# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_new
_database_code_depnum_ccdc_archive 'CCDC 1860890'
loop_
_audit_author_name
_audit_author_address
'Anastasios Keramidas'
;University of Cyprus
Cyprus
;
_audit_update_record             
;
2018-11-29 deposited with the CCDC.	2019-02-14 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C87 H128 K12 N36 O61 Ti12'
_chemical_formula_sum            'C87 H132 K12 N36 O61 Ti12'
_chemical_formula_weight         3697.74

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'
K K 0.2009 0.2494 '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'

_symmetry_cell_setting           Trigonal
_symmetry_space_group_name_H-M   P-31c

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

_cell_length_a                   20.265(5)
_cell_length_b                   20.265(5)
_cell_length_c                   13.335(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     4742.6(19)
_cell_formula_units_Z            1
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    8231
_cell_measurement_theta_min      2.317
_cell_measurement_theta_max      25.237

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1886
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8538
_exptl_absorpt_correction_T_max  0.9229
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_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  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            61400
_diffrn_reflns_av_R_equivalents  0.1084
_diffrn_reflns_av_sigmaI/netI    0.0489
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.92
_diffrn_reflns_theta_max         26.51
_reflns_number_total             3215
_reflns_number_gt                1612
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_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 > 2σ(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)+(0.2000P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3215
_refine_ls_number_parameters     179
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.1463
_refine_ls_R_factor_gt           0.0826
_refine_ls_wR_factor_ref         0.3239
_refine_ls_wR_factor_gt          0.2615
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.057
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.9324(4) 0.4227(6) 0.3748(4) 0.073(2) Uani 1 1 d . A 1
C2 C 1.0022(5) 0.4161(6) 0.3707(5) 0.087(3) Uani 1 1 d . A 1
H2A H 1.0229 0.4195 0.4389 0.105 Uiso 1 1 calc R A 1
H2B H 1.0417 0.4573 0.3290 0.105 Uiso 1 1 calc R A 1
C3 C 0.9764(6) 0.3336(7) 0.3215(7) 0.112(4) Uani 1 1 d . . 1
H3A H 0.9636 0.3342 0.2500 0.134 Uiso 1 1 calc R . 1
H3B H 1.0196 0.3238 0.3246 0.134 Uiso 1 1 calc R . 1
C4 C 0.9096(6) 0.2710(7) 0.3736(7) 0.096(3) Uani 1 1 d . A 1
H4A H 0.9245 0.2644 0.4420 0.115 Uiso 1 1 calc R A 1
H4B H 0.8918 0.2226 0.3365 0.115 Uiso 1 1 calc R A 1
C5 C 0.8460(5) 0.2898(5) 0.3796(4) 0.067(2) Uani 1 1 d . A 1
C16 C 0.7862(6) 0.4480(6) 0.6120(5) 0.098(3) Uani 1 1 d . B 1
H16A H 0.8212 0.5005 0.5909 0.147 Uiso 1 1 calc R B 1
H16B H 0.7987 0.4404 0.6804 0.147 Uiso 1 1 calc R B 1
H16C H 0.7337 0.4384 0.6102 0.147 Uiso 1 1 calc R B 1
K1 K 0.90862(13) 0.36308(13) 0.62795(13) 0.0965(8) Uani 1 1 d . . 1
N1 N 0.9359(3) 0.4878(5) 0.3750(3) 0.0656(17) Uani 1 1 d . . 1
H1 H 0.9799 0.5305 0.3713 0.079 Uiso 1 1 calc R . 1
N2 N 0.8619(4) 0.3639(4) 0.3793(3) 0.0643(17) Uani 1 1 d . A 1
N3 N 0.7780(4) 0.2388(4) 0.3864(4) 0.0644(16) Uani 1 1 d . A 1
O5 O 0.7931(3) 0.3964(3) 0.5455(3) 0.0694(13) Uani 1 1 d . B 1
O1 O 0.8696(3) 0.4884(3) 0.3812(3) 0.0691(14) Uani 1 1 d . C 1
O2 O 0.7305(3) 0.2700(3) 0.4015(3) 0.0620(13) Uani 1 1 d . . 1
O3 O 0.6667 0.3333 0.4193(4) 0.0511(18) Uani 1 3 d S . 1
O4 O 0.7651(3) 0.38253(17) 0.2500 0.0538(15) Uani 1 2 d S . 1
O11 O 0.8488(12) 0.1911(10) 0.6534(16) 0.072(6) Uani 0.25 1 d P . 1
Ti1 Ti 0.77343(7) 0.38687(7) 0.38416(7) 0.0535(5) Uani 1 1 d . . 1
O6B O 0.0666(16) 0.3028(19) 0.561(2) 0.100(8) Uiso 0.25 1 d PD D 2
C10B C 0.004(3) 0.234(2) 0.596(4) 0.141(17) Uiso 0.25 1 d PD D 2
O6 O 0.1073(11) 0.3492(11) 0.5201(15) 0.058(4) Uiso 0.25 1 d PD E 3
C10 C 0.1125(19) 0.3272(18) 0.6173(17) 0.072(8) Uiso 0.25 1 d PD E 3
O6C O 0.0850(16) 0.3482(18) 0.572(2) 0.090(7) Uiso 0.25 1 d PD F 4
C10C C 0.091(4) 0.300(4) 0.500(5) 0.18(2) Uiso 0.25 1 d PD F 4
O7 O 0.9248(16) 0.1219(17) 0.248(3) 0.134(12) Uiso 0.25 1 d PD . .
C11 C 0.970(4) 0.130(5) 0.335(4) 0.20(3) Uiso 0.25 1 d PD . .
C20 C 0.8104(14) 0.1896(14) 0.7500 0.171(16) Uiso 0.50 2 d SP . .


