# Electronic Supplementary Material (ESI) for Chemical Science.
# 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_trial2_a
_database_code_depnum_ccdc_archive 'CCDC 1859034'
_audit_update_record             
;
2018-07-29 deposited with the CCDC.
2018-12-19 downloaded from the CCDC.
;
_audit_creation_date             2018-07-13
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            Ti3-BPDC
_chemical_name_systematic        Ti3-BPDC
_chemical_formula_moiety         '0.67(C63 H37.5 O21 Ti4.5)'
_chemical_formula_sum            'C42 H30 O14 Ti3'
_chemical_formula_weight         902.36
_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'
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      trigonal
_space_group_IT_number           166
_space_group_name_H-M_alt        'R -3 m'
_space_group_name_Hall           '-R 3 2"'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z+1/3'
'-x+y+2/3, y+1/3, z+1/3'
'x+2/3, x-y+1/3, z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+2/3'
'-x+y+1/3, y+2/3, z+2/3'
'x+1/3, x-y+2/3, z+2/3'

_cell_length_a                   25.8366(16)
_cell_length_b                   25.8366(16)
_cell_length_c                   13.6675(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     7901.1(11)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    8282
_cell_measurement_temperature    297(2)
_cell_measurement_theta_max      49.454
_cell_measurement_theta_min      4.706
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.248
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.5804
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0802 before and 0.0448 after correction.
The Ratio of minimum to maximum transmission is 0.7790.
The λ/2 correction factor is 0.00150.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    0.569
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       Cubic
_exptl_crystal_F_000             1380
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0157
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            16826
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.727
_diffrn_reflns_theta_max         24.727
_diffrn_reflns_theta_min         2.353
_diffrn_ambient_temperature      296.96
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1332
_reflns_number_total             1614
_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 v8.34A (Bruker, 2013)'
_computing_data_collection       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.976
_refine_diff_density_min         -1.412
_refine_diff_density_rms         0.095
_refine_ls_extinction_coef       0.0018(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.607
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     64
_refine_ls_number_reflns         1614
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.1213
_refine_ls_R_factor_gt           0.1129
_refine_ls_restrained_S_all      1.604
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3430
_refine_ls_wR_factor_ref         0.3547
_refine_special_details          SQUEEZE
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O3-H3A
 1 with sigma of 0.96
3. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Riding coordinates:
 C6(H3A)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C3(H3), C7(H7), C6(H6)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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 0.3333 0.6667 0.44892(9) 0.0544(7) Uani 1 6 d S T P . .
Ti2 Ti 0.3333 0.6667 0.1667 0.0725(9) Uani 1 12 d S T P . .
O1 O 0.29078(12) 0.5816(2) 0.4254(5) 0.128(2) Uani 1 2 d S T P . .
O2 O 0.29220(15) 0.5844(3) 0.2670(6) 0.178(4) Uani 1 2 d S T P . .
C1 C 0.27866(18) 0.5573(4) 0.3427(7) 0.117(2) Uani 1 2 d S T P . .
C2 C 0.24551(17) 0.4910(3) 0.3420(7) 0.139(3) Uani 1 2 d S T P . .
C5 C 0.1835(2) 0.3669(4) 0.3349(8) 0.161(4) Uani 1 2 d S T P . .
C4 C 0.1992(2) 0.3985(4) 0.4209(8) 0.165(5) Uani 1 2 d S T P . .
H4 H 0.1889 0.3777 0.4799 0.198 Uiso 1 2 calc RS T P . .
C3 C 0.22864(19) 0.4573(4) 0.4222(8) 0.167(5) Uani 1 2 d S T P . .
H3 H 0.2382 0.4764 0.4827 0.200 Uiso 1 2 calc RS T P . .
O3 O 0.3333 0.6667 0.5998(19) 0.219(6) Uani 1 6 d DS TU P . .
C7 C 0.2300(2) 0.4601(5) 0.2563(10) 0.236(9) Uani 1 2 d S T P . .
H7 H 0.2405 0.4810 0.1975 0.284 Uiso 1 2 calc RS T P . .
C6 C 0.2009(2) 0.4018(5) 0.2544(10) 0.248(11) Uani 1 2 d S T P . .
H6 H 0.1916 0.3831 0.1936 0.297 Uiso 1 2 calc RS T P . .
H3A H 0.3333 0.6667 0.6667 0.297 Uiso 1 12 d DRS T P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Ti1 0.0582(8) 0.0582(8) 0.0468(10) 0.000 0.000 0.0291(4)
Ti2 0.0688(11) 0.0688(11) 0.0798(17) 0.000 0.000 0.0344(5)
O1 0.155(4) 0.085(3) 0.120(5) 0.010(3) 0.0050(14) 0.0425(16)
O2 0.244(8) 0.091(4) 0.147(6) 0.052(4) 0.0262(18) 0.0457(18)
C1 0.133(5) 0.079(4) 0.122(7) 0.029(4) 0.014(2) 0.039(2)
C2 0.188(8) 0.068(4) 0.119(6) 0.017(4) 0.008(2) 0.034(2)
C5 0.220(11) 0.086(5) 0.131(8) 0.026(5) 0.013(3) 0.043(2)
C4 0.237(12) 0.088(5) 0.121(7) 0.019(5) 0.009(3) 0.044(3)
C3 0.239(11) 0.081(5) 0.127(7) 0.022(5) 0.011(2) 0.040(3)
O3 0.223(7) 0.223(7) 0.210(10) 0.000 0.000 0.112(3)
C7 0.39(2) 0.088(6) 0.136(9) 0.038(6) 0.019(3) 0.044(3)
C6 0.42(3) 0.084(6) 0.131(9) 0.014(5) 0.007(3) 0.042(3)

