . . ?
O10 Ti2 O15 80.9(3) . . ?
O10 Ti2 O9 91.8(4) . . ?
O9 Ti2 O16 172.7(4) . . ?
O9 Ti2 O15 82.5(4) . . ?
O14 Ti2 O17 98.9(4) . . ?
O14 Ti2 O16 95.4(4) . . ?
O14 Ti2 O15 174.2(4) . . ?
O14 Ti2 O10 100.9(4) . . ?
O14 Ti2 O9 91.9(4) . . ?
O33 Ti4 O41 162.1(4) . . ?
O33 Ti4 O30 92.6(4) . . ?
O33 Ti4 O31 86.1(4) . . ?
O33 Ti4 O32 83.8(3) . . ?
O41 Ti4 O31 85.9(4) . . ?
O41 Ti4 O32 79.8(4) . . ?
O30 Ti4 O41 92.6(4) . . ?
O30 Ti4 O31 170.2(4) . . ?
O30 Ti4 O32 83.4(4) . . ?
O27 Ti4 O33 99.1(4) . . ?
O27 Ti4 O41 97.8(4) . . ?
O27 Ti4 O30 92.2(4) . . ?
O27 Ti4 O31 97.6(4) . . ?
O27 Ti4 O32 174.9(4) . . ?
O31 Ti4 O32 86.8(4) . . ?
O33 Ti3 O14 99.7(4) . . ?
O33 Ti3 O4 99.6(4) . . ?
O33 Ti3 O6 93.9(4) . . ?
O33 Ti3 O34 91.2(4) . . ?
O33 Ti3 O5 176.3(5) . . ?
O14 Ti3 O4 160.6(4) . . ?
O14 Ti3 O6 87.0(4) . . ?
O14 Ti3 O34 90.4(4) . . ?
O14 Ti3 O5 79.9(3) . . ?
O4 Ti3 O6 89.6(4) . . ?
O4 Ti3 O34 91.2(4) . . ?
O4 Ti3 O5 81.0(4) . . ?
O6 Ti3 O5 89.8(5) . . ?
O34 Ti3 O6 174.6(4) . . ?
O34 Ti3 O5 85.1(5) . . ?
O11 S6 O10 107.1(5) . . ?
O11 S6 O13 110.2(6) . . ?
O13 S6 O10 107.2(5) . . ?
O12 S6 O10 109.3(5) . . ?
O12 S6 O11 112.1(6) . . ?
O12 S6 O13 110.7(5) . . ?
O20 S4 O16 108.6(5) . . ?
O19 S4 O20 107.5(5) . . ?
O19 S4 O16 106.9(5) . . ?
O18 S4 O20 109.3(5) . . ?
O18 S4 O16 109.9(5) . . ?
O18 S4 O19 114.5(6) . . ?
O24 S3 O21 105.0(5) . . ?
O22 S3 O21 107.9(6) . . ?
O22 S3 O24 110.8(6) . . ?
O22 S3 O23 112.6(7) . . ?
O23 S3 O21 107.8(6) . . ?
O23 S3 O24 112.2(6) . . ?
O3 S8 O4 107.5(6) . . ?
O3 S8 O2 110.6(7) . . ?
O2 S8 O4 108.2(7) . . ?
O1 S8 O4 108.7(6) . . ?
O1 S8 O3 110.1(7) . . ?
O1 S8 O2 111.6(7) . . ?
O34 S7 O31 108.2(6) . . ?
O36 S7 O34 108.5(6) . . ?
O36 S7 O31 109.3(6) . . ?
O35 S7 O34 108.3(6) . . ?
O35 S7 O31 109.3(6) . . ?
O35 S7 O36 113.1(7) . . ?
O6 S5 O9 107.5(5) . . ?
O7 S5 O9 109.3(6) . . ?
O7 S5 O6 109.2(7) . . ?
O7 S5 O8 113.5(9) . . ?
O8 S5 O9 107.5(6) . . ?
O8 S5 O6 109.7(7) . . ?
O30 S2 O26 108.3(6) . . ?
O29 S2 O26 106.5(6) . . ?
O29 S2 O30 104.5(7) . . ?
O28 S2 O26 112.1(7) . . ?
O28 S2 O30 112.4(8) . . ?
O28 S2 O29 112.6(10) . . ?
O41 S1 O44 106.7(7) . . ?
O42 S1 O41 108.5(6) . . ?