_geom_special_details            
;
 All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell s.u.'s are taken
 into account individually in the estimation of s.u.'s in distances, angles
 and torsion angles; correlations between s.u.'s in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell s.u.'s is used for estimating s.u.'s 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 N1 1.284(10) . ?
C1 N2 1.328(10) . ?
C1 C2 1.486(12) . ?
C1 K1 3.537(6) . ?
C2 C3 1.620(13) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C4 1.486(14) . ?
C3 K1 3.519(9) 11_765 ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 C5 1.518(12) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 N3 1.245(11) . ?
C5 N2 1.371(10) . ?
C16 O5 1.430(11) . ?
C16 H16A 0.9800 . ?
C16 H16B 0.9800 . ?
C16 H16C 0.9800 . ?
K1 O5 2.954(6) . ?
K1 O11 3.082(18) . ?
K1 N1 3.089(7) 7_766 ?
K1 N2 3.450(5) . ?
K1 C20 3.460(18) . ?
K1 C3 3.519(9) 11_766 ?
K1 K1 4.926(5) 5_556 ?
N1 O1 1.353(8) . ?
N1 K1 3.089(7) 7_766 ?
N1 H1 0.8800 . ?
N2 Ti1 2.066(7) . ?
N3 O2 1.407(8) . ?
O5 Ti1 2.180(4) . ?
O1 Ti1 2.006(5) . ?
O2 Ti1 2.088(5) . ?
O2 Ti1 2.089(5) 4_665 ?
O3 Ti1 1.9312(19) . ?
O3 Ti1 1.9312(19) 4_665 ?
O3 Ti1 1.9312(19) 2_655 ?
O4 Ti1 1.7951(11) . ?
O4 Ti1 1.7951(11) 5 ?
O11 C20 1.50(3) . ?
Ti1 O2 2.089(5) 2_655 ?
Ti1 Ti1 3.245(2) 4_665 ?
Ti1 Ti1 3.245(2) 2_655 ?
O6B C10B 1.42(2) . ?
O6 C10 1.391(18) . ?
O6C C10C 1.41(2) . ?
O7 O7 0.95(6) 3_665 ?
O7 C11 1.44(2) . ?
C20 O11 1.50(3) 3_666 ?
C20 K1 3.460(18) 3_666 ?

