# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_UP9182
_database_code_depnum_ccdc_archive 'CCDC 1472932'
_audit_update_record             
;
2016-05-10 deposited with the CCDC.
2016-06-13 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_CHEMW03_UP9182              
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: This out-of-range value is due to disordered, co-crystallized diethyl ether solvent and the use of SQUEEZE to correct the presence of such solvent.
;
_vrf_PLAT244_UP9182              
;
PROBLEM: Low    'Solvent' Ueq as Compared to Neighbors of        C43 Check
RESPONSE: This alert is a result of a disordered diethyl ether molecule in the unit cell that was not corrected by SQUEEZE.
;
_vrf_PLAT360_UP9182              
;
PROBLEM: Short  C(sp3)-C(sp3) Bond   C43    -   C44    ..       1.41 Ang.
RESPONSE: This alert is a result of a disordered diethyl ether molecule in the unit cell that was not corrected by SQUEEZE.
;
# Added during the CSD deposition process: Tuesday 10 May 2016 04:11 PM
# end Validation Reply Form

#Compound 2

# Crystallographer: Brian C. Manor

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C40 H50 F3 N O4 P2 S Ti, 2.5(C4 H10 O1).'
_chemical_formula_sum            'C50 H75 F3 N O7.50 P2 S Ti'
_chemical_formula_weight         1009.01

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'
F F 0.0171 0.0103 '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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   16.5327(12)
_cell_length_b                   12.0477(8)
_cell_length_c                   27.564(2)
_cell_angle_alpha                90
_cell_angle_beta                 97.271(4)
_cell_angle_gamma                90
_cell_volume                     5446.2(7)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9703
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.42
_cell_measurement_theta_min      2.42

_exptl_crystal_description       prism
_exptl_crystal_colour            purple
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_F_000             2148
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.13
_exptl_absorpt_coefficient_mu    0.312
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6834
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   'SADABS v2014/4'
_diffrn_ambient_temperature      100(1)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device       'CCD Area Detector'
_diffrn_measurement_device_type  'Bruker APEXII'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_reflns_number            85632
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_theta_min         1.489
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             12515
_reflns_number_gt                9264
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
Three sites occupied by Et2O molecules were identified in the asymmetric unit. One site was ordered and fully occupied. The second and third sites were considerably disordered and were treated by SQUEEZE as a diffuse contribution. In the resulting void space, a contribution of 250 e- per unit cell was found and taken to represent 1.5 Et2O molecules for each Ti complex, giving a total of 2.5 Et2O in the asymmetric unit. 
;