O42 S1 O44 108.1(8) . . ?
O43 S1 O41 110.5(10) . . ?
O43 S1 O42 114.4(11) . . ?
O43 S1 O44 108.4(12) . . ?
Ti3 O33 Ti4 146.7(5) . . ?
S4 O20 Ti1 132.2(5) . . ?
Ti1 O17 Ti2 145.8(5) . . ?
S4 O16 Ti2 135.8(5) . . ?
Ti1 O25 H25A 110.7 . . ?
Ti1 O25 H25B 110.3 . . ?
H25A O25 H25B 103.4 . . ?
Ti2 O15 H15A 111.8 . . ?
Ti2 O15 H15B 111.9 . . ?
H15A O15 H15B 102.0 . . ?
S6 O10 Ti2 138.5(6) . . ?
S5 O9 Ti2 137.0(6) . . ?
Ti2 O14 Ti3 146.7(6) . . ?
S2 O26 Ti1 139.7(6) . . ?
S1 O41 Ti4 141.9(6) . . ?
S2 O30 Ti4 137.8(6) . . ?
S8 O4 Ti3 138.2(6) . . ?
S5 O6 Ti3 141.6(6) . . ?
S7 O34 Ti3 138.7(6) . . ?
Ti4 O27 Ti1 145.8(6) . . ?
S3 O21 Ti1 135.7(5) . . ?
S7 O31 Ti4 142.3(6) . . ?
Ti4 O32 H32A 111.4 . . ?
Ti4 O32 H32B 111.0 . . ?
H32A O32 H32B 102.6 . . ?
Ti3 O5 H5A 117.0 . . ?
Ti3 O5 H5B 134.6 . . ?
H5A O5 H5B 104.6 . . ?
H8A N8 H8B 109.5 . . ?
H8A N8 H8C 109.5 . . ?
H8B N8 H8C 109.5 . . ?
C20 N8 H8A 109.5 . . ?
C20 N8 H8B 109.5 . . ?
C20 N8 H8C 109.5 . . ?
H7A N7 H7B 109.5 . . ?
H7A N7 H7C 109.5 . . ?
H7B N7 H7C 109.5 . . ?
C12 N7 H7A 109.5 . . ?
C12 N7 H7B 109.5 . . ?
C12 N7 H7C 109.5 . . ?
H9A N9 H9B 109.5 . . ?
H9A N9 H9C 109.5 . . ?
H9B N9 H9C 109.5 . . ?
C13 N9 H9A 109.5 . . ?
C13 N9 H9B 109.5 . . ?
C13 N9 H9C 109.5 . . ?
H3A N3 H3B 109.5 . . ?
H3A N3 H3C 109.5 . . ?
H3B N3 H3C 109.5 . . ?
C28 N3 H3A 109.5 . . ?
C28 N3 H3B 109.5 . . ?
C28 N3 H3C 109.5 . . ?
H2A N2 H2B 109.5 . . ?
H2A N2 H2C 109.5 . . ?
H2B N2 H2C 109.5 . . ?
C21 N2 H2A 109.5 . . ?
C21 N2 H2B 109.5 . . ?
C21 N2 H2C 109.5 . . ?
N8 C20 H20A 109.5 . . ?
N8 C20 H20B 109.5 . . ?
N8 C20 C19 110.8(14) . . ?
H20A C20 H20B 108.1 . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H5C N5 H5D 109.5 . . ?
H5C N5 H5E 109.5 . . ?
H5D N5 H5E 109.5 . . ?
C36 N5 H5C 109.5 . . ?
C36 N5 H5D 109.5 . . ?
C36 N5 H5E 109.5 . . ?
H4A N4 H4B 109.5 . . ?
H4A N4 H4C 109.5 . . ?
H4B N4 H4C 109.5 . . ?
C29 N4 H4A 109.5 . . ?
C29 N4 H4B 109.5 . . ?
C29 N4 H4C 109.5 . . ?
N2 C21 H21A 108.8 . . ?
N2 C21 H21B 108.8 . . ?
N2 C21 C22 113.8(18) . . ?
H21A C21 H21B 107.7 . . ?
C22 C21 H21A 108.8 . . ?
C22 C21 H21B 108.8 . . ?
N9 C13 H13A 109.2 . . ?
N9 C13 H13B 109.2 . . ?
H13A C13 H13B 107.9 . . ?
C14 C13 N9 112.0(15) . . ?
