# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_l
_database_code_depnum_ccdc_archive 'CCDC 1424027'
_audit_update_record             
;
2016-01-20 deposited with the CCDC.
2016-02-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C68 H86 N12 O17 Ti4'
_chemical_formula_weight         1535.02

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

_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_H-M_alt        'P -4 21 c'
_space_group_name_Hall           'P -4 2n'

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

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'y, -x, -z'
'-y, x, -z'
'-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'

_cell_length_a                   17.367(3)
_cell_length_b                   17.367(3)
_cell_length_c                   13.730(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4141.2(14)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4108
_cell_measurement_theta_min      3.7
_cell_measurement_theta_max      24.3

_exptl_crystal_description       block
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_F_000             1548
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.700
_exptl_crystal_size_mid          0.400
_exptl_crystal_size_min          0.300
_exptl_absorpt_coefficient_mu    0.437
_shelx_estimated_absorpt_T_min   0.750
_shelx_estimated_absorpt_T_max   0.880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8468
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication '
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Rigaku Saturn'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            12612
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.967
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_full        24.994
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_point_group_measured_fraction_full 0.973
_reflns_number_total             3549
_reflns_number_gt                2951
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.743
_reflns_Friedel_fraction_max     0.942
_reflns_Friedel_fraction_full    0.942

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0016P)²+16.1241P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1023 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.035(16)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3549
_refine_ls_number_parameters     211
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0940
_refine_ls_R_factor_gt           0.0807
_refine_ls_wR_factor_ref         0.1887
_refine_ls_wR_factor_gt          0.1827
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_restrained_S_all      1.141
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.23277(11) 0.60651(11) 0.85179(18) 0.0637(6) Uani 1 1 d . . . . .
O1 O 0.2914(4) 0.6835(4) 0.9268(5) 0.0632(19) Uani 1 1 d . . . . .
O2 O 0.2302(4) 0.5359(4) 0.9651(5) 0.0627(19) Uani 1 1 d . . . . .
O3 O 0.1321(5) 0.6255(5) 0.8634(10) 0.116(4) Uani 1 1 d . . . . .
O4 O 0.2473(6) 0.6529(5) 0.7379(6) 0.089(3) Uani 1 1 d . . . . .
N1 N 0.3525(4) 0.5694(4) 0.8395(6) 0.052(2) Uani 1 1 d . . . . .
N2 N 0.3741(5) 0.5077(5) 0.7926(7) 0.062(2) Uani 1 1 d . . . . .
N3 N 0.2394(6) 0.4962(5) 0.7743(7) 0.067(3) Uani 1 1 d . . . . .
C1 C 0.4046(6) 0.6189(5) 0.8776(7) 0.053(2) Uani 1 1 d . . . . .
C2 C 0.3671(6) 0.6805(6) 0.9288(8) 0.052(2) Uani 1 1 d . . . . .
C3 C 0.4122(6) 0.7314(6) 0.9812(8) 0.056(3) Uani 1 1 d . . . . .
H3 H 0.3890 0.7709 1.0162 0.067 Uiso 1 1 calc R U . . .
C4 C 0.2763(6) 0.4936(6) 1.0180(7) 0.053(2) Uani 1 1 d . . . . .
C5 C 0.5283(6) 0.6646(6) 0.9259(8) 0.058(3) Uani 1 1 d . . . . .
H5 H 0.5817 0.6622 0.9225 0.069 Uiso 1 1 calc R U . . .
C6 C 0.4861(6) 0.6116(6) 0.8772(8) 0.057(3) Uani 1 1 d . . . . .
H6 H 0.5099 0.5713 0.8443 0.069 Uiso 1 1 calc R U . . .
C7 C 0.1792(9) 0.4556(7) 0.7415(10) 0.086(4) Uani 1 1 d . . . . .
H7 H 0.1301 0.4749 0.7532 0.104 Uiso 1 1 calc R U . . .
C8 C 0.1853(10) 0.3878(8) 0.6918(11) 0.098(5) Uani 1 1 d . . . . .
H8 H 0.1413 0.3623 0.6705 0.118 Uiso 1 1 calc R U . . .
C9 C 0.2567(10) 0.3574(8) 0.6737(11) 0.102(5) Uani 1 1 d . . . . .
H9 H 0.2624 0.3122 0.6382 0.122 Uiso 1 1 calc R U . . .
C10 C 0.3209(9) 0.3967(7) 0.7103(10) 0.087(4) Uani 1 1 d . . . . .
H10 H 0.3702 0.3766 0.7027 0.105 Uiso 1 1 calc R U . . .
C11 C 0.3095(7) 0.4669(6) 0.7589(8) 0.062(3) Uani 1 1 d . . . . .
C15 C 0.2879(17) 0.6702(17) 0.640(2) 0.199(11) Uiso 1 1 d . . . . .
C16 C 0.3263(16) 0.7307(15) 0.6285(15) 0.203(12) Uani 1 1 d . . . . .
C17 C 0.232(2) 0.6387(19) 0.575(3) 0.266(17) Uiso 1 1 d . . . . .
C12 C 0.0831(18) 0.6778(19) 0.774(2) 0.098(9) Uiso 0.5 1 d . . P A 1
C13 C 0.049(2) 0.623(2) 0.700(3) 0.143(14) Uiso 0.5 1 d . . P A 1
C12' C 0.000(3) 0.615(3) 0.922(3) 0.169(17) Uiso 0.5 1 d . . P B 2
C13' C -0.016(6) 0.526(6) 0.994(5) 0.30(4) Uiso 0.5 1 d . . P B 2
C14 C 0.0386(15) 0.7134(15) 0.8230(18) 0.190(11) Uiso 1 1 d . . . . .
O5 O 0.5000 0.5000 0.5000 0.41(4) Uani 1 4 d S T P . .