_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 1.931(6) 3_565 ?
Ti1 O1 1.931(6) . ?
Ti1 O1 1.931(6) 2_665 ?
Ti1 O3 2.06(3) . ?
Ti2 O2 2.296(5) 26_455 ?
Ti2 O2 2.296(5) 25_565 ?
Ti2 O2 2.296(5) 3_565 ?
Ti2 O2 2.296(5) 27 ?
Ti2 O2 2.296(5) 2_665 ?
Ti2 O2 2.296(5) . ?
O1 C1 1.254(11) . ?
O2 C1 1.198(10) . ?
C1 C2 1.483(12) . ?
C2 C3 1.332(13) . ?
C2 C7 1.361(15) . ?
C5 C5 1.504(19) 31 ?
C5 C4 1.372(15) . ?
C5 C6 1.349(15) . ?
C4 H4 0.9300 . ?
C4 C3 1.316(13) . ?
C3 H3 0.9300 . ?
O3 H3A 0.9140 . ?
C7 H7 0.9300 . ?
C7 C6 1.303(15) . ?
C6 H6 0.9300 . ?

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 117.28(11) 3_565 . ?
O1 Ti1 O1 117.28(11) 3_565 2_665 ?
O1 Ti1 O1 117.28(11) . 2_665 ?
O1 Ti1 O3 99.59(19) 3_565 . ?
O1 Ti1 O3 99.59(19) . . ?
O1 Ti1 O3 99.6(2) 2_665 . ?
O2 Ti2 O2 92.0(3) 3_565 26_455 ?
O2 Ti2 O2 180.0 26_455 2_665 ?
O2 Ti2 O2 88.0(3) 3_565 . ?
O2 Ti2 O2 92.0(3) 3_565 25_565 ?
O2 Ti2 O2 88.0(3) 25_565 27 ?
O2 Ti2 O2 88.0(3) 26_455 25_565 ?
O2 Ti2 O2 88.0(3) 3_565 2_665 ?
O2 Ti2 O2 88.0(3) 26_455 27 ?
O2 Ti2 O2 92.0(3) 25_565 2_665 ?
O2 Ti2 O2 180.0 25_565 . ?
O2 Ti2 O2 92.0(3) 27 2_665 ?
O2 Ti2 O2 88.0(3) . 2_665 ?
O2 Ti2 O2 92.0(3) 26_455 . ?
O2 Ti2 O2 92.0(3) . 27 ?
O2 Ti2 O2 180.0 3_565 27 ?
C1 O1 Ti1 125.2(5) . . ?
C1 O2 Ti2 157.1(7) . . ?
O1 C1 C2 116.0(7) . . ?
O2 C1 O1 124.0(8) . . ?
O2 C1 C2 120.0(9) . . ?
C3 C2 C1 124.2(9) . . ?
C3 C2 C7 114.9(8) . . ?
C7 C2 C1 121.0(8) . . ?
C4 C5 C5 122.5(10) . 31 ?
C6 C5 C5 123.8(13) . 31 ?
C6 C5 C4 113.7(9) . . ?
C5 C4 H4 119.1 . . ?
C3 C4 C5 121.8(9) . . ?
C3 C4 H4 119.1 . . ?
C2 C3 H3 118.1 . . ?
C4 C3 C2 123.7(10) . . ?
C4 C3 H3 118.1 . . ?
Ti1 O3 H3A 180.0 . . ?
C2 C7 H7 119.1 . . ?
C6 C7 C2 121.7(10) . . ?
C6 C7 H7 119.1 . . ?
C5 C6 H6 117.9 . . ?
C7 C6 C5 124.2(13) . . ?
C7 C6 H6 117.9 . . ?