_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'
_computing_publication_material  'Yadokari-XG 2009 (Wakita,Nemoto et al., 2009)'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0927P)²+2.8904P] 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_number_reflns         12515
_refine_ls_number_parameters     536
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0539
_refine_ls_wR_factor_ref         0.1618
_refine_ls_wR_factor_gt          0.1519
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.001
_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 0.46918(3) 0.74686(3) 0.33073(2) 0.01761(11) Uani 1 1 d . . . . .
S1 S 0.46444(4) 0.63294(5) 0.22446(2) 0.02284(14) Uani 1 1 d . . . . .
P1 P 0.32234(4) 0.82979(5) 0.31756(2) 0.01865(14) Uani 1 1 d . . . . .
P2 P 0.61140(4) 0.72318(5) 0.38379(2) 0.02023(14) Uani 1 1 d . . . . .
F1 F 0.42283(12) 0.78009(16) 0.15565(7) 0.0473(5) Uani 1 1 d . . . . .
F2 F 0.55019(12) 0.73359(17) 0.16395(7) 0.0496(5) Uani 1 1 d . . . . .
F3 F 0.45854(15) 0.62181(19) 0.12959(7) 0.0637(6) Uani 1 1 d . . . . .
O1 O 0.45279(10) 0.61473(13) 0.33974(6) 0.0227(4) Uani 1 1 d . . . . .
O2 O 0.51206(10) 0.92019(13) 0.31009(6) 0.0204(4) Uani 1 1 d . . . . .
O3 O 0.47551(10) 0.73299(13) 0.25568(6) 0.0214(4) Uani 1 1 d . . . . .
O4 O 0.38378(12) 0.58903(17) 0.21900(8) 0.0359(5) Uani 1 1 d . . . . .
O5 O 0.53119(12) 0.55725(16) 0.23245(8) 0.0336(5) Uani 1 1 d . . . . .
O6 O 0.5446(3) 0.2051(4) 0.13068(16) 0.1051(12) Uani 1 1 d . . . . .
N1 N 0.45241(12) 0.81325(16) 0.39739(7) 0.0194(4) Uani 1 1 d . . . . .
C1 C 0.40464(14) 0.90758(18) 0.40274(9) 0.0179(5) Uani 1 1 d . . . . .
C2 C 0.42182(15) 0.98364(19) 0.44086(9) 0.0216(5) Uani 1 1 d . . . . .
H2 H 0.4652 0.9701 0.4651 0.029 Uiso 1 1 calc R U . . .
C3 C 0.37534(15) 1.0794(2) 0.44336(9) 0.0217(5) Uani 1 1 d . . . . .
H3 H 0.3888 1.1292 0.4689 0.029 Uiso 1 1 calc R U . . .
C4 C 0.30895(15) 1.1020(2) 0.40818(9) 0.0214(5) Uani 1 1 d . . . . .
C5 C 0.29174(15) 1.0270(2) 0.36954(9) 0.0208(5) Uani 1 1 d . . . . .
H5 H 0.2483 1.0411 0.3454 0.028 Uiso 1 1 calc R U . . .
C6 C 0.33854(14) 0.93143(19) 0.36651(9) 0.0183(5) Uani 1 1 d . . . . .
C7 C 0.25708(17) 1.2043(2) 0.41204(10) 0.0285(6) Uani 1 1 d . . . . .
H7A H 0.2078 1.1840 0.4249 0.043 Uiso 1 1 calc R U . . .
H7B H 0.2438 1.2367 0.3802 0.043 Uiso 1 1 calc R U . . .
H7C H 0.2868 1.2571 0.4335 0.043 Uiso 1 1 calc R U . . .
C8 C 0.27846(15) 0.9045(2) 0.26181(9) 0.0233(5) Uani 1 1 d . . . . .
H8 H 0.2322 0.9492 0.2695 0.031 Uiso 1 1 calc R U . . .
C9 C 0.34164(17) 0.9815(2) 0.24383(10) 0.0301(6) Uani 1 1 d . . . . .
H9A H 0.3887 0.9391 0.2380 0.045 Uiso 1 1 calc R U . . .
H9B H 0.3574 1.0371 0.2682 0.045 Uiso 1 1 calc R U . . .
H9C H 0.3186 1.0167 0.2140 0.045 Uiso 1 1 calc R U . . .
C10 C 0.24775(17) 0.8201(2) 0.22178(10) 0.0300(6) Uani 1 1 d . . . . .
H10A H 0.2300 0.8587 0.1919 0.045 Uiso 1 1 calc R U . . .
H10B H 0.2030 0.7788 0.2318 0.045 Uiso 1 1 calc R U . . .
H10C H 0.2911 0.7701 0.2168 0.045 Uiso 1 1 calc R U . . .
C11 C 0.23919(16) 0.7386(2) 0.33333(11) 0.0282(6) Uani 1 1 d . . . . .
H11 H 0.2277 0.6855 0.3064 0.037 Uiso 1 1 calc R U . . .
C12 C 0.26728(19) 0.6715(3) 0.37889(12) 0.0396(7) Uani 1 1 d . . . . .
H12A H 0.2785 0.7206 0.4064 0.059 Uiso 1 1 calc R U . . .
H12B H 0.3159 0.6313 0.3743 0.059 Uiso 1 1 calc R U . . .
H12C H 0.2252 0.6202 0.3849 0.059 Uiso 1 1 calc R U . . .
C13 C 0.15968(17) 0.8009(3) 0.33731(13) 0.0386(7) Uani 1 1 d . . . . .
H13A H 0.1173 0.7486 0.3416 0.058 Uiso 1 1 calc R U . . .
H13B H 0.1445 0.8430 0.3080 0.058 Uiso 1 1 calc R U . . .
H13C H 0.1672 0.8502 0.3649 0.058 Uiso 1 1 calc R U . . .
C14 C 0.48725(15) 0.75610(18) 0.43964(9) 0.0195(5) Uani 1 1 d . . . . .
C15 C 0.44932(16) 0.7455(2) 0.48222(9) 0.0223(5) Uani 1 1 d . . . . .
H15 H 0.4007 0.7829 0.4844 0.030 Uiso 1 1 calc R U . . .
C16 C 0.48320(16) 0.6800(2) 0.52108(9) 0.0245(5) Uani 1 1 d . . . . .
H16 H 0.4567 0.6748 0.5488 0.033 Uiso 1 1 calc R U . . .
C17 C 0.55586(15) 0.62203(19) 0.51971(9) 0.0225(5) Uani 1 1 d . . . . .
C18 C 0.59486(15) 0.63475(19) 0.47822(9) 0.0223(5) Uani 1 1 d . . . . .