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
N1 C1 N2 113.7(7) . . ?
N1 C1 C2 121.8(8) . . ?
N2 C1 C2 124.5(9) . . ?
N1 C1 K1 106.1(4) . . ?
N2 C1 K1 75.4(3) . . ?
C2 C1 K1 88.7(4) . . ?
C1 C2 C3 106.2(8) . . ?
C1 C2 H2A 110.5 . . ?
C3 C2 H2A 110.5 . . ?
C1 C2 H2B 110.5 . . ?
C3 C2 H2B 110.5 . . ?
H2A C2 H2B 108.7 . . ?
C4 C3 C2 112.2(8) . . ?
C4 C3 K1 160.2(7) . 11_765 ?
C2 C3 K1 79.6(5) . 11_765 ?
C4 C3 H3A 109.2 . . ?
C2 C3 H3A 109.2 . . ?
K1 C3 H3A 51.1 11_765 . ?
C4 C3 H3B 109.2 . . ?
C2 C3 H3B 109.2 . . ?
K1 C3 H3B 80.0 11_765 . ?
H3A C3 H3B 107.9 . . ?
C3 C4 C5 109.6(8) . . ?
C3 C4 H4A 109.8 . . ?
C5 C4 H4A 109.8 . . ?
C3 C4 H4B 109.8 . . ?
C5 C4 H4B 109.8 . . ?
H4A C4 H4B 108.2 . . ?
N3 C5 N2 117.8(7) . . ?
N3 C5 C4 121.4(8) . . ?
N2 C5 C4 120.8(8) . . ?
O5 K1 O11 113.0(4) . . ?
O5 K1 N1 107.99(18) . 7_766 ?
O11 K1 N1 137.7(4) . 7_766 ?
O5 K1 N2 52.45(14) . . ?
O11 K1 N2 99.1(4) . . ?
N1 K1 N2 97.52(15) 7_766 . ?
O5 K1 C20 106.8(7) . . ?
O11 K1 C20 25.6(6) . . ?
N1 K1 C20 141.9(5) 7_766 . ?
N2 K1 C20 115.93(15) . . ?
O5 K1 C3 153.5(2) . 11_766 ?
O11 K1 C3 76.9(5) . 11_766 ?
N1 K1 C3 71.0(2) 7_766 11_766 ?
N2 K1 C3 153.2(2) . 11_766 ?
C20 K1 C3 71.0(4) . 11_766 ?
O5 K1 C1 63.57(16) . . ?
O11 K1 C1 113.6(4) . . ?
N1 K1 C1 75.83(17) 7_766 . ?
N2 K1 C1 21.86(17) . . ?
C20 K1 C1 135.0(2) . . ?
C3 K1 C1 137.1(2) 11_766 . ?
O5 K1 K1 77.11(10) . 5_556 ?
O11 K1 K1 128.9(4) . 5_556 ?
N1 K1 K1 69.93(14) 7_766 5_556 ?
N2 K1 K1 121.88(14) . 5_556 ?
C20 K1 K1 103.6(5) . 5_556 ?
C3 K1 K1 77.85(19) 11_766 5_556 ?
C1 K1 K1 115.2(2) . 5_556 ?
C1 N1 O1 117.7(7) . . ?
C1 N1 K1 120.7(5) . 7_766 ?
O1 N1 K1 121.6(5) . 7_766 ?
C1 N1 H1 121.1 . . ?
O1 N1 H1 121.1 . . ?
K1 N1 H1 2.6 7_766 . ?
C1 N2 C5 122.8(8) . . ?
C1 N2 Ti1 117.7(6) . . ?
C5 N2 Ti1 119.5(5) . . ?
C1 N2 K1 82.7(3) . . ?
C5 N2 K1 84.7(3) . . ?
