# 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. 
# 
#######################################################################

data_2b
_database_code_depnum_ccdc_archive 'CCDC 1584442'
_audit_update_record             
;
2017-11-09 deposited with the CCDC.
2018-01-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H50 N4 O4 Ti, C H2 Cl2'
_chemical_formula_sum            'C45 H52 Cl2 N4 O4 Ti'
_chemical_formula_weight         831.71

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   C2/c
_symmetry_space_group_name_Hall  '-C 2yc'

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

_cell_length_a                   16.232(3)
_cell_length_b                   16.059(3)
_cell_length_c                   16.430(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 96.520(3)
_cell_angle_gamma                90.00
_cell_volume                     4255.1(1)
_cell_formula_units_Z            4
_cell_measurement_temperature    123(1)
_cell_measurement_reflns_used    6447
_cell_measurement_theta_min      2.262
_cell_measurement_theta_max      27.725

_exptl_crystal_description       plate
_exptl_crystal_colour            Red
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1752
_exptl_absorpt_coefficient_mu    0.374
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8898
_exptl_absorpt_correction_T_max  0.9707
_exptl_absorpt_process_details   'Bruker SADABS V2.05'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      123(1)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            22391
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_sigmaI/netI    0.0333
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.26
_diffrn_reflns_theta_max         27.00
_reflns_number_total             4635
_reflns_number_gt                4323
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0487P)²+7.3547P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4635
_refine_ls_number_parameters     362
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0607
_refine_ls_wR_factor_ref         0.1331
_refine_ls_wR_factor_gt          0.1306
_refine_ls_goodness_of_fit_ref   1.247
_refine_ls_restrained_S_all      1.247
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.07448(14) 0.14330(14) 0.41678(13) 0.0158(4) Uani 1 1 d . . .
C2 C 0.08239(14) 0.06108(14) 0.44882(13) 0.0172(5) Uani 1 1 d . . .
C3 C 0.11692(16) 0.05232(15) 0.53149(14) 0.0219(5) Uani 1 1 d . . .
H3 H 0.1222(17) -0.0032(18) 0.5526(17) 0.026(7) Uiso 1 1 d . . .
C4 C 0.14320(15) 0.11832(15) 0.57937(14) 0.0198(5) Uani 1 1 d . . .
H4 H 0.1673(17) 0.1082(16) 0.6318(17) 0.019(7) Uiso 1 1 d . . .
C5 C 0.13753(14) 0.20090(14) 0.54705(13) 0.0174(5) Uani 1 1 d . . .
C6 C 0.10160(14) 0.21121(14) 0.46534(13) 0.0167(4) Uani 1 1 d . . .
H6 H 0.0956(14) 0.2637(15) 0.4431(14) 0.006(5) Uiso 1 1 d . . .
C7 C 0.17418(17) 0.35023(15) 0.56001(16) 0.0248(5) Uani 1 1 d . . .
H7A H 0.1876(16) 0.3464(16) 0.5047(17) 0.018(6) Uiso 1 1 d . . .
H7B H 0.2230(18) 0.3737(17) 0.5885(17) 0.022(7) Uiso 1 1 d . . .
C8 C 0.0991(2) 0.4048(2) 0.5656(2) 0.0389(7) Uani 1 1 d . . .
H8A H 0.054(2) 0.382(2) 0.538(2) 0.036(9) Uiso 1 1 d . . .
H8B H 0.106(2) 0.458(3) 0.543(2) 0.056(11) Uiso 1 1 d . . .
H8C H 0.089(2) 0.412(2) 0.621(2) 0.048(10) Uiso 1 1 d . . .
C9 C 0.19319(15) 0.25683(16) 0.68202(14) 0.0202(5) Uani 1 1 d . . .
H9A H 0.1572(15) 0.2208(15) 0.7052(14) 0.009(6) Uiso 1 1 d . . .
H9B H 0.1859(15) 0.3107(16) 0.7088(15) 0.012(6) Uiso 1 1 d . . .
C10 C 0.28263(16) 0.22927(17) 0.70099(16) 0.0241(5) Uani 1 1 d . . .
H10A H 0.2930(18) 0.178(2) 0.6712(19) 0.033(8) Uiso 1 1 d . . .