H18 H 0.6439 0.5979 0.4766 0.030 Uiso 1 1 calc R U . . .
C19 C 0.56271(15) 0.70131(19) 0.43864(9) 0.0212(5) Uani 1 1 d . . . . .
C20 C 0.59068(17) 0.5462(2) 0.56062(10) 0.0272(6) Uani 1 1 d . . . . .
H20A H 0.6062 0.4770 0.5472 0.041 Uiso 1 1 calc R U . . .
H20B H 0.5504 0.5330 0.5821 0.041 Uiso 1 1 calc R U . . .
H20C H 0.6377 0.5804 0.5786 0.041 Uiso 1 1 calc R U . . .
C21 C 0.68559(15) 0.8369(2) 0.40045(10) 0.0249(5) Uani 1 1 d . . . . .
H21 H 0.7094 0.8570 0.3708 0.033 Uiso 1 1 calc R U . . .
C22 C 0.75607(17) 0.8042(3) 0.43954(11) 0.0347(7) Uani 1 1 d . . . . .
H22A H 0.7904 0.8675 0.4477 0.052 Uiso 1 1 calc R U . . .
H22B H 0.7874 0.7460 0.4271 0.052 Uiso 1 1 calc R U . . .
H22C H 0.7345 0.7785 0.4683 0.052 Uiso 1 1 calc R U . . .
C23 C 0.64256(16) 0.9409(2) 0.41717(10) 0.0279(6) Uani 1 1 d . . . . .
H23A H 0.6274 0.9285 0.4492 0.042 Uiso 1 1 calc R U . . .
H23B H 0.5946 0.9558 0.3946 0.042 Uiso 1 1 calc R U . . .
H23C H 0.6789 1.0033 0.4181 0.042 Uiso 1 1 calc R U . . .
C24 C 0.67572(16) 0.6000(2) 0.37727(10) 0.0269(6) Uani 1 1 d . . . . .
H24 H 0.7117 0.5887 0.4080 0.036 Uiso 1 1 calc R U . . .
C25 C 0.72837(18) 0.6212(2) 0.33622(11) 0.0362(7) Uani 1 1 d . . . . .
H25A H 0.7604 0.5564 0.3317 0.054 Uiso 1 1 calc R U . . .
H25B H 0.7639 0.6831 0.3448 0.054 Uiso 1 1 calc R U . . .
H25C H 0.6938 0.6374 0.3064 0.054 Uiso 1 1 calc R U . . .
C26 C 0.62372(17) 0.4960(2) 0.36630(12) 0.0333(6) Uani 1 1 d . . . . .
H26A H 0.5911 0.5039 0.3351 0.050 Uiso 1 1 calc R U . . .
H26B H 0.5888 0.4862 0.3913 0.050 Uiso 1 1 calc R U . . .
H26C H 0.6586 0.4324 0.3656 0.050 Uiso 1 1 calc R U . . .
C27 C 0.55511(14) 0.99744(19) 0.29883(9) 0.0194(5) Uani 1 1 d . . . . .
C28 C 0.52618(14) 1.11389(19) 0.30113(9) 0.0205(5) Uani 1 1 d . . . . .
C29 C 0.48162(15) 1.1441(2) 0.33834(10) 0.0237(5) Uani 1 1 d . . . . .
H29 H 0.4705 1.0918 0.3614 0.031 Uiso 1 1 calc R U . . .
C30 C 0.45352(16) 1.2524(2) 0.34129(11) 0.0277(6) Uani 1 1 d . . . . .
H30 H 0.4256 1.2734 0.3671 0.037 Uiso 1 1 calc R U . . .
C31 C 0.46727(15) 1.3291(2) 0.30565(11) 0.0291(6) Uani 1 1 d . . . . .
H31 H 0.4479 1.4013 0.3074 0.039 Uiso 1 1 calc R U . . .
C32 C 0.50957(16) 1.2986(2) 0.26759(11) 0.0284(6) Uani 1 1 d . . . . .
H32 H 0.5172 1.3497 0.2433 0.038 Uiso 1 1 calc R U . . .
C33 C 0.54096(15) 1.1914(2) 0.26551(10) 0.0254(5) Uani 1 1 d . . . . .
H33 H 0.5714 1.1717 0.2407 0.034 Uiso 1 1 calc R U . . .
C34 C 0.63710(15) 0.9756(2) 0.28444(9) 0.0220(5) Uani 1 1 d . . . . .
C35 C 0.65188(16) 0.8762(2) 0.26099(10) 0.0275(6) Uani 1 1 d . . . . .
H35 H 0.6099 0.8255 0.2528 0.037 Uiso 1 1 calc R U . . .
C36 C 0.73004(17) 0.8538(2) 0.24998(12) 0.0356(7) Uani 1 1 d . . . . .
H36 H 0.7400 0.7889 0.2335 0.047 Uiso 1 1 calc R U . . .
C37 C 0.79276(18) 0.9272(2) 0.26338(13) 0.0396(7) Uani 1 1 d . . . . .
H37 H 0.8450 0.9111 0.2562 0.053 Uiso 1 1 calc R U . . .
C38 C 0.77857(17) 1.0251(2) 0.28753(12) 0.0364(7) Uani 1 1 d . . . . .
H38 H 0.8213 1.0739 0.2969 0.048 Uiso 1 1 calc R U . . .
C39 C 0.70082(16) 1.0497(2) 0.29755(10) 0.0272(6) Uani 1 1 d . . . . .
H39 H 0.6910 1.1160 0.3131 0.036 Uiso 1 1 calc R U . . .
C40 C 0.47421(19) 0.6959(3) 0.16518(11) 0.0379(7) Uani 1 1 d . . . . .
C41 C 0.5683(5) 0.3959(6) 0.1222(3) 0.119(2) Uani 1 1 d . . . . .
H41A H 0.5429 0.4085 0.1512 0.179 Uiso 1 1 calc R U . . .
H41B H 0.5601 0.4595 0.1012 0.179 Uiso 1 1 calc R U . . .
H41C H 0.6257 0.3839 0.1311 0.179 Uiso 1 1 calc R U . . .
C42 C 0.5315(4) 0.2969(6) 0.0962(3) 0.114(2) Uani 1 1 d . . . . .
H42A H 0.4737 0.3083 0.0864 0.152 Uiso 1 1 calc R U . . .
H42B H 0.5575 0.2818 0.0673 0.152 Uiso 1 1 calc R U . . .
C43 C 0.5218(4) 0.1058(5) 0.1098(3) 0.112(2) Uani 1 1 d . . . . .
H43A H 0.5549 0.0897 0.0840 0.148 Uiso 1 1 calc R U . . .
H43B H 0.4653 0.1096 0.0952 0.148 Uiso 1 1 calc R U . . .
C44 C 0.5310(6) 0.0200(6) 0.1449(3) 0.150(3) Uani 1 1 d . . . . .
H44A H 0.5772 -0.0250 0.1399 0.224 Uiso 1 1 calc R U . . .
H44B H 0.4827 -0.0251 0.1416 0.224 Uiso 1 1 calc R U . . .
H44C H 0.5394 0.0516 0.1771 0.224 Uiso 1 1 calc R U . . .


