# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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. 
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data_tj150315_3_0m
_database_code_depnum_ccdc_archive 'CCDC 1544077'
_audit_update_record             
;
2017-10-20 deposited with the CCDC.
2017-12-11 downloaded from the CCDC.
;
_audit_creation_date             2017-10-20
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C36 H32 Cl8 N4 O14 Ti4, 2(H4 O2)'
_chemical_formula_sum            'C36 H40 Cl8 N4 O18 Ti4'
_chemical_formula_weight         1291.92
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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           141
_space_group_name_H-M_alt        'I 41/a m d'
_space_group_name_Hall           '-I 4bd 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+1/4, x+3/4, z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'y+1/4, x+3/4, -z+1/4'
'-y+1/4, -x+1/4, -z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+3/4, x+5/4, z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-x+1, y+1/2, -z+1'
'x+1/2, -y+1/2, -z+1/2'
'y+3/4, x+5/4, -z+3/4'
'-y+3/4, -x+3/4, -z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-1/4, -x-3/4, -z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'x-1/2, -y, z-1/2'
'-x, y, z'
'-y-1/4, -x-3/4, z-1/4'
'y-1/4, x-1/4, z-3/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y+1/4, -x-1/4, -z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'x, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'
'-y+1/4, -x-1/4, z+1/4'
'y+1/4, x+1/4, z-1/4'

_cell_length_a                   18.0920(19)
_cell_length_b                   18.0920(19)
_cell_length_c                   17.592(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5758.2(17)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    3990
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      24.46
_cell_measurement_theta_min      2.25
_shelx_estimated_absorpt_T_max   0.909
_shelx_estimated_absorpt_T_min   0.822
_exptl_absorpt_coefficient_mu    0.970
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.490
_exptl_crystal_density_meas      .
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             2608
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0932
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            18898
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.498
_diffrn_reflns_theta_min         2.251
_diffrn_ambient_temperature      298(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                891
_reflns_number_total             1430
_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       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_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    'olex2.solve (Bourhis et al., 2015)'
_refine_diff_density_max         1.009
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.124
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     123
_refine_ls_number_reflns         1430
_refine_ls_number_restraints     13
_refine_ls_R_factor_all          0.1243
_refine_ls_R_factor_gt           0.0739
_refine_ls_restrained_S_all      1.023
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1613P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2008
_refine_ls_wR_factor_ref         0.2291
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C4_$1-C4_$2
 2.2 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(C3)=Sof(H3)=1-FVAR(1)
 Sof(C8)=Sof(H8)=FVAR(1)
 Sof(C4)=Sof(H4)=1-FVAR(2)
 Sof(C9)=Sof(H9)=FVAR(2)
 Fixed Sof: C7(0.5) H7A(0.5) H7B(0.5) H7C(0.5) O5(0.25) H5A(0.25) H5B(0.25)
 O4(0.25) H4A(0.25) H4B(0.25)
5.a Riding coordinates:
 O5(H5A,H5B), O4(H4A,H4B)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C8(H8), C9(H9)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_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
Cl1 Cl 0.40655(9) 0.61466(10) 0.04271(10) 0.0682(6) Uani 1 1 d . . . . .
Ti1 Ti 0.5000 0.65763(8) 0.11703(6) 0.0432(5) Uani 1 2 d S T P . .
O1 O 0.5000 0.7500 0.0784(4) 0.0412(17) Uani 1 4 d S T P . .
O2 O 0.5747(3) 0.6896(2) 0.1963(2) 0.0724(15) Uani 1 1 d . . . . .
C1 C 0.5943(4) 0.7500 0.2216(3) 0.0355(17) Uani 1 2 d S T P A .
C2 C 0.6450(4) 0.7500 0.2885(3) 0.0321(15) Uani 1 2 d S T P . .
N1 N 0.5000 0.4752(4) 0.2648(4) 0.078(3) Uani 1 2 d S T P B .
H1 H 0.5000 0.4282 0.2714 0.094 Uiso 1 2 calc RS T P . .
C3 C 0.6394(7) 0.8075(6) 0.3427(6) 0.051(4) Uani 0.527(15) 1 d . . . A 2
H3 H 0.6054 0.8452 0.3345 0.061 Uiso 0.527(15) 1 calc R . . A 2
C4 C 0.6825(8) 0.8097(3) 0.4073(6) 0.065(5) Uani 0.506(15) 1 d D . . A 2
H4 H 0.6802 0.8488 0.4415 0.079 Uiso 0.506(15) 1 calc R . . A 2
O3 O 0.5000 0.5638(3) 0.1801(3) 0.0705(19) Uani 1 2 d S T P B .
C6 C 0.5000 0.4990(5) 0.1938(4) 0.050(2) Uani 1 2 d S T P . .
C7 C 0.489(9) 0.4439(7) 0.1337(6) 0.11(3) Uani 0.5 1 d . . . B -1
H7A H 0.5180 0.4568 0.0901 0.162 Uiso 0.5 1 calc GR . . B -1
H7B H 0.4374 0.4428 0.1197 0.162 Uiso 0.5 1 calc GR . . B -1
H7C H 0.5033 0.3961 0.1519 0.162 Uiso 0.5 1 calc GR . . B -1
C5 C 0.7299(4) 0.7500 0.4182(4) 0.0448(19) Uani 1 2 d S T P . .