Ti1 N2 K1 104.03(19) . . ?
C5 N3 O2 111.1(6) . . ?
C16 O5 Ti1 126.6(5) . . ?
C16 O5 K1 108.4(4) . . ?
Ti1 O5 K1 118.6(2) . . ?
N1 O1 Ti1 116.8(5) . . ?
N3 O2 Ti1 120.2(4) . . ?
N3 O2 Ti1 133.1(4) . 4_665 ?
Ti1 O2 Ti1 101.9(2) . 4_665 ?
Ti1 O3 Ti1 114.32(13) . 4_665 ?
Ti1 O3 Ti1 114.32(13) . 2_655 ?
Ti1 O3 Ti1 114.32(13) 4_665 2_655 ?
Ti1 O4 Ti1 170.6(4) . 5 ?
C20 O11 K1 91.4(14) . . ?
O4 Ti1 O3 99.3(3) . . ?
O4 Ti1 O1 92.9(2) . . ?
O3 Ti1 O1 145.28(19) . . ?
O4 Ti1 N2 91.67(19) . . ?
O3 Ti1 N2 137.4(2) . . ?
O1 Ti1 N2 73.9(3) . . ?
O4 Ti1 O2 94.53(14) . . ?
O3 Ti1 O2 67.76(14) . . ?
O1 Ti1 O2 143.7(2) . . ?
N2 Ti1 O2 70.4(2) . . ?
O4 Ti1 O2 94.71(14) . 2_655 ?
O3 Ti1 O2 67.74(14) . 2_655 ?
O1 Ti1 O2 79.0(2) . 2_655 ?
N2 Ti1 O2 152.4(3) . 2_655 ?
O2 Ti1 O2 135.4(2) . 2_655 ?
O4 Ti1 O5 175.6(2) . . ?
O3 Ti1 O5 85.1(2) . . ?
O1 Ti1 O5 83.54(18) . . ?
N2 Ti1 O5 84.82(19) . . ?
O2 Ti1 O5 86.87(18) . . ?
O2 Ti1 O5 87.21(19) 2_655 . ?
O4 Ti1 Ti1 85.89(17) . 4_665 ?
O3 Ti1 Ti1 32.84(7) . 4_665 ?
O1 Ti1 Ti1 177.18(17) . 4_665 ?
N2 Ti1 Ti1 108.7(2) . 4_665 ?
O2 Ti1 Ti1 39.05(14) . 4_665 ?
O2 Ti1 Ti1 98.53(14) 2_655 4_665 ?
O5 Ti1 Ti1 97.80(14) . 4_665 ?
O4 Ti1 Ti1 85.99(17) . 2_655 ?
O3 Ti1 Ti1 32.84(7) . 2_655 ?
O1 Ti1 Ti1 117.40(18) . 2_655 ?
N2 Ti1 Ti1 168.5(2) . 2_655 ?
O2 Ti1 Ti1 98.55(14) . 2_655 ?
O2 Ti1 Ti1 39.02(14) 2_655 2_655 ?
O5 Ti1 Ti1 97.98(14) . 2_655 ?
Ti1 Ti1 Ti1 60.0 4_665 2_655 ?
O7 O7 C11 110(6) 3_665 . ?
O11 C20 O11 129(4) 3_666 . ?
O11 C20 K1 141.7(9) 3_666 . ?
O11 C20 K1 62.9(10) . . ?
O11 C20 K1 62.9(10) 3_666 3_666 ?
O11 C20 K1 141.7(9) . 3_666 ?
K1 C20 K1 135.1(15) . 3_666 ?

_diffrn_measured_fraction_theta_max 0.975
_diffrn_reflns_theta_full        26.51
_diffrn_measured_fraction_theta_full 0.975
_refine_diff_density_max         0.735
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.129