_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 1.6389(17) . ?
Ti1 N1 2.055(2) . ?
Ti1 O3 2.0912(18) . ?
Ti1 O2 2.2998(16) . ?
Ti1 P1 2.6077(8) . ?
Ti1 P2 2.6227(7) . ?
S1 O4 1.425(2) . ?
S1 O5 1.4270(19) . ?
S1 O3 1.4789(17) . ?
S1 C40 1.827(3) . ?
P1 C6 1.817(2) . ?
P1 C8 1.848(3) . ?
P1 C11 1.854(3) . ?
P2 C19 1.820(3) . ?
P2 C24 1.848(3) . ?
P2 C21 1.858(3) . ?
F1 C40 1.328(4) . ?
F2 C40 1.340(4) . ?
F3 C40 1.328(4) . ?
O2 C27 1.235(3) . ?
O6 C43 1.360(6) . ?
O6 C42 1.456(7) . ?
N1 C1 1.402(3) . ?
N1 C14 1.411(3) . ?
C1 C2 1.396(3) . ?
C1 C6 1.413(3) . ?
C2 C3 1.393(3) . ?
C3 C4 1.396(3) . ?
C4 C5 1.398(3) . ?
C4 C7 1.513(3) . ?
C5 C6 1.396(3) . ?
C8 C9 1.525(4) . ?
C8 C10 1.539(3) . ?
C11 C12 1.516(4) . ?
C11 C13 1.529(4) . ?
C14 C15 1.405(4) . ?
C14 C19 1.415(3) . ?
C15 C16 1.390(3) . ?
C16 C17 1.394(4) . ?
C17 C18 1.391(4) . ?
C17 C20 1.507(3) . ?
C18 C19 1.403(3) . ?
C21 C22 1.535(4) . ?
C21 C23 1.540(4) . ?
C24 C26 1.528(4) . ?
C24 C25 1.534(4) . ?
C27 C34 1.483(3) . ?
C27 C28 1.486(3) . ?
C28 C29 1.385(4) . ?
C28 C33 1.399(3) . ?
C29 C30 1.391(3) . ?
C30 C31 1.388(4) . ?
C31 C32 1.382(4) . ?
C32 C33 1.396(4) . ?
C34 C39 1.393(4) . ?
C34 C35 1.397(4) . ?
C35 C36 1.391(4) . ?
C36 C37 1.377(4) . ?
C37 C38 1.389(4) . ?
C38 C39 1.381(4) . ?
C41 C42 1.482(9) . ?
C43 C44 1.411(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 Ti1 N1 101.48(9) . . ?
O1 Ti1 O3 95.87(8) . . ?
N1 Ti1 O3 160.92(7) . . ?
O1 Ti1 O2 168.95(8) . . ?
N1 Ti1 O2 87.04(7) . . ?
O3 Ti1 O2 76.84(6) . . ?
O1 Ti1 P1 102.97(6) . . ?
N1 Ti1 P1 75.33(6) . . ?
O3 Ti1 P1 93.17(5) . . ?
O2 Ti1 P1 85.89(5) . . ?
O1 Ti1 P2 87.91(6) . . ?
N1 Ti1 P2 75.91(6) . . ?
O3 Ti1 P2 112.91(5) . . ?
O2 Ti1 P2 87.36(5) . . ?
P1 Ti1 P2 150.74(3) . . ?
O4 S1 O5 118.30(12) . . ?
O4 S1 O3 114.16(11) . . ?
O5 S1 O3 113.25(11) . . ?
O4 S1 C40 104.31(14) . . ?
O5 S1 C40 104.43(14) . . ?
O3 S1 C40 99.41(12) . . ?
C6 P1 C8 107.13(11) . . ?
C6 P1 C11 105.62(12) . . ?
C8 P1 C11 105.00(12) . . ?
C6 P1 Ti1 96.19(8) . . ?
C8 P1 Ti1 124.25(9) . . ?
C11 P1 Ti1 116.45(9) . . ?
C19 P2 C24 106.56(12) . . ?
C19 P2 C21 104.42(12) . . ?
C24 P2 C21 104.26(12) . . ?
C19 P2 Ti1 91.12(8) . . ?
C24 P2 Ti1 121.30(9) . . ?
C21 P2 Ti1 125.10(8) . . ?
C27 O2 Ti1 162.17(16) . . ?
S1 O3 Ti1 128.51(10) . . ?
C43 O6 C42 112.5(6) . . ?
C1 N1 C14 119.0(2) . . ?
C1 N1 Ti1 123.44(15) . . ?
C14 N1 Ti1 117.44(15) . . ?
C2 C1 N1 123.2(2) . . ?
C2 C1 C6 117.6(2) . . ?
N1 C1 C6 119.1(2) . . ?
C3 C2 C1 121.3(2) . . ?
C2 C3 C4 121.1(2) . . ?
C3 C4 C5 118.0(2) . . ?
C3 C4 C7 120.8(2) . . ?
C5 C4 C7 121.2(2) . . ?
C6 C5 C4 121.2(2) . . ?
C5 C6 C1 120.7(2) . . ?
C5 C6 P1 124.74(18) . . ?
C1 C6 P1 114.57(17) . . ?
C9 C8 C10 110.3(2) . . ?
C9 C8 P1 110.69(17) . . ?
C10 C8 P1 109.45(17) . . ?
C12 C11 C13 112.2(3) . . ?
C12 C11 P1 110.58(18) . . ?
C13 C11 P1 113.33(19) . . ?
C15 C14 N1 123.7(2) . . ?
C15 C14 C19 117.5(2) . . ?
N1 C14 C19 118.7(2) . . ?
C16 C15 C14 121.1(2) . . ?
C15 C16 C17 121.9(2) . . ?
C18 C17 C16 117.2(2) . . ?
C18 C17 C20 120.6(2) . . ?
C16 C17 C20 122.2(2) . . ?
C17 C18 C19 122.2(2) . . ?
C18 C19 C14 120.0(2) . . ?
C18 C19 P2 124.39(19) . . ?
C14 C19 P2 115.62(18) . . ?
C22 C21 C23 109.7(2) . . ?
C22 C21 P2 113.74(18) . . ?
C23 C21 P2 111.02(17) . . ?
C26 C24 C25 110.4(2) . . ?
C26 C24 P2 111.20(18) . . ?
C25 C24 P2 108.97(18) . . ?
O2 C27 C34 120.6(2) . . ?
O2 C27 C28 120.1(2) . . ?
C34 C27 C28 119.3(2) . . ?
C29 C28 C33 120.1(2) . . ?
C29 C28 C27 118.9(2) . . ?
C33 C28 C27 121.0(2) . . ?
C28 C29 C30 120.2(2) . . ?
C31 C30 C29 119.8(3) . . ?
C32 C31 C30 120.3(2) . . ?
C31 C32 C33 120.2(2) . . ?
C32 C33 C28 119.4(3) . . ?
C39 C34 C35 119.9(2) . . ?
C39 C34 C27 120.2(2) . . ?
C35 C34 C27 119.7(2) . . ?
C36 C35 C34 119.3(2) . . ?
C37 C36 C35 120.4(3) . . ?
C36 C37 C38 120.4(3) . . ?
C39 C38 C37 119.8(3) . . ?
C38 C39 C34 120.2(3) . . ?
F3 C40 F1 107.9(3) . . ?
F3 C40 F2 107.8(3) . . ?
F1 C40 F2 108.3(3) . . ?
F3 C40 S1 110.5(2) . . ?
F1 C40 S1 111.6(2) . . ?
F2 C40 S1 110.6(2) . . ?
O6 C42 C41 106.2(6) . . ?
O6 C43 C44 110.8(6) . . ?