C14 C13 H13A 109.2 . . ?
C14 C13 H13B 109.2 . . ?
C20 C19 H19A 109.6 . . ?
C20 C19 H19B 109.6 . . ?
H19A C19 H19B 108.1 . . ?
C18 C19 C20 110.4(17) . . ?
C18 C19 H19A 109.6 . . ?
C18 C19 H19B 109.6 . . ?
N5 C36 H36A 108.3 . . ?
N5 C36 H36B 108.3 . . ?
N5 C36 C35 116(2) . . ?
H36A C36 H36B 107.4 . . ?
C35 C36 H36A 108.3 . . ?
C35 C36 H36B 108.3 . . ?
N7 C12 H12A 109.4 . . ?
N7 C12 H12B 109.4 . . ?
N7 C12 C11 111.1(16) . . ?
H12A C12 H12B 108.0 . . ?
C11 C12 H12A 109.4 . . ?
C11 C12 H12B 109.4 . . ?
C19 C18 H18A 108.5 . . ?
C19 C18 H18B 108.5 . . ?
H18A C18 H18B 107.5 . . ?
C17 C18 C19 115(2) . . ?
C17 C18 H18A 108.5 . . ?
C17 C18 H18B 108.5 . . ?
N3 C28 H28A 108.5 . . ?
N3 C28 H28B 108.5 . . ?
H28A C28 H28B 107.5 . . ?
C27 C28 N3 115.3(19) . . ?
C27 C28 H28A 108.5 . . ?
C27 C28 H28B 108.5 . . ?
C18 C17 H17A 108.8 . . ?
C18 C17 H17B 108.8 . . ?
C18 C17 C16 114(2) . . ?
H17A C17 H17B 107.7 . . ?
C16 C17 H17A 108.8 . . ?
C16 C17 H17B 108.8 . . ?
C17 C16 H16A 108.5 . . ?
C17 C16 H16B 108.5 . . ?
H16A C16 H16B 107.5 . . ?
C15 C16 C17 115(2) . . ?
C15 C16 H16A 108.5 . . ?
C15 C16 H16B 108.5 . . ?
C16 C15 H15C 109.3 . . ?
C16 C15 H15D 109.3 . . ?
C16 C15 C14 112(2) . . ?
H15C C15 H15D 108.0 . . ?
C14 C15 H15C 109.3 . . ?
C14 C15 H15D 109.3 . . ?
C13 C14 C15 113.7(18) . . ?
C13 C14 H14A 108.8 . . ?
C13 C14 H14B 108.8 . . ?
C15 C14 H14A 108.8 . . ?
C15 C14 H14B 108.8 . . ?
H14A C14 H14B 107.7 . . ?
C12 C11 H11A 108.2 . . ?
C12 C11 H11B 108.2 . . ?
H11A C11 H11B 107.4 . . ?
C10 C11 C12 116.3(19) . . ?
C10 C11 H11A 108.2 . . ?
C10 C11 H11B 108.2 . . ?
H37A C37 H37B 107.3 . . ?
C7 C37 H37A 108.1 . . ?
C7 C37 H37B 108.1 . . ?
C7 C37 C5 117(2) . . ?
C5 C37 H37A 108.1 . . ?
C5 C37 H37B 108.1 . . ?
C21 C22 H22A 108.9 . . ?
C21 C22 H22B 108.9 . . ?
C21 C22 C23 113(2) . . ?
H22A C22 H22B 107.7 . . ?
C23 C22 H22A 108.9 . . ?
C23 C22 H22B 108.9 . . ?
H9D C9 H9E 107.4 . . ?
C8 C9 H9D 108.3 . . ?
C8 C9 H9E 108.3 . . ?
C8 C9 C10 116(2) . . ?
C10 C9 H9D 108.3 . . ?
C10 C9 H9E 108.3 . . ?
C37 C7 H7D 108.2 . . ?
C37 C7 H7E 108.2 . . ?
H7D C7 H7E 107.4 . . ?
C8 C7 C37 116(3) . . ?
C8 C7 H7D 108.2 . . ?
C8 C7 H7E 108.2 . . ?
H24A C24 H24B 106.5 . . ?
C25 C24 H24A 106.5 . . ?
C25 C24 H24B 106.5 . . ?
C23 C24 H24A 106.5 . . ?
C23 C24 H24B 106.5 . . ?
C23 C24 C25 123(3) . . ?