H10B H 0.2934(19) 0.2181(19) 0.760(2) 0.038(8) Uiso 1 1 d . . .
H10C H 0.3190(17) 0.2695(18) 0.6867(17) 0.023(7) Uiso 1 1 d . . .
C11 C 0.05927(15) -0.01238(14) 0.40438(14) 0.0190(5) Uani 1 1 d . . .
H11 H 0.0669(16) -0.0610(17) 0.4350(16) 0.020(7) Uiso 1 1 d . . .
C12 C 0.01534(14) -0.09941(13) 0.29177(13) 0.0166(5) Uani 1 1 d . . .
C13 C 0.03020(15) -0.17540(15) 0.33257(15) 0.0208(5) Uani 1 1 d . . .
H13 H 0.0480(16) -0.1758(17) 0.3863(17) 0.021(7) Uiso 1 1 d . . .
C14 C 0.01523(15) -0.24985(15) 0.29118(15) 0.0216(5) Uani 1 1 d . . .
H14 H 0.0280(15) -0.2990(16) 0.3175(15) 0.012(6) Uiso 1 1 d . . .
C15 C 0.18132(15) 0.08322(15) 0.19002(14) 0.0200(5) Uani 1 1 d . . .
C16 C 0.24381(15) 0.02944(15) 0.22653(15) 0.0238(5) Uani 1 1 d . . .
C17 C 0.31967(17) 0.02740(18) 0.19541(19) 0.0323(6) Uani 1 1 d . . .
H17 H 0.360(2) -0.007(2) 0.2190(19) 0.037(9) Uiso 1 1 d . . .
C18 C 0.33577(19) 0.0768(2) 0.1302(2) 0.0385(7) Uani 1 1 d . . .
H18 H 0.387(3) 0.073(2) 0.109(2) 0.062(11) Uiso 1 1 d . . .
C19 C 0.27497(19) 0.13093(19) 0.09605(18) 0.0351(7) Uani 1 1 d . . .
H19 H 0.2834(19) 0.165(2) 0.0518(19) 0.034(8) Uiso 1 1 d . . .
C20 C 0.19760(16) 0.13587(16) 0.12449(15) 0.0257(5) Uani 1 1 d . . .
C21 C 0.22756(17) -0.02523(17) 0.29715(17) 0.0266(5) Uani 1 1 d . . .
H21A H 0.278(2) -0.0538(19) 0.3165(18) 0.033(8) Uiso 1 1 d . . .
H21B H 0.1860(18) -0.0670(18) 0.2833(17) 0.025(7) Uiso 1 1 d . . .
H21C H 0.2075(19) 0.007(2) 0.3418(19) 0.036(8) Uiso 1 1 d . . .
C22 C 0.13173(19) 0.19303(19) 0.08547(17) 0.0307(6) Uani 1 1 d . . .
H22A H 0.153(2) 0.231(2) 0.051(2) 0.052(10) Uiso 1 1 d . . .
H22B H 0.1084(19) 0.229(2) 0.124(2) 0.035(8) Uiso 1 1 d . . .
H22C H 0.084(2) 0.165(2) 0.055(2) 0.039(9) Uiso 1 1 d . . .
N1 N 0.16650(12) 0.26678(12) 0.59407(11) 0.0197(4) Uani 1 1 d . . .
N2 N 0.02929(12) -0.01881(11) 0.32722(11) 0.0160(4) Uani 1 1 d . . .
O1 O 0.04078(10) 0.15560(9) 0.34032(9) 0.0171(3) Uani 1 1 d . . .
O2 O 0.10680(10) 0.08477(10) 0.21709(10) 0.0193(3) Uani 1 1 d . . .
Ti1 Ti 0.0000 0.08715(3) 0.2500 0.01225(15) Uani 1 2 d S . .
C1C C 0.0000 0.3343(2) 0.2500 0.0300(8) Uani 1 2 d S . .
H1C1 H -0.041(5) 0.289(5) 0.238(6) 0.04(3) Uiso 0.50 1 d P . .
H1C2 H 0.055(5) 0.309(5) 0.261(5) 0.02(2) Uiso 0.50 1 d P . .
Cl1 Cl 0.01192(5) 0.39611(4) 0.16320(4) 0.0405(2) Uani 1 1 d . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 O1 1.327(3) . ?