_refine_diff_density_max         1.400
_refine_diff_density_min         -0.779
_refine_diff_density_rms         0.078


loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.500 0.002 0.000 603 125 ' '
2 0.000 -0.013 0.500 603 125 ' '
_platon_squeeze_details          
;
;
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_solvent_exptl_crystal_recrystallization_method 'diethyl ether, pentane'
_chemical_properties_physical    
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
####################################################################### 
# 
# 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_UP9223
_database_code_depnum_ccdc_archive 'CCDC 1472933'
_audit_update_record             
;
2016-05-10 deposited with the CCDC.
2016-06-13 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT413_UP9223              
;
PROBLEM: Short Inter XH3 .. XHn     H67    ..  H47F    ..       1.94 Ang.
RESPONSE: This alert corresponds to disorder present in the tert-butyl group of the aryloxide ligand. 
;
_vrf_PLAT094_UP9223              
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       2.14 Report
RESPONSE: This alert corresponds to disorder present in the tert-butyl group of the aryloxide ligand. 
;
_vrf_PLAT220_UP9223              
;
PROBLEM: Non-Solvent Resd 1   C   Ueq(max)/Ueq(min) Range        4.3 Ratio
RESPONSE: This alert corresponds to disorder present in the tert-butyl group of the aryloxide ligand. 
;
_vrf_PLAT234_UP9223              
;
PROBLEM: Large Hirshfeld Difference C46    --  C48'    ..       0.17 Ang.
RESPONSE: This alert corresponds to disorder present in the tert-butyl group of the aryloxide ligand. 
;
_vrf_PLAT243_UP9223              
;
PROBLEM: High   'Solvent' Ueq as Compared to Neighbors of        C66 Check
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
_vrf_PLAT244_UP9223              
;
PROBLEM: Low    'Solvent' Ueq as Compared to Neighbors of        C64 Check
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
_vrf_PLAT250_UP9223              
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.1 Note
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
_vrf_PLAT331_UP9223              
;
PROBLEM: Small Average Phenyl   C-C Dist. C64    -C69           1.37 Ang.
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
_vrf_PLAT332_UP9223              
;
PROBLEM: Large Phenyl C-C Range           C64    -C69           0.17 Ang.
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
_vrf_PLAT362_UP9223              
;
PROBLEM: Short   C(sp3)-C(sp2) Bond  C63    -   C64    ..       1.37 Ang.
RESPONSE: This alert corresponds to disorder present in a co-crystallized toluene molecule in the unit cell. 
;
# Added during the CSD deposition process: Tuesday 10 May 2016 04:11 PM
# end Validation Reply Form

#Compound 3

# Crystallographer: Brian C. Manor

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C62 H73 N O2 P2 Ti, C7 H8'
_chemical_formula_sum            'C69 H81 N O2 P2 Ti'
_chemical_formula_weight         1066.18

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'
P P 0.1023 0.0942 '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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   11.4489(3)
_cell_length_b                   21.9022(6)
_cell_length_c                   23.9798(6)
_cell_angle_alpha                90
_cell_angle_beta                 101.442(2)
_cell_angle_gamma                90
_cell_volume                     5893.6(3)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.53
_cell_measurement_theta_min      2.35