C24 C25 H25C 107.4 . . ?
C24 C25 H25D 107.4 . . ?
C24 C25 C26 120(3) . . ?
H25C C25 H25D 106.9 . . ?
C26 C25 H25C 107.4 . . ?
C26 C25 H25D 107.4 . . ?
C36 C35 H35A 107.1 . . ?
C36 C35 H35B 107.1 . . ?
H35A C35 H35B 106.8 . . ?
C34 C35 C36 121(3) . . ?
C34 C35 H35A 107.1 . . ?
C34 C35 H35B 107.1 . . ?
C9 C8 C7 117(3) . . ?
C9 C8 H8D 108.0 . . ?
C9 C8 H8E 108.0 . . ?
C7 C8 H8D 108.0 . . ?
C7 C8 H8E 108.0 . . ?
H8D C8 H8E 107.3 . . ?
N4 C29 H29A 107.1 . . ?
N4 C29 H29B 107.1 . . ?
H29A C29 H29B 106.8 . . ?
C30 C29 N4 121(3) . . ?
C30 C29 H29A 107.1 . . ?
C30 C29 H29B 107.1 . . ?
C28 C27 H27A 108.7 . . ?
C28 C27 H27B 108.7 . . ?
C28 C27 C26 114(3) . . ?
H27A C27 H27B 107.6 . . ?
C26 C27 H27A 108.7 . . ?
C26 C27 H27B 108.7 . . ?
C29 C30 H30A 109.8 . . ?
C29 C30 H30B 109.8 . . ?
C29 C30 C31 109(3) . . ?
H30A C30 H30B 108.3 . . ?
C31 C30 H30A 109.8 . . ?
C31 C30 H30B 109.8 . . ?
H32C C32 H32D 108.0 . . ?
C31 C32 H32C 109.3 . . ?
C31 C32 H32D 109.3 . . ?
C31 C32 C33 112(3) . . ?
C33 C32 H32C 109.3 . . ?
C33 C32 H32D 109.3 . . ?
C30 C31 H31A 105.2 . . ?
C30 C31 H31B 105.2 . . ?
C32 C31 C30 128(3) . . ?
C32 C31 H31A 105.2 . . ?
C32 C31 H31B 105.2 . . ?
H31A C31 H31B 105.9 . . ?
C11 C10 C9 117(2) . . ?
C11 C10 H10A 108.1 . . ?
C11 C10 H10B 108.1 . . ?
C9 C10 H10A 108.1 . . ?
C9 C10 H10B 108.1 . . ?
H10A C10 H10B 107.3 . . ?
C22 C23 H23A 107.1 . . ?
C22 C23 H23B 107.1 . . ?
C24 C23 C22 121(3) . . ?
C24 C23 H23A 107.1 . . ?
C24 C23 H23B 107.1 . . ?
H23A C23 H23B 106.8 . . ?
C25 C26 C27 114(3) . . ?
C25 C26 H26A 108.8 . . ?
C25 C26 H26B 108.8 . . ?
C27 C26 H26A 108.8 . . ?
C27 C26 H26B 108.8 . . ?
H26A C26 H26B 107.7 . . ?
C32 C33 H33A 108.3 . . ?
C32 C33 H33B 108.3 . . ?
H33A C33 H33B 107.4 . . ?
C34 C33 C32 116(3) . . ?
C34 C33 H33A 108.3 . . ?
C34 C33 H33B 108.3 . . ?
H1A N1 H1B 109.5 . . ?
H1A N1 H1C 109.5 . . ?
H1B N1 H1C 109.5 . . ?
C1 N1 H1A 109.5 . . ?
C1 N1 H1B 109.5 . . ?
C1 N1 H1C 109.5 . . ?
N1 C1 H1D 108.9 . . ?
N1 C1 H1E 108.9 . . ?
H1D C1 H1E 107.7 . . ?
C2 C1 N1 113.3(13) . . ?
C2 C1 H1D 108.9 . . ?
C2 C1 H1E 108.9 . . ?
C1 C2 H2D 108.8 . . ?
C1 C2 H2E 108.8 . . ?
C1 C2 C3 113.6(14) . . ?
H2D C2 H2E 107.7 . . ?
C3 C2 H2D 108.8 . . ?
C3 C2 H2E 108.8 . . ?
C2 C3 H3D 108.2 . . ?
C2 C3 H3E 108.2 . . ?
H3D C3 H3E 107.4 . . ?