O5 O 0.7273(17) 0.4773(17) 0.1250 0.297(16) Uani 0.5 2 d S TU P C 2
H5A H 0.7370 0.4877 0.1697 0.446 Uiso 0.25 1 d R . . C 2
H5B H 0.7541 0.4961 0.0933 0.446 Uiso 0.25 1 d R . . C 2
C8 C 0.6941(6) 0.8066(6) 0.2990(6) 0.038(4) Uani 0.473(15) 1 d . . . A 1
H8 H 0.6986 0.8432 0.2622 0.046 Uiso 0.473(15) 1 calc R . . A 1
C9 C 0.7371(6) 0.8098(7) 0.3639(6) 0.047(4) Uani 0.494(15) 1 d . . . A 1
H9 H 0.7695 0.8488 0.3723 0.057 Uiso 0.494(15) 1 calc R . . A 1
O4 O 0.7500 0.5148(14) 0.2500 0.193(10) Uani 0.5 2 d S TU P D 1
H4A H 0.7403 0.4999 0.2053 0.290 Uiso 0.25 1 d R . . D 1
H4B H 0.7563 0.4777 0.2782 0.290 Uiso 0.25 1 d 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
Cl1 Ti1 2.2742(17) . ?
Ti1 Cl1 2.2743(17) 22_655 ?
Ti1 Ti1 3.342(3) 10_564 ?
Ti1 O1 1.804(3) . ?
Ti1 O2 2.026(4) . ?
Ti1 O2 2.026(4) 22_655 ?
Ti1 O3 2.027(6) . ?
O1 Ti1 1.804(3) 10_564 ?
O2 C1 1.232(5) . ?
C1 O2 1.232(5) 29_565 ?
C1 C2 1.492(8) . ?
C2 C3 1.415(10) 29_565 ?
C2 C3 1.415(10) . ?
C2 C8 1.368(12) 29_565 ?
C2 C8 1.368(12) . ?
N1 C6 1.321(10) . ?
N1 C5 1.431(10) 19_576 ?
C3 C4 1.379(14) . ?
C4 C5 1.391(10) . ?
O3 C6 1.197(10) . ?
C6 C7 1.47(2) . ?
C5 N1 1.431(10) 28_656 ?
C5 C4 1.391(10) 29_565 ?
C5 C9 1.450(13) 29_565 ?
C5 C9 1.450(13) . ?
C8 C9 1.382(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
Cl1 Ti1 Cl1 96.04(9) . 22_655 ?
Cl1 Ti1 Ti1 109.99(6) . 10_564 ?
Cl1 Ti1 Ti1 109.99(6) 22_655 10_564 ?
O1 Ti1 Cl1 95.74(14) . . ?
O1 Ti1 Cl1 95.74(14) . 22_655 ?
O1 Ti1 Ti1 22.13(19) . 10_564 ?
O1 Ti1 O2 89.69(19) . 22_655 ?
O1 Ti1 O2 89.69(19) . . ?
O1 Ti1 O3 168.9(2) . . ?
O2 Ti1 Cl1 89.85(16) 22_655 . ?
O2 Ti1 Cl1 89.85(16) . 22_655 ?
O2 Ti1 Cl1 171.53(15) . . ?
O2 Ti1 Cl1 171.53(15) 22_655 22_655 ?
O2 Ti1 Ti1 73.40(12) 22_655 10_564 ?
O2 Ti1 Ti1 73.41(12) . 10_564 ?
O2 Ti1 O2 83.7(3) 22_655 . ?
O2 Ti1 O3 82.09(17) . . ?
O2 Ti1 O3 82.09(17) 22_655 . ?
O3 Ti1 Cl1 91.64(13) . 22_655 ?
O3 Ti1 Cl1 91.64(13) . . ?
O3 Ti1 Ti1 146.81(16) . 10_564 ?
Ti1 O1 Ti1 135.7(4) 10_564 . ?
C1 O2 Ti1 134.0(4) . . ?
O2 C1 O2 124.9(6) 29_565 . ?
O2 C1 C2 117.6(3) 29_565 . ?
O2 C1 C2 117.6(3) . . ?
C3 C2 C1 119.2(6) 29_565 . ?
C3 C2 C1 119.2(6) . . ?
C3 C2 C3 94.7(10) . 29_565 ?
C8 C2 C1 120.4(5) 29_565 . ?
C8 C2 C1 120.4(5) . . ?
C8 C2 C8 96.9(9) 29_565 . ?
C6 N1 C5 126.4(7) . 19_576 ?
C4 C3 C2 122.3(9) . . ?
C3 C4 C5 116.2(8) . . ?
C6 O3 Ti1 158.4(5) . . ?
N1 C6 C7 117.4(9) . . ?
O3 C6 N1 120.6(7) . . ?
O3 C6 C7 121.4(9) . . ?
N1 C5 C9 119.5(6) 28_656 29_565 ?
N1 C5 C9 119.5(6) 28_656 . ?
C4 C5 N1 117.6(5) . 28_656 ?
C4 C5 N1 117.6(5) 29_565 28_656 ?
C4 C5 C4 101.8(10) . 29_565 ?
C9 C5 C9 96.5(9) . 29_565 ?
C2 C8 C9 120.5(9) . . ?
C8 C9 C5 117.6(9) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