_exptl_crystal_description       prism
_exptl_crystal_colour            orange
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_exptl_absorpt_coefficient_mu    0.245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7205
_exptl_absorpt_process_details   'SADABS v2014/4'
_diffrn_ambient_temperature      100(1)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device       'CCD Area Detector'
_diffrn_measurement_device_type  'Bruker APEXII'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_reflns_number            135355
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_av_R_equivalents  0.0791
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         1.271
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             13521
_reflns_number_gt                9482
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'
_computing_publication_material  'Yadokari-XG 2009 (Wakita,Nemoto et al., 2009)'
_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)+(0.0837P)²+4.9007P] 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_number_reflns         13521
_refine_ls_number_parameters     721
_refine_ls_number_restraints     45
_refine_ls_R_factor_all          0.0958
_refine_ls_R_factor_gt           0.0595
_refine_ls_wR_factor_ref         0.1704
_refine_ls_wR_factor_gt          0.1466
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_restrained_S_all      1.065
_refine_ls_shift/su_max          0.001
_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 0.25291(4) 0.62698(2) 0.57806(2) 0.01649(12) Uani 1 1 d . . . . .
P1 P 0.04421(6) 0.59536(3) 0.59389(3) 0.01537(14) Uani 1 1 d . . . . .
P2 P 0.47748(7) 0.63988(3) 0.62177(3) 0.02508(17) Uani 1 1 d . . . . .
O1 O 0.27148(17) 0.57130(9) 0.53393(8) 0.0254(4) Uani 1 1 d . . . . .
O2 O 0.22147(16) 0.70307(8) 0.54308(7) 0.0179(4) Uani 1 1 d . . . . .
N1 N 0.27595(19) 0.59633(10) 0.66300(9) 0.0186(4) Uani 1 1 d . . . . .
C1 C 0.1904(2) 0.60673(11) 0.69648(11) 0.0180(5) Uani 1 1 d . . . . .
C2 C 0.2182(3) 0.61655(12) 0.75531(11) 0.0224(6) Uani 1 1 d . . . . .
H2 H 0.2974 0.6163 0.7741 0.030 Uiso 1 1 calc R U . . .
C3 C 0.1292(3) 0.62671(12) 0.78600(11) 0.0237(6) Uani 1 1 d . . . . .
H3 H 0.1503 0.6333 0.8250 0.032 Uiso 1 1 calc R U . . .
C4 C 0.0096(3) 0.62731(12) 0.76011(11) 0.0236(6) Uani 1 1 d . . . . .
C5 C -0.0188(2) 0.61943(12) 0.70150(11) 0.0204(5) Uani 1 1 d . . . . .
H5 H -0.0983 0.6208 0.6831 0.027 Uiso 1 1 calc R U . . .
C6 C 0.0688(2) 0.60945(11) 0.66966(10) 0.0156(5) Uani 1 1 d . . . . .
C7 C -0.0875(3) 0.63570(16) 0.79387(12) 0.0343(7) Uani 1 1 d . . . . .
H7A H -0.1251 0.6746 0.7849 0.051 Uiso 1 1 calc R U . . .
H7B H -0.0535 0.6340 0.8338 0.051 Uiso 1 1 calc R U . . .
H7C H -0.1456 0.6038 0.7844 0.051 Uiso 1 1 calc R U . . .
C8 C 0.0106(2) 0.51275(11) 0.58699(11) 0.0213(6) Uani 1 1 d . . . . .
H8 H 0.0029 0.5020 0.5468 0.028 Uiso 1 1 calc R U . . .
C9 C 0.1136(3) 0.47558(12) 0.62050(12) 0.0250(6) Uani 1 1 d . . . . .
H9A H 0.1217 0.4840 0.6604 0.037 Uiso 1 1 calc R U . . .
H9B H 0.1860 0.4864 0.6085 0.037 Uiso 1 1 calc R U . . .
H9C H 0.0980 0.4329 0.6138 0.037 Uiso 1 1 calc R U . . .
C10 C -0.1068(3) 0.49597(13) 0.60443(13) 0.0306(7) Uani 1 1 d . . . . .
H10A H -0.1201 0.4528 0.5999 0.046 Uiso 1 1 calc R U . . .
H10B H -0.1711 0.5176 0.5808 0.046 Uiso 1 1 calc R U . . .
H10C H -0.1029 0.5069 0.6435 0.046 Uiso 1 1 calc R U . . .
C11 C -0.0940(2) 0.63385(12) 0.55993(11) 0.0186(5) Uani 1 1 d . . . . .
H11 H -0.1583 0.6211 0.5789 0.025 Uiso 1 1 calc R U . . .
C12 C -0.1250(3) 0.61397(13) 0.49754(11) 0.0249(6) Uani 1 1 d . . . . .
H12A H -0.1924 0.6369 0.4781 0.037 Uiso 1 1 calc R U . . .
H12B H -0.1439 0.5712 0.4955 0.037 Uiso 1 1 calc R U . . .
H12C H -0.0581 0.6213 0.4799 0.037 Uiso 1 1 calc R U . . .
C13 C -0.0791(3) 0.70293(12) 0.56543(12) 0.0247(6) Uani 1 1 d . . . . .
H13A H -0.0180 0.7160 0.5458 0.037 Uiso 1 1 calc R U . . .
H13B H -0.0569 0.7137 0.6049 0.037 Uiso 1 1 calc R U . . .
H13C H -0.1529 0.7225 0.5490 0.037 Uiso 1 1 calc R U . . .
C14 C 0.3782(2) 0.56201(12) 0.68626(11) 0.0188(5) Uani 1 1 d . . . . .
C15 C 0.3774(2) 0.51198(12) 0.72303(11) 0.0205(5) Uani 1 1 d . . . . .
H15 H 0.3074 0.5019 0.7350 0.027 Uiso 1 1 calc R U . . .
C16 C 0.4787(3) 0.47771(12) 0.74165(11) 0.0228(6) Uani 1 1 d . . . . .
H16 H 0.4749 0.4444 0.7653 0.030 Uiso 1 1 calc R U . . .
C17 C 0.5870(2) 0.49161(12) 0.72602(11) 0.0226(6) Uani 1 1 d . . . . .
C18 C 0.5886(2) 0.54116(12) 0.69016(11) 0.0209(5) Uani 1 1 d . . . . .
H18 H 0.6594 0.5515 0.6791 0.028 Uiso 1 1 calc R U . . .
C19 C 0.4869(2) 0.57581(12) 0.67031(11) 0.0200(5) Uani 1 1 d . . . . .
C20 C 0.6968(3) 0.45324(14) 0.74587(12) 0.0301(7) Uani 1 1 d . . . . .
H20A H 0.6851 0.4135 0.7288 0.045 Uiso 1 1 calc R U . . .
H20B H 0.7111 0.4493 0.7865 0.045 Uiso 1 1 calc R U . . .
H20C H 0.7642 0.4725 0.7349 0.045 Uiso 1 1 calc R U . . .
C21 C 0.5877(3) 0.62752(14) 0.57691(13) 0.0313(7) Uani 1 1 d . . . . .
H21 H 0.6674 0.6272 0.6012 0.042 Uiso 1 1 calc R U . . .
C22 C 0.5679(3) 0.56718(15) 0.54549(13) 0.0334(7) Uani 1 1 d . . . . .
H22A H 0.4879 0.5656 0.5238 0.050 Uiso 1 1 calc R U . . .
H22B H 0.5801 0.5342 0.5724 0.050 Uiso 1 1 calc R U . . .
H22C H 0.6232 0.5635 0.5203 0.050 Uiso 1 1 calc R U . . .
C23 C 0.5791(3) 0.68200(16) 0.53598(15) 0.0391(8) Uani 1 1 d . . . . .
H23A H 0.6372 0.6775 0.5124 0.059 Uiso 1 1 calc R U . . .
H23B H 0.5941 0.7191 0.5575 0.059 Uiso 1 1 calc R U . . .
H23C H 0.5008 0.6834 0.5125 0.059 Uiso 1 1 calc R U . . .
C24 C 0.5301(3) 0.70661(14) 0.66714(15) 0.0364(7) Uani 1 1 d . . . . .
H24 H 0.5089 0.7435 0.6442 0.048 Uiso 1 1 calc R U . . .
C25 C 0.4655(4) 0.70924(17) 0.71717(18) 0.0527(10) Uani 1 1 d . . . . .
H25A H 0.4882 0.6747 0.7415 0.079 Uiso 1 1 calc R U . . .
H25B H 0.3810 0.7085 0.7031 0.079 Uiso 1 1 calc R U . . .
H25C H 0.4869 0.7462 0.7383 0.079 Uiso 1 1 calc R U . . .
C26 C 0.6637(3) 0.70772(18) 0.68964(17) 0.0498(9) Uani 1 1 d . . . . .
H26A H 0.6844 0.7434 0.7128 0.075 Uiso 1 1 calc R U . . .
H26B H 0.7044 0.7086 0.6583 0.075 Uiso 1 1 calc R U . . .
H26C H 0.6869 0.6718 0.7121 0.075 Uiso 1 1 calc R U . . .
C27 C 0.2004(2) 0.75336(11) 0.51029(10) 0.0159(5) Uani 1 1 d . . . . .