_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 O4 1.777(9) . ?
Ti1 O3 1.786(9) . ?
Ti1 O1 1.971(7) . ?
Ti1 O2 1.982(8) . ?
Ti1 N1 2.184(8) . ?
Ti1 N3 2.195(9) . ?
O1 C2 1.317(11) . ?
O2 C4 1.307(12) . ?
O3 C12 1.75(3) . ?
O4 C15 1.55(3) . ?
N1 N2 1.306(11) . ?
N1 C1 1.352(12) . ?
N2 C11 1.405(14) . ?
N3 C11 1.337(14) . ?
N3 C7 1.338(14) . ?
C1 C6 1.421(13) . ?
C1 C2 1.436(14) . ?
C2 C3 1.382(13) . ?
C3 C4 1.420(14) 3_567 ?
C4 C5 1.417(14) 4_657 ?
C4 C3 1.420(14) 4_657 ?
C5 C6 1.354(14) . ?
C5 C4 1.417(14) 3_567 ?
C7 C8 1.366(18) . ?
C8 C9 1.371(19) . ?
C9 C10 1.400(19) . ?
C10 C11 1.405(15) . ?
C15 C16 1.25(3) . ?
C15 C17 1.43(4) . ?
C12 C14 1.20(3) . ?
C12 C13 1.52(5) . ?
C12' C13' 1.85(10) . ?
C13' C13' 1.08(15) 2_565 ?

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
O4 Ti1 O3 97.7(5) . . ?
O4 Ti1 O1 94.5(4) . . ?
O3 Ti1 O1 109.5(4) . . ?
O4 Ti1 O2 167.1(4) . . ?
O3 Ti1 O2 91.3(5) . . ?
O1 Ti1 O2 91.2(3) . . ?
O4 Ti1 N1 86.0(4) . . ?
O3 Ti1 N1 173.4(4) . . ?
O1 Ti1 N1 75.4(3) . . ?
O2 Ti1 N1 84.2(3) . . ?
O4 Ti1 N3 87.8(4) . . ?
O3 Ti1 N3 104.8(4) . . ?
O1 Ti1 N3 145.0(3) . . ?
O2 Ti1 N3 80.9(3) . . ?
N1 Ti1 N3 69.8(3) . . ?
C2 O1 Ti1 120.0(7) . . ?
C4 O2 Ti1 140.4(7) . . ?
C12 O3 Ti1 120.7(13) . . ?
C15 O4 Ti1 156.5(13) . . ?
N2 N1 C1 121.4(8) . . ?
N2 N1 Ti1 123.7(6) . . ?
C1 N1 Ti1 114.8(6) . . ?
N1 N2 C11 110.3(9) . . ?
C11 N3 C7 117.3(11) . . ?
C11 N3 Ti1 117.1(7) . . ?
C7 N3 Ti1 125.6(9) . . ?
N1 C1 C6 127.4(9) . . ?
N1 C1 C2 111.1(8) . . ?
C6 C1 C2 121.3(9) . . ?
O1 C2 C3 123.5(10) . . ?
O1 C2 C1 118.1(9) . . ?
C3 C2 C1 118.3(9) . . ?
C2 C3 C4 120.5(10) . 3_567 ?
O2 C4 C5 120.4(10) . 4_657 ?
O2 C4 C3 120.5(9) . 4_657 ?
C5 C4 C3 119.1(10) 4_657 4_657 ?
C6 C5 C4 122.0(10) . 3_567 ?
C5 C6 C1 118.5(10) . . ?
N3 C7 C8 124.2(15) . . ?
C7 C8 C9 119.5(14) . . ?
C8 C9 C10 117.9(13) . . ?
C9 C10 C11 118.8(14) . . ?
N3 C11 C10 122.2(12) . . ?
N3 C11 N2 119.0(9) . . ?
C10 C11 N2 118.8(12) . . ?
C16 C15 C17 127(3) . . ?
C16 C15 O4 121(3) . . ?
C17 C15 O4 99(2) . . ?
C14 C12 C13 117(3) . . ?
C14 C12 O3 101(3) . . ?
C13 C12 O3 110(2) . . ?
C13' C13' C12' 129(10) 2_565 . ?