C1 C6 1.393(3) . ?
C1 C2 1.422(3) . ?
C2 C11 1.415(3) . ?
C2 C3 1.416(3) . ?
C3 C4 1.359(3) . ?
C3 H3 0.96(3) . ?
C4 C5 1.428(3) . ?
C4 H4 0.92(3) . ?
C5 N1 1.362(3) . ?
C5 C6 1.411(3) . ?
C6 H6 0.92(2) . ?
C7 N1 1.463(3) . ?
C7 C8 1.512(4) . ?
C7 H7A 0.96(3) . ?
C7 H7B 0.95(3) . ?
C8 H8A 0.89(4) . ?
C8 H8B 0.94(4) . ?
C8 H8C 0.96(4) . ?
C9 N1 1.469(3) . ?
C9 C10 1.516(4) . ?
C9 H9A 0.93(2) . ?
C9 H9B 0.98(3) . ?
C10 H10A 0.98(3) . ?
C10 H10B 0.98(3) . ?
C10 H10C 0.92(3) . ?
C11 N2 1.309(3) . ?
C11 H11 0.93(3) . ?
C12 C13 1.400(3) . ?
C12 C12 1.406(4) 2 ?
C12 N2 1.427(3) . ?
C13 C14 1.383(3) . ?
C13 H13 0.90(3) . ?
C14 C14 1.387(5) 2 ?
C14 H14 0.91(3) . ?
C15 O2 1.336(3) . ?
C15 C16 1.413(3) . ?
C15 C20 1.417(3) . ?
C16 C17 1.386(4) . ?
C16 C21 1.502(4) . ?
C17 C18 1.381(5) . ?
C17 H17 0.91(3) . ?
C18 C19 1.385(5) . ?
C18 H18 0.94(4) . ?
C19 C20 1.391(4) . ?
C19 H19 0.94(3) . ?
C20 C22 1.497(4) . ?
C21 H21A 0.96(3) . ?
C21 H21B 0.96(3) . ?
C21 H21C 0.98(3) . ?
C22 H22A 0.92(4) . ?
C22 H22B 0.96(3) . ?
C22 H22C 0.99(3) . ?
N2 Ti1 2.1434(19) . ?
O1 Ti1 1.9041(15) . ?
O2 Ti1 1.8741(16) . ?
Ti1 O2 1.8741(16) 2 ?
Ti1 O1 1.9041(15) 2 ?
Ti1 N2 2.1434(19) 2 ?
C1C Cl1 1.766(2) 2 ?
C1C Cl1 1.766(2) . ?
C1C H1C1 0.98(9) . ?
C1C H1C2 0.97(9) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 C1 C6 119.7(2) . . ?
O1 C1 C2 119.93(19) . . ?
C6 C1 C2 120.38(19) . . ?
C11 C2 C3 117.7(2) . . ?
C11 C2 C1 125.1(2) . . ?
C3 C2 C1 117.2(2) . . ?
C4 C3 C2 122.8(2) . . ?
C4 C3 H3 120.5(17) . . ?
C2 C3 H3 116.7(17) . . ?
C3 C4 C5 120.4(2) . . ?
C3 C4 H4 118.5(16) . . ?
C5 C4 H4 121.0(16) . . ?
N1 C5 C6 121.8(2) . . ?
N1 C5 C4 120.5(2) . . ?
C6 C5 C4 117.7(2) . . ?
C1 C6 C5 121.5(2) . . ?
C1 C6 H6 118.5(14) . . ?
C5 C6 H6 120.0(14) . . ?
N1 C7 C8 113.8(2) . . ?
N1 C7 H7A 110.0(16) . . ?
C8 C7 H7A 111.4(16) . . ?
N1 C7 H7B 106.1(17) . . ?
C8 C7 H7B 111.9(17) . . ?
H7A C7 H7B 103(2) . . ?
C7 C8 H8A 111(2) . . ?
C7 C8 H8B 112(2) . . ?
H8A C8 H8B 107(3) . . ?
C7 C8 H8C 111(2) . . ?
H8A C8 H8C 109(3) . . ?
H8B C8 H8C 108(3) . . ?
N1 C9 C10 113.7(2) . . ?
N1 C9 H9A 109.9(14) . . ?
C10 C9 H9A 111.4(15) . . ?