C28 C 0.1727(2) 0.74917(11) 0.45047(10) 0.0187(5) Uani 1 1 d . . . . .
C29 C 0.1447(3) 0.80230(12) 0.41882(11) 0.0227(6) Uani 1 1 d . . . . .
H29 H 0.1239 0.7991 0.3794 0.030 Uiso 1 1 calc R U . . .
C30 C 0.1463(3) 0.85984(12) 0.44317(11) 0.0226(6) Uani 1 1 d . . . . .
C31 C 0.1789(2) 0.86322(12) 0.50231(11) 0.0212(6) Uani 1 1 d . . . . .
H31 H 0.1841 0.9014 0.5197 0.028 Uiso 1 1 calc R U . . .
C32 C 0.2040(2) 0.81153(11) 0.53614(10) 0.0174(5) Uani 1 1 d . . . . .
C33 C 0.1745(3) 0.68773(11) 0.42079(10) 0.0209(6) Uani 1 1 d . . . . .
H33 H 0.1672 0.6565 0.4492 0.028 Uiso 1 1 calc R U . . .
C34 C 0.2930(3) 0.67565(12) 0.40247(11) 0.0241(6) Uani 1 1 d . . . . .
C35 C 0.3514(3) 0.62045(13) 0.41464(12) 0.0250(6) Uani 1 1 d . . . . .
H35 H 0.3202 0.5915 0.4360 0.033 Uiso 1 1 calc R U . . .
C36 C 0.4559(3) 0.60734(15) 0.39560(12) 0.0307(7) Uani 1 1 d . . . . .
H36 H 0.4934 0.5699 0.4041 0.041 Uiso 1 1 calc R U . . .
C37 C 0.5037(3) 0.64957(15) 0.36424(14) 0.0390(8) Uani 1 1 d . . . . .
H37 H 0.5730 0.6408 0.3511 0.052 Uiso 1 1 calc R U . . .
C38 C 0.4486(4) 0.70455(16) 0.35257(18) 0.0568(12) Uani 1 1 d . . . . .
H38 H 0.4812 0.7335 0.3317 0.076 Uiso 1 1 calc R U . . .
C39 C 0.3442(4) 0.71804(15) 0.37144(16) 0.0498(10) Uani 1 1 d . . . . .
H39 H 0.3081 0.7559 0.3632 0.066 Uiso 1 1 calc R U . . .
C40 C 0.0675(3) 0.67915(12) 0.37179(11) 0.0240(6) Uani 1 1 d . . . . .
C41 C 0.0764(3) 0.64815(13) 0.32200(11) 0.0314(7) Uani 1 1 d . . . . .
H41 H 0.1508 0.6353 0.3167 0.042 Uiso 1 1 calc R U . . .
C42 C -0.0237(3) 0.63609(14) 0.28022(13) 0.0379(8) Uani 1 1 d . . . . .
H42 H -0.0158 0.6147 0.2477 0.050 Uiso 1 1 calc R U . . .
C43 C -0.1335(3) 0.65542(14) 0.28670(13) 0.0384(8) Uani 1 1 d . . . . .
H43 H -0.2002 0.6470 0.2587 0.051 Uiso 1 1 calc R U . . .
C44 C -0.1456(3) 0.68797(14) 0.33550(13) 0.0360(7) Uani 1 1 d . . . . .
H44 H -0.2200 0.7020 0.3398 0.048 Uiso 1 1 calc R U . . .
C45 C -0.0450(3) 0.69912(13) 0.37757(12) 0.0286(6) Uani 1 1 d . . . . .
H45 H -0.0531 0.7203 0.4102 0.038 Uiso 1 1 calc R U . . .
C46 C 0.1125(3) 0.91660(13) 0.40565(12) 0.0316(7) Uani 1 1 d D . . . .
C47 C 0.1912(5) 0.9219(2) 0.3637(2) 0.0423(14) Uani 0.719(6) 1 d D U P A 1
H47A H 0.1667 0.9562 0.3392 0.063 Uiso 0.719(6) 1 calc R U P A 1
H47B H 0.1859 0.8853 0.3413 0.063 Uiso 0.719(6) 1 calc R U P A 1
H47C H 0.2720 0.9277 0.3833 0.063 Uiso 0.719(6) 1 calc R U P A 1
C48 C -0.0196(4) 0.9091(2) 0.3732(2) 0.0418(13) Uani 0.719(6) 1 d D U P A 1
H48A H -0.0403 0.9423 0.3471 0.063 Uiso 0.719(6) 1 calc R U P A 1
H48B H -0.0716 0.9092 0.4001 0.063 Uiso 0.719(6) 1 calc R U P A 1
H48C H -0.0280 0.8712 0.3527 0.063 Uiso 0.719(6) 1 calc R U P A 1
C49 C 0.1152(6) 0.97520(19) 0.44013(19) 0.0390(13) Uani 0.719(6) 1 d D U P A 1
H49A H 0.1942 0.9817 0.4618 0.058 Uiso 0.719(6) 1 calc R U P A 1
H49B H 0.0603 0.9718 0.4655 0.058 Uiso 0.719(6) 1 calc R U P A 1
H49C H 0.0928 1.0090 0.4148 0.058 Uiso 0.719(6) 1 calc R U P A 1
C47' C 0.2377(11) 0.9533(6) 0.4046(6) 0.053(4) Uani 0.281(6) 1 d D U P A 2
H47D H 0.2207 0.9897 0.3821 0.079 Uiso 0.281(6) 1 calc R U P A 2
H47E H 0.2900 0.9275 0.3884 0.079 Uiso 0.281(6) 1 calc R U P A 2
H47F H 0.2753 0.9642 0.4428 0.079 Uiso 0.281(6) 1 calc R U P A 2
C48' C 0.0783(14) 0.9003(6) 0.3423(4) 0.054(4) Uani 0.281(6) 1 d D U P A 2
H48D H 0.0090 0.8746 0.3360 0.081 Uiso 0.281(6) 1 calc R U P A 2
H48E H 0.1432 0.8790 0.3310 0.081 Uiso 0.281(6) 1 calc R U P A 2
H48F H 0.0615 0.9370 0.3203 0.081 Uiso 0.281(6) 1 calc R U P A 2
C49' C 0.0333(16) 0.9569(7) 0.4272(7) 0.065(5) Uani 0.281(6) 1 d D U P A 2
H49D H 0.0227 0.9936 0.4048 0.098 Uiso 0.281(6) 1 calc R U P A 2
H49E H 0.0665 0.9669 0.4661 0.098 Uiso 0.281(6) 1 calc R U P A 2
H49F H -0.0424 0.9372 0.4250 0.098 Uiso 0.281(6) 1 calc R U P A 2
C50 C 0.2344(3) 0.81698(12) 0.60077(10) 0.0204(5) Uani 1 1 d . . . . .
H50 H 0.2806 0.7805 0.6148 0.027 Uiso 1 1 calc R U . . .
C51 C 0.3155(3) 0.87179(12) 0.61984(11) 0.0248(6) Uani 1 1 d . . . . .
C52 C 0.4304(3) 0.87164(14) 0.60980(13) 0.0328(7) Uani 1 1 d . . . . .
H52 H 0.4567 0.8381 0.5920 0.044 Uiso 1 1 calc R U . . .
C53 C 0.5076(3) 0.92052(17) 0.62567(14) 0.0431(9) Uani 1 1 d . . . . .
H53 H 0.5844 0.9195 0.6184 0.057 Uiso 1 1 calc R U . . .
C54 C 0.4698(4) 0.97029(16) 0.65214(14) 0.0477(10) Uani 1 1 d . . . . .
H54 H 0.5211 1.0030 0.6630 0.063 Uiso 1 1 calc R U . . .
C55 C 0.3563(4) 0.97175(15) 0.66262(14) 0.0444(9) Uani 1 1 d . . . . .
H55 H 0.3308 1.0055 0.6805 0.059 Uiso 1 1 calc R U . . .
C56 C 0.2788(3) 0.92278(13) 0.64647(12) 0.0331(7) Uani 1 1 d . . . . .
H56 H 0.2019 0.9242 0.6536 0.044 Uiso 1 1 calc R U . . .
C57 C 0.1243(3) 0.81627(12) 0.62735(11) 0.0257(6) Uani 1 1 d . . . . .
C58 C 0.1281(3) 0.78421(14) 0.67837(12) 0.0351(8) Uani 1 1 d . . . . .
H58 H 0.1961 0.7623 0.6943 0.047 Uiso 1 1 calc R U . . .
C59 C 0.0321(4) 0.78489(17) 0.70520(15) 0.0497(11) Uani 1 1 d . . . . .
H59 H 0.0356 0.7630 0.7387 0.066 Uiso 1 1 calc R U . . .
C60 C -0.0680(4) 0.81745(17) 0.68293(19) 0.0572(13) Uani 1 1 d . . . . .
H60 H -0.1316 0.8184 0.7017 0.076 Uiso 1 1 calc R U . . .
C61 C -0.0750(4) 0.84919(15) 0.63213(19) 0.0495(10) Uani 1 1 d . . . . .
H61 H -0.1436 0.8708 0.6166 0.066 Uiso 1 1 calc R U . . .
C62 C 0.0216(3) 0.84838(13) 0.60458(15) 0.0347(7) Uani 1 1 d . . . . .
H62 H 0.0170 0.8696 0.5706 0.046 Uiso 1 1 calc R U . . .
C63 C 0.7894(7) 0.8083(3) 0.4439(3) 0.129(3) Uani 1 1 d . . . . .
H63A H 0.8043 0.8170 0.4067 0.194 Uiso 1 1 calc R U . . .
H63B H 0.7735 0.7655 0.4468 0.194 Uiso 1 1 calc R U . . .
H63C H 0.8580 0.8193 0.4721 0.194 Uiso 1 1 calc R U . . .
C64 C 0.6926(5) 0.8414(3) 0.4525(2) 0.0777(15) Uani 1 1 d . . . . .
C65 C 0.5854(5) 0.8131(2) 0.4538(2) 0.0721(13) Uani 1 1 d . . . . .
H65 H 0.5759 0.7714 0.4471 0.096 Uiso 1 1 calc R U . . .
C66 C 0.4963(8) 0.8465(3) 0.4648(2) 0.120(3) Uani 1 1 d . . . . .
H66 H 0.4278 0.8248 0.4674 0.160 Uiso 1 1 calc R U . . .
C67 C 0.4904(6) 0.9034(4) 0.4723(3) 0.109(2) Uani 1 1 d . . . . .
H67 H 0.4218 0.9235 0.4776 0.145 Uiso 1 1 calc R U . . .
C68 C 0.6015(7) 0.9337(4) 0.4718(3) 0.115(2) Uani 1 1 d . . . . .
H68 H 0.6058 0.9756 0.4781 0.153 Uiso 1 1 calc R U . . .
C69 C 0.7005(6) 0.9045(2) 0.4627(2) 0.0896(18) Uani 1 1 d . . . . .
H69 H 0.7712 0.9256 0.4632 0.119 Uiso 1 1 calc R U . . .