_shelx_res_file                  
;
    trial2_a.res created by SHELXL-2014/7

TITL trial2_a.res in R-3m
REM Old TITL trial2 in R3m
REM SHELXT solution in R-3m
REM R1 0.224, Rweak 0.037, Alpha 0.048, Orientation as input
REM Formula found by SHELXT: C45 O12 Ti I2
CELL 0.71073 25.8366 25.8366 13.6675 90 90 120
ZERR 3 0.0016 0.0016 0.0009 0 0 0
LATT 3
SYMM -Y,+X-Y,+Z
SYMM +Y-X,-X,+Z
SYMM +Y,+X,-Z
SYMM -Y+X,-Y,-Z
SYMM -X,-X+Y,-Z
SFAC C H O Ti
UNIT 126 90 42 9
DFIX 1 0.96 O3 H3a
ISOR 0.005 0.01 O3

L.S. 32
PLAN  10
TEMP 23.81
BOND $H
LIST 6
fmap 2
acta
OMIT -3 4 5
OMIT -2 2 5
OMIT 0 0 3
OMIT -3 10 5
OMIT -7 12 2
REM <olex2.extras>
REM <HklSrc "%.\\trial2_a.hkl">
REM </olex2.extras>

WGHT    0.200000
EXTI    0.001790
FVAR       1.98063
TI1   4    0.333333    0.666667    0.448917    10.16667    0.05816    0.05816 =
         0.04685    0.00000    0.00000    0.02908
TI2   4    0.333333    0.666667    0.166667    10.08333    0.06882    0.06882 =
         0.07984    0.00000    0.00000    0.03441
O1    3    0.290779    0.581557    0.425380    10.50000    0.15549    0.08499 =
         0.11996    0.01005    0.00503    0.04250
O2    3    0.292196    0.584393    0.267023    10.50000    0.24363    0.09138 =
         0.14688    0.05246    0.02623    0.04569
C1    1    0.278661    0.557323    0.342660    10.50000    0.13291    0.07896 =
         0.12191    0.02890    0.01445    0.03948
C2    1    0.245514    0.491028    0.341961    10.50000    0.18831    0.06841 =
         0.11922    0.01675    0.00838    0.03421
C5    1    0.183466    0.366932    0.334854    10.50000    0.22049    0.08566 =
         0.13100    0.02574    0.01287    0.04283
C4    1    0.199232    0.398464    0.420910    10.50000    0.23666    0.08791 =
         0.12115    0.01897    0.00948    0.04395
AFIX  43
H4    2    0.188866    0.377733    0.479887    10.50000   -1.20000
AFIX   0
C3    1    0.228638    0.457276    0.422245    10.50000    0.23941    0.08099 =
         0.12659    0.02191    0.01096    0.04050
AFIX  43
H3    2    0.238180    0.476361    0.482692    10.50000   -1.20000
AFIX   0
O3    3    0.333333    0.666667    0.599795    10.16667    0.22346    0.22346 =
         0.21044    0.00000    0.00000    0.11173
C7    1    0.230031    0.460062    0.256264    10.50000    0.38604    0.08789 =
         0.13553    0.03751    0.01875    0.04395
AFIX  43
H7    2    0.240504    0.481008    0.197492    10.50000   -1.20000
AFIX   0
C6    1    0.200917    0.401835    0.254381    10.50000    0.41710    0.08369 =
         0.13147    0.01395    0.00698    0.04185
AFIX  43
H6    2    0.191565    0.383129    0.193617    10.50000   -1.20000
AFIX   3
H3A   2    0.333331    0.666667    0.666668    10.08333   -1.20000
AFIX   0
HKLF 4

REM  trial2_a.res in R-3m
REM R1 =  0.1129 for    1332 Fo > 4sig(Fo)  and  0.1213 for all    1614 data
REM     64 parameters refined using      7 restraints

END

WGHT      0.2000      0.0000

REM Highest difference peak  1.976,  deepest hole -1.412,  1-sigma level  0.095
Q1    1   0.3181  0.6362  0.5810  10.50000  0.05    0.68
Q2    1   0.3495  0.6505  0.3193  10.50000  0.05    0.47
Q3    1   0.3333  0.6667  0.0797  10.16667  0.05    0.43
Q4    1   0.3098  0.6196  0.1095  10.50000  0.05    0.42
Q5    1   0.2862  0.6123  0.1888  11.00000  0.05    0.40
Q6    1   0.3707  0.6293  0.3454  10.50000  0.05    0.37
Q7    1   0.3673  0.6327  0.2754  10.50000  0.05    0.35
Q8    1   0.2708  0.6354  0.1639  10.50000  0.05    0.35
Q9    1   0.2893  0.6278  0.3733  11.00000  0.05    0.27
Q10   1   0.2864  0.5728  0.1188  10.50000  0.05    0.24
;
_shelx_res_checksum              30291
_olex2_submission_special_instructions 'No special instructions were received'
_exptl_crystal_recrystallization_method Solvothermal
_chemical_compound_source        No
_exptl_crystal_preparation       Catalysis
