# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2013

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_p21n
#TrackingRef 'P21N.CIF'


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C11 H16 Cl F2 O4 Ti'
_chemical_formula_weight         333.59

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'
F F 0.0171 0.0103 '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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P2(1)/n

loop_
_symmetry_equiv_pos_as_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                   7.348(2)
_cell_length_b                   15.929(5)
_cell_length_c                   12.843(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 91.637(4)
_cell_angle_gamma                90.00
_cell_volume                     1502.6(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5327
_cell_measurement_theta_min      2.5575
_cell_measurement_theta_max      28.179

_exptl_crystal_description       plate
_exptl_crystal_colour            pale-yellow
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.475
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             684
_exptl_absorpt_coefficient_mu    0.774
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8421
_exptl_absorpt_correction_T_max  0.8927
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            7195
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_sigmaI/netI    0.0570
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.04
_diffrn_reflns_theta_max         26.00
_reflns_number_total             2926
_reflns_number_gt                2802
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.0417P)^2^+18.8955P] where P=(Fo^2^+2Fc^2^)/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         2926
_refine_ls_number_parameters     176
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.1073
_refine_ls_R_factor_gt           0.1051
_refine_ls_wR_factor_ref         0.2550
_refine_ls_wR_factor_gt          0.2541
_refine_ls_goodness_of_fit_ref   1.210
_refine_ls_restrained_S_all      1.210
_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 0.7603(10) 0.0385(5) 0.4013(7) 0.0319(17) Uani 1 1 d . . .
H1A H 0.8280 0.0577 0.3411 0.048 Uiso 1 1 calc R . .
H1B H 0.7869 -0.0209 0.4143 0.048 Uiso 1 1 calc R . .
H1C H 0.7968 0.0716 0.4627 0.048 Uiso 1 1 calc R . .
C2 C 0.5597(9) 0.0494(4) 0.3793(6) 0.0242(15) Uani 1 1 d . . .
C3 C 0.4505(11) -0.0166(5) 0.3444(7) 0.0338(18) Uani 1 1 d . . .
H3 H 0.5045 -0.0704 0.3368 0.041 Uiso 1 1 calc R . .
C4 C 0.2663(10) -0.0078(5) 0.3201(6) 0.0268(15) Uani 1 1 d . . .
C5 C 0.1566(12) -0.0826(5) 0.2858(8) 0.042(2) Uani 1 1 d . . .
H5A H 0.0920 -0.1053 0.3452 0.063 Uiso 1 1 calc R . .
H5B H 0.2379 -0.1256 0.2585 0.063 Uiso 1 1 calc R . .
H5C H 0.0683 -0.0658 0.2311 0.063 Uiso 1 1 calc R . .
C6 C 0.3120(12) 0.2088(7) 0.0370(6) 0.042(2) Uani 1 1 d . . .
H6A H 0.3959 0.2565 0.0342 0.063 Uiso 1 1 calc R . .
H6B H 0.2204 0.2134 -0.0196 0.063 Uiso 1 1 calc R . .
H6C H 0.3802 0.1563 0.0295 0.063 Uiso 1 1 calc R . .
C7 C 0.2194(10) 0.2089(5) 0.1397(5) 0.0258(15) Uani 1 1 d . . .
C8 C 0.0349(10) 0.2312(6) 0.1450(6) 0.0333(18) Uani 1 1 d . . .
H8 H -0.0310 0.2427 0.0819 0.040 Uiso 1 1 calc R . .
C9 C -0.0555(9) 0.2373(5) 0.2382(6) 0.0242(15) Uani 1 1 d . . .
C10 C -0.2476(10) 0.2664(6) 0.2406(7) 0.0354(19) Uani 1 1 d . . .
H10A H -0.3243 0.2212 0.2667 0.053 Uiso 1 1 calc R . .
H10B H -0.2895 0.2819 0.1700 0.053 Uiso 1 1 calc R . .
H10C H -0.2557 0.3153 0.2865 0.053 Uiso 1 1 calc R . .
F1 F 0.1754(5) 0.1577(3) 0.4990(3) 0.0247(9) Uani 1 1 d . . .
F2 F 0.3641(6) 0.2766(3) 0.4003(3) 0.0282(9) Uani 1 1 d . . .
O1 O 0.4969(6) 0.1245(3) 0.3923(4) 0.0224(10) Uani 1 1 d . . .
O2 O 0.1818(6) 0.0607(3) 0.3274(4) 0.0222(10) Uani 1 1 d . . .
O3 O 0.3164(6) 0.1906(3) 0.2202(4) 0.0225(10) Uani 1 1 d . . .
O4 O 0.0216(6) 0.2189(3) 0.3251(4) 0.0227(10) Uani 1 1 d . . .
Ti1 Ti 0.25822(16) 0.17681(7) 0.37068(9) 0.0165(3) Uani 1 1 d . . .
Cl1 Cl 0.7576(14) 0.0189(5) 0.0883(7) 0.204(4) Uani 1 1 d D . .
C30 C 0.942(4) 0.0389(11) 0.005(3) 0.24(2) Uani 1 1 d D . .
H30A H 0.8946 0.0558 -0.0650 0.284 Uiso 1 1 calc R . .
H30B H 1.0176 0.0855 0.0334 0.284 Uiso 1 1 calc R . .