_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 1.6558(19) . ?
Ti1 O2 1.8685(17) . ?
Ti1 N1 2.111(2) . ?
Ti1 P1 2.5870(8) . ?
Ti1 P2 2.5923(9) . ?
P1 C6 1.809(2) . ?
P1 C11 1.835(3) . ?
P1 C8 1.850(3) . ?
P2 C19 1.813(3) . ?
P2 C21 1.834(3) . ?
P2 C24 1.850(3) . ?
O2 C27 1.347(3) . ?
N1 C1 1.403(3) . ?
N1 C14 1.410(3) . ?
C1 C2 1.400(4) . ?
C1 C6 1.414(4) . ?
C2 C3 1.388(4) . ?
C3 C4 1.386(4) . ?
C4 C5 1.389(4) . ?
C4 C7 1.511(4) . ?
C5 C6 1.393(4) . ?
C8 C9 1.524(4) . ?
C8 C10 1.530(4) . ?
C11 C13 1.525(4) . ?
C11 C12 1.531(4) . ?
C14 C19 1.405(4) . ?
C14 C15 1.408(4) . ?
C15 C16 1.379(4) . ?
C16 C17 1.398(4) . ?
C17 C18 1.387(4) . ?
C17 C20 1.509(4) . ?
C18 C19 1.392(4) . ?
C21 C22 1.516(4) . ?
C21 C23 1.536(4) . ?
C24 C26 1.519(5) . ?
C24 C25 1.530(5) . ?
C27 C28 1.409(3) . ?
C27 C32 1.414(3) . ?
C28 C29 1.392(4) . ?
C28 C33 1.524(3) . ?
C29 C30 1.388(4) . ?
C30 C31 1.395(4) . ?
C30 C46 1.538(4) . ?
C31 C32 1.389(3) . ?
C32 C50 1.524(3) . ?
C33 C34 1.530(4) . ?
C33 C40 1.532(4) . ?
C34 C35 1.384(4) . ?
C34 C39 1.390(4) . ?
C35 C36 1.392(4) . ?
C36 C37 1.373(4) . ?
C37 C38 1.363(5) . ?
C38 C39 1.391(5) . ?
C40 C45 1.393(4) . ?
C40 C41 1.395(4) . ?
C41 C42 1.389(5) . ?
C42 C43 1.364(5) . ?
C43 C44 1.401(5) . ?
C44 C45 1.394(4) . ?
C46 C49' 1.433(12) . ?
C46 C47 1.483(5) . ?
C46 C49 1.524(5) . ?
C46 C48' 1.534(11) . ?
C46 C48 1.566(5) . ?
C46 C47' 1.648(11) . ?
C50 C57 1.521(4) . ?
C50 C51 1.531(4) . ?
C51 C52 1.383(4) . ?
C51 C56 1.392(4) . ?
C52 C53 1.392(4) . ?
C53 C54 1.374(5) . ?
C54 C55 1.372(5) . ?
C55 C56 1.397(4) . ?
C57 C62 1.386(5) . ?
C57 C58 1.404(4) . ?
C58 C59 1.380(5) . ?
C59 C60 1.365(6) . ?
C60 C61 1.391(6) . ?
C61 C62 1.396(4) . ?
C63 C64 1.373(8) . ?
C64 C65 1.381(7) . ?
C64 C69 1.404(8) . ?
C65 C66 1.323(8) . ?
C66 C67 1.264(9) . ?
C67 C68 1.437(10) . ?
C68 C69 1.356(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 Ti1 O2 114.06(9) . . ?
O1 Ti1 N1 112.04(9) . . ?
O2 Ti1 N1 133.86(8) . . ?
O1 Ti1 P1 97.82(7) . . ?
O2 Ti1 P1 101.73(6) . . ?
N1 Ti1 P1 73.47(6) . . ?
O1 Ti1 P2 95.51(7) . . ?
O2 Ti1 P2 99.88(6) . . ?
N1 Ti1 P2 73.77(6) . . ?
P1 Ti1 P2 147.22(3) . . ?
C6 P1 C11 108.42(12) . . ?
C6 P1 C8 104.17(11) . . ?
C11 P1 C8 105.30(12) . . ?
C6 P1 Ti1 97.90(8) . . ?
C11 P1 Ti1 123.52(9) . . ?
C8 P1 Ti1 115.50(9) . . ?
C19 P2 C21 107.58(13) . . ?
C19 P2 C24 105.25(14) . . ?
C21 P2 C24 106.27(15) . . ?
C19 P2 Ti1 95.92(9) . . ?
C21 P2 Ti1 119.31(11) . . ?
C24 P2 Ti1 120.32(11) . . ?
C27 O2 Ti1 171.01(16) . . ?
C1 N1 C14 118.7(2) . . ?
C1 N1 Ti1 122.20(16) . . ?
C14 N1 Ti1 119.08(16) . . ?
C2 C1 N1 123.8(2) . . ?
C2 C1 C6 117.3(2) . . ?
N1 C1 C6 118.9(2) . . ?
C3 C2 C1 121.0(3) . . ?
C4 C3 C2 121.8(2) . . ?
C3 C4 C5 117.6(2) . . ?
C3 C4 C7 121.8(2) . . ?
C5 C4 C7 120.5(3) . . ?
C4 C5 C6 121.6(3) . . ?
C5 C6 C1 120.5(2) . . ?
C5 C6 P1 126.3(2) . . ?
C1 C6 P1 113.11(18) . . ?
C9 C8 C10 111.0(2) . . ?
C9 C8 P1 110.46(19) . . ?
C10 C8 P1 112.89(19) . . ?
C13 C11 C12 111.5(2) . . ?
C13 C11 P1 110.20(18) . . ?
C12 C11 P1 108.39(18) . . ?
C19 C14 C15 117.0(2) . . ?
C19 C14 N1 119.2(2) . . ?
C15 C14 N1 123.7(2) . . ?
C16 C15 C14 121.1(3) . . ?
C15 C16 C17 121.9(3) . . ?
C18 C17 C16 117.3(2) . . ?
C18 C17 C20 121.2(3) . . ?
C16 C17 C20 121.5(3) . . ?
C17 C18 C19 121.7(3) . . ?
C18 C19 C14 121.0(2) . . ?
C18 C19 P2 125.5(2) . . ?
C14 C19 P2 113.45(19) . . ?
C22 C21 C23 112.1(3) . . ?
C22 C21 P2 111.6(2) . . ?
C23 C21 P2 107.2(2) . . ?
C26 C24 C25 109.3(3) . . ?
C26 C24 P2 114.1(2) . . ?
C25 C24 P2 109.8(2) . . ?
O2 C27 C28 121.3(2) . . ?
O2 C27 C32 119.6(2) . . ?
C28 C27 C32 119.1(2) . . ?
C29 C28 C27 118.8(2) . . ?
C29 C28 C33 120.4(2) . . ?
C27 C28 C33 120.8(2) . . ?
C30 C29 C28 123.2(2) . . ?
C29 C30 C31 117.0(2) . . ?
C29 C30 C46 120.5(2) . . ?
C31 C30 C46 122.5(2) . . ?
C32 C31 C30 122.2(2) . . ?
C31 C32 C27 119.6(2) . . ?
C31 C32 C50 120.6(2) . . ?
C27 C32 C50 119.8(2) . . ?
C28 C33 C34 112.4(2) . . ?
C28 C33 C40 112.6(2) . . ?
C34 C33 C40 112.2(2) . . ?
C35 C34 C39 117.3(3) . . ?
C35 C34 C33 120.6(2) . . ?
C39 C34 C33 122.0(3) . . ?
C34 C35 C36 121.4(3) . . ?
C37 C36 C35 120.2(3) . . ?
C38 C37 C36 119.3(3) . . ?
C37 C38 C39 120.9(3) . . ?
C34 C39 C38 120.9(3) . . ?
C45 C40 C41 117.6(3) . . ?
C45 C40 C33 120.0(2) . . ?
C41 C40 C33 122.2(3) . . ?
C42 C41 C40 121.4(3) . . ?
C43 C42 C41 120.4(3) . . ?
C42 C43 C44 120.0(3) . . ?
C45 C44 C43 119.3(3) . . ?
C40 C45 C44 121.4(3) . . ?
C47 C46 C49 110.7(4) . . ?
C49' C46 C48' 116.4(9) . . ?
C49' C46 C30 113.0(6) . . ?
C47 C46 C30 110.1(3) . . ?
C49 C46 C30 112.8(3) . . ?
C48' C46 C30 112.1(5) . . ?
C47 C46 C48 109.2(3) . . ?
C49 C46 C48 105.7(4) . . ?
C30 C46 C48 108.1(3) . . ?
C49' C46 C47' 108.6(10) . . ?
C48' C46 C47' 98.7(8) . . ?
C30 C46 C47' 106.5(5) . . ?
C57 C50 C32 112.6(2) . . ?
C57 C50 C51 112.7(2) . . ?
C32 C50 C51 111.6(2) . . ?
C52 C51 C56 117.8(3) . . ?
C52 C51 C50 119.2(3) . . ?
C56 C51 C50 123.1(3) . . ?
C51 C52 C53 121.6(3) . . ?
C54 C53 C52 119.7(4) . . ?
C55 C54 C53 120.0(3) . . ?
C54 C55 C56 120.3(3) . . ?
C51 C56 C55 120.7(3) . . ?
C62 C57 C58 118.3(3) . . ?
C62 C57 C50 122.6(2) . . ?
C58 C57 C50 119.0(3) . . ?
C59 C58 C57 120.8(4) . . ?
C60 C59 C58 120.5(3) . . ?
C59 C60 C61 120.1(3) . . ?
C60 C61 C62 119.7(4) . . ?
C57 C62 C61 120.6(3) . . ?
C63 C64 C65 121.0(7) . . ?
C63 C64 C69 121.3(7) . . ?
C65 C64 C69 117.7(5) . . ?
C66 C65 C64 118.8(6) . . ?
C67 C66 C65 129.7(9) . . ?
C66 C67 C68 112.5(7) . . ?
C69 C68 C67 123.6(7) . . ?
C68 C69 C64 117.8(6) . . ?

_refine_diff_density_max         1.162
_refine_diff_density_min         -0.544
_refine_diff_density_rms         0.086

_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_solvent_exptl_crystal_recrystallization_method 'toluene, pentane'
_chemical_properties_physical    
Air-sensitive,Moisture-sensitive,Heat-sensitive,Oxygen-sensitive