N1 C9 H9B 107.8(14) . . ?
C10 C9 H9B 109.1(14) . . ?
H9A C9 H9B 104(2) . . ?
C9 C10 H10A 110.9(18) . . ?
C9 C10 H10B 108.4(18) . . ?
H10A C10 H10B 109(3) . . ?
C9 C10 H10C 111.6(17) . . ?
H10A C10 H10C 108(2) . . ?
H10B C10 H10C 109(2) . . ?
N2 C11 C2 127.8(2) . . ?
N2 C11 H11 118.1(17) . . ?
C2 C11 H11 114.1(17) . . ?
C13 C12 C12 119.35(13) . 2 ?
C13 C12 N2 125.8(2) . . ?
C12 C12 N2 114.88(11) 2 . ?
C14 C13 C12 120.5(2) . . ?
C14 C13 H13 119.8(17) . . ?
C12 C13 H13 119.7(17) . . ?
C13 C14 C14 120.20(14) . 2 ?
C13 C14 H14 119.8(16) . . ?
C14 C14 H14 119.9(15) 2 . ?
O2 C15 C16 120.2(2) . . ?
O2 C15 C20 119.7(2) . . ?
C16 C15 C20 120.0(2) . . ?
C17 C16 C15 118.9(2) . . ?
C17 C16 C21 120.8(2) . . ?
C15 C16 C21 120.3(2) . . ?
C18 C17 C16 121.8(3) . . ?
C18 C17 H17 119(2) . . ?
C16 C17 H17 119(2) . . ?
C17 C18 C19 119.1(3) . . ?
C17 C18 H18 120(2) . . ?
C19 C18 H18 121(2) . . ?
C18 C19 C20 121.9(3) . . ?
C18 C19 H19 121.7(19) . . ?
C20 C19 H19 116.4(19) . . ?
C19 C20 C15 118.3(3) . . ?
C19 C20 C22 121.3(3) . . ?
C15 C20 C22 120.4(2) . . ?
C16 C21 H21A 108.6(18) . . ?
C16 C21 H21B 113.9(17) . . ?
H21A C21 H21B 107(2) . . ?
C16 C21 H21C 112.0(18) . . ?
H21A C21 H21C 110(3) . . ?
H21B C21 H21C 105(2) . . ?
C20 C22 H22A 112(2) . . ?
C20 C22 H22B 113.8(19) . . ?
H22A C22 H22B 102(3) . . ?
C20 C22 H22C 114.6(19) . . ?
H22A C22 H22C 109(3) . . ?
H22B C22 H22C 105(3) . . ?
C5 N1 C7 122.24(19) . . ?
C5 N1 C9 121.2(2) . . ?
C7 N1 C9 116.58(19) . . ?
C11 N2 C12 119.41(19) . . ?
C11 N2 Ti1 122.93(15) . . ?
C12 N2 Ti1 117.66(14) . . ?
C1 O1 Ti1 136.17(14) . . ?
C15 O2 Ti1 177.34(15) . . ?
O2 Ti1 O2 177.67(10) 2 . ?
O2 Ti1 O1 92.18(7) 2 . ?
O2 Ti1 O1 89.17(7) . . ?
O2 Ti1 O1 89.17(7) 2 2 ?
O2 Ti1 O1 92.18(7) . 2 ?
O1 Ti1 O1 109.47(9) . 2 ?
O2 Ti1 N2 90.25(7) 2 2 ?
O2 Ti1 N2 87.90(7) . 2 ?
O1 Ti1 N2 162.51(7) . 2 ?
O1 Ti1 N2 87.88(7) 2 2 ?
O2 Ti1 N2 87.90(7) 2 . ?
O2 Ti1 N2 90.25(7) . . ?
O1 Ti1 N2 87.88(7) . . ?
O1 Ti1 N2 162.51(7) 2 . ?
N2 Ti1 N2 74.90(10) 2 . ?
Cl1 C1C Cl1 111.6(2) 2 . ?
Cl1 C1C H1C1 117(5) 2 . ?
Cl1 C1C H1C1 112(5) . . ?
Cl1 C1C H1C2 106(5) 2 . ?
Cl1 C1C H1C2 101(5) . . ?
H1C1 C1C H1C2 109(6) . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        27.00
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.578
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.068