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
O4 Ti1 O3 C12 -0.9(14) . . . . ?
O1 Ti1 O3 C12 96.7(14) . . . . ?
O2 Ti1 O3 C12 -171.5(14) . . . . ?
N3 Ti1 O3 C12 -90.6(14) . . . . ?
O3 Ti1 O4 C15 -157(3) . . . . ?
O1 Ti1 O4 C15 92(3) . . . . ?
O2 Ti1 O4 C15 -24(4) . . . . ?
N1 Ti1 O4 C15 17(3) . . . . ?
N3 Ti1 O4 C15 -53(3) . . . . ?
C1 N1 N2 C11 -178.9(9) . . . . ?
Ti1 N1 N2 C11 -4.4(12) . . . . ?
N2 N1 C1 C6 -2.6(16) . . . . ?
Ti1 N1 C1 C6 -177.6(8) . . . . ?
N2 N1 C1 C2 -177.7(9) . . . . ?
Ti1 N1 C1 C2 7.4(10) . . . . ?
Ti1 O1 C2 C3 -178.7(8) . . . . ?
Ti1 O1 C2 C1 -1.7(12) . . . . ?
N1 C1 C2 O1 -4.1(13) . . . . ?
C6 C1 C2 O1 -179.5(9) . . . . ?
N1 C1 C2 C3 173.0(9) . . . . ?
C6 C1 C2 C3 -2.4(15) . . . . ?
O1 C2 C3 C4 178.5(10) . . . 3_567 ?
C1 C2 C3 C4 1.6(15) . . . 3_567 ?
Ti1 O2 C4 C5 63.8(14) . . . 4_657 ?
Ti1 O2 C4 C3 -115.1(11) . . . 4_657 ?
C4 C5 C6 C1 4.1(16) 3_567 . . . ?
N1 C1 C6 C5 -175.1(10) . . . . ?
C2 C1 C6 C5 -0.4(15) . . . . ?
C11 N3 C7 C8 -1.5(19) . . . . ?
Ti1 N3 C7 C8 178.7(11) . . . . ?
N3 C7 C8 C9 0(2) . . . . ?
C7 C8 C9 C10 2(2) . . . . ?
C8 C9 C10 C11 -3(2) . . . . ?
C7 N3 C11 C10 0.1(17) . . . . ?
Ti1 N3 C11 C10 179.9(9) . . . . ?
C7 N3 C11 N2 -179.8(10) . . . . ?
Ti1 N3 C11 N2 0.0(14) . . . . ?
C9 C10 C11 N3 2.4(19) . . . . ?
C9 C10 C11 N2 -177.8(12) . . . . ?
N1 N2 C11 N3 2.7(14) . . . . ?
N1 N2 C11 C10 -177.2(10) . . . . ?
Ti1 O4 C15 C16 -106(4) . . . . ?
Ti1 O4 C15 C17 110(3) . . . . ?
Ti1 O3 C12 C14 -144(2) . . . . ?
Ti1 O3 C12 C13 93(2) . . . . ?

_refine_diff_density_max         0.867
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.085