C4 C3 C2 116.2(15) . . ?
C4 C3 H3D 108.2 . . ?
C4 C3 H3E 108.2 . . ?
C3 C4 C4 118.8(19) . 2_577 ?
C3 C4 H4D 107.6 . . ?
C3 C4 H4E 107.6 . . ?
C4 C4 H4D 107.6 2_577 . ?
C4 C4 H4E 107.6 2_577 . ?
H4D C4 H4E 107.0 . . ?
C35 C34 H34A 108.9 . . ?
C35 C34 H34B 108.9 . . ?
C33 C34 C35 113(3) . . ?
C33 C34 H34A 108.9 . . ?
C33 C34 H34B 108.9 . . ?
H34A C34 H34B 107.7 . . ?
H6A N6 H6B 109.5 . . ?
C5 N6 H6A 107.3 . . ?
C5 N6 H6B 112.4 . . ?
C37 C5 H5F 108.5 . . ?
C37 C5 H5G 108.5 . . ?
N6 C5 C37 115(2) . . ?
N6 C5 H5F 108.5 . . ?
N6 C5 H5G 108.5 . . ?
H5F C5 H5G 107.5 . . ?
H39A O39 H39B 104.5 . . ?
H38A O38 H38B 104.5 . . ?
H37C O37 H37D 104.5 . . ?
O1_1 S1_1 O2_1 108.3(18) . . ?
O1_1 S1_1 O4_1 109.5(17) . . ?
O3_1 S1_1 O1_1 115.4(17) . . ?
O3_1 S1_1 O2_1 108.1(18) . . ?
O3_1 S1_1 O4_1 109.0(18) . . ?
O4_1 S1_1 O2_1 106.1(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
O33 Ti4 O27 Ti1 70.6(9) . . . . ?
O20 Ti1 O17 Ti2 27.6(9) . . . . ?
O20 S4 O16 Ti2 -48.7(8) . . . . ?
O17 Ti2 O14 Ti3 68.4(8) . . . . ?
O16 Ti2 O14 Ti3 155.5(8) . . . . ?
O16 S4 O20 Ti1 40.9(9) . . . . ?
O19 S4 O20 Ti1 156.2(7) . . . . ?
O19 S4 O16 Ti2 -164.4(7) . . . . ?
O10 Ti2 O14 Ti3 -116.3(8) . . . . ?
O11 S6 O10 Ti2 -98.0(9) . . . . ?
O9 Ti2 O14 Ti3 -24.1(8) . . . . ?
O9 S5 O6 Ti3 -29.1(12) . . . . ?
O13 S6 O10 Ti2 143.7(8) . . . . ?
O14 Ti3 O33 Ti4 -63.8(9) . . . . ?
O26 Ti1 O17 Ti2 -153.0(8) . . . . ?
O26 S2 O30 Ti4 -21.8(10) . . . . ?
O41 Ti4 O27 Ti1 -115.3(9) . . . . ?
O30 Ti4 O27 Ti1 -22.4(9) . . . . ?
O30 S2 O26 Ti1 34.1(10) . . . . ?
O4 Ti3 O33 Ti4 118.3(9) . . . . ?
O12 S6 O10 Ti2 23.7(10) . . . . ?
O6 Ti3 O33 Ti4 -151.5(9) . . . . ?
O6 S5 O9 Ti2 26.9(10) . . . . ?
O34 Ti3 O33 Ti4 26.8(9) . . . . ?
O34 S7 O31 Ti4 0.5(12) . . . . ?
O27 Ti1 O17 Ti2 -64.8(9) . . . . ?
O18 S4 O20 Ti1 -79.0(9) . . . . ?
O18 S4 O16 Ti2 70.8(9) . . . . ?
O21 Ti1 O17 Ti2 118.9(8) . . . . ?
O24 S3 O21 Ti1 -177.1(8) . . . . ?
O31 Ti4 O27 Ti1 157.8(8) . . . . ?
O31 S7 O34 Ti3 -17.1(11) . . . . ?
O36 S7 O34 Ti3 101.3(9) . . . . ?
O36 S7 O31 Ti4 -117.4(11) . . . . ?
O42 S1 O41 Ti4 -44.6(14) . . . . ?
O22 S3 O21 Ti1 64.7(10) . . . . ?
O3 S8 O4 Ti3 140.9(10) . . . . ?
O35 S7 O34 Ti3 -135.5(9) . . . . ?
O35 S7 O31 Ti4 118.3(11) . . . . ?
N8 C20 C19 C18 -178.1(16) . . . . ?
O23 S3 O21 Ti1 -57.3(10) . . . . ?
O2 S8 O4 Ti3 -99.5(11) . . . . ?
O7 S5 O9 Ti2 -91.5(10) . . . . ?
O7 S5 O6 Ti3 89.4(11) . . . . ?
O8 S5 O9 Ti2 144.9(9) . . . . ?
O8 S5 O6 Ti3 -145.6(10) . . . . ?
O1 S8 O4 Ti3 21.8(13) . . . . ?
N7 C12 C11 C10 166(2) . . . . ?
O29 S2 O26 Ti1 -77.8(11) . . . . ?
O29 S2 O30 Ti4 91.4(10) . . . . ?
N9 C13 C14 C15 -71(2) . . . . ?
N3 C28 C27 C26 175(3) . . . . ?
O28 S2 O26 Ti1 158.6(10) . . . . ?
O28 S2 O30 Ti4 -146.2(10) . . . . ?
O44 S1 O41 Ti4 -160.8(12) . . . . ?
N2 C21 C22 C23 154(3) . . . . ?
C20 C19 C18 C17 -169.6(19) . . . . ?
N5 C36 C35 C34 160(3) . . . . ?
N4 C29 C30 C31 175(3) . . . . ?
C21 C22 C23 C24 -169(3) . . . . ?
C19 C18 C17 C16 168(2) . . . . ?
C36 C35 C34 C33 87(5) . . . . ?
C12 C11 C10 C9 -175(3) . . . . ?
C18 C17 C16 C15 -165(2) . . . . ?
C28 C27 C26 C25 112(4) . . . . ?
C17 C16 C15 C14 169(2) . . . . ?
C16 C15 C14 C13 -170.7(18) . . . . ?
C37 C7 C8 C9 -66(4) . . . . ?
C7 C37 C5 N6 179(3) . . . . ?
C24 C25 C26 C27 176(3) . . . . ?
C25 C24 C23 C22 58(6) . . . . ?
C8 C9 C10 C11 176(3) . . . . ?
C29 C30 C31 C32 -92(6) . . . . ?
C32 C33 C34 C35 170(4) . . . . ?
C31 C32 C33 C34 155(4) . . . . ?
C10 C9 C8 C7 -175(3) . . . . ?
C23 C24 C25 C26 171(4) . . . . ?
C33 C32 C31 C30 -167(4) . . . . ?
O43 S1 O41 Ti4 81.6(15) . . . . ?
N1 C1 C2 C3 -178.7(14) . . . . ?
C1 C2 C3 C4 179.1(15) . . . . ?
C2 C3 C4 C4 178.3(19) . . . 2_577 ?
C5 C37 C7 C8 -150(3) . . . . ?

_smtbx_masks_special_details     
;
A solvent mask was calculated and 76 electrons were
found in a volume of 222Å^3 in 3 voids per unit cell.
This is consistent with the presence of 4[H2O] per Formula Unit 
which account for 80 electrons per unit cell.
;
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 0.000 0.000 0.500 80.0 29.0 '3 water'
2 0.200 0.228 0.174 11.8 0.0 ?
3 0.500 0.000 0.500 117.6 46.6 '5 water'
4 0.800 0.772 0.826 11.8 0.0 ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.814
_oxdiff_exptl_absorpt_empirical_full_min 0.304


# start Validation Reply Form
_vrf_PLAT417_ti4-ocda            
;
PROBLEM: Short Inter D-H..H-D H38A ..H39A . 1.66 Ang.
RESPONSE: This problem is caused by the disorder of the atoms.
;
_vrf_PLAT084_ti4-ocda            
;
PROBLEM: High wR2 Value (i.e. > 0.25) ................... 0.42 Report
RESPONSE: This problem is caused by the poor quality of the crystals.
;
_vrf_PLAT341_ti4-ocda            
;
PROBLEM: Low Bond Precision on C-C Bonds ............... 0.03875 Ang.
RESPONSE: This problem is caused by the disorder of the atoms.
;
_vrf_PLAT430_ti4-ocda            
;
PROBLEM: Short Inter D...A Contact O4_1 ..O44 . 2.70 Ang.
RESPONSE: This problem is caused by the disorder of the atoms.
;
# end Validation Reply Form