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
C1 0.021(4) 0.035(4) 0.041(4) 0.010(3) 0.005(3) 0.001(3)
C2 0.024(4) 0.024(4) 0.025(3) 0.009(3) 0.010(3) 0.004(3)
C3 0.033(4) 0.021(4) 0.048(5) -0.005(3) 0.013(3) 0.004(3)
C4 0.034(4) 0.022(4) 0.025(4) -0.005(3) 0.008(3) -0.003(3)
C5 0.041(5) 0.024(4) 0.061(6) -0.017(4) 0.007(4) -0.004(3)
C6 0.038(5) 0.073(6) 0.016(4) 0.005(4) 0.007(3) -0.012(4)
C7 0.030(4) 0.036(4) 0.011(3) 0.004(3) 0.005(3) -0.014(3)
C8 0.027(4) 0.054(5) 0.018(4) 0.016(3) -0.004(3) -0.012(3)
C9 0.018(3) 0.027(4) 0.027(4) 0.009(3) -0.002(3) -0.005(3)
C10 0.021(4) 0.050(5) 0.034(4) 0.015(4) -0.003(3) -0.002(3)
F1 0.028(2) 0.030(2) 0.0163(19) 0.0026(16) 0.0030(15) 0.0043(17)
F2 0.036(2) 0.020(2) 0.028(2) -0.0016(17) -0.0062(18) 0.0002(17)
O1 0.020(2) 0.023(2) 0.024(2) 0.0008(19) -0.0003(18) 0.0026(19)
O2 0.021(2) 0.021(2) 0.025(3) -0.0021(19) 0.0025(19) -0.0025(19)
O3 0.022(2) 0.029(3) 0.017(2) 0.0020(19) 0.0014(18) -0.0025(19)
O4 0.021(2) 0.027(3) 0.020(2) 0.0040(19) 0.0001(18) 0.0038(19)
Ti1 0.0196(6) 0.0163(6) 0.0137(6) 0.0001(4) -0.0001(4) 0.0017(4)
Cl1 0.277(11) 0.157(7) 0.181(8) -0.029(6) 0.030(7) -0.040(7)
C30 0.33(6) 0.26(6) 0.12(2) 0.07(4) 0.05(3) -0.04(4)

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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.503(10) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C2 O1 1.295(8) . ?
C2 C3 1.389(11) . ?
C3 C4 1.387(11) . ?
C3 H3 0.9500 . ?
C4 O2 1.260(9) . ?
C4 C5 1.498(10) . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
C6 C7 1.501(10) . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
C7 O3 1.272(8) . ?
C7 C8 1.405(11) . ?
C8 C9 1.390(10) . ?
C8 H8 0.9500 . ?
C9 O4 1.271(8) . ?
C9 C10 1.487(10) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
F1 Ti1 1.799(4) . ?
F2 Ti1 1.806(4) . ?
O1 Ti1 1.954(5) . ?
O2 Ti1 2.006(5) . ?
O3 Ti1 2.004(5) . ?
O4 Ti1 1.938(5) . ?
Cl1 C30 1.784(10) . ?
C30 C30 1.507(10) 3_755 ?
C30 H30A 0.9900 . ?
C30 H30B 0.9900 . ?

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
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
O1 C2 C3 122.4(6) . . ?
O1 C2 C1 115.7(6) . . ?
C3 C2 C1 121.8(7) . . ?
C4 C3 C2 123.1(7) . . ?
C4 C3 H3 118.4 . . ?
C2 C3 H3 118.4 . . ?
O2 C4 C3 123.4(7) . . ?
O2 C4 C5 116.7(7) . . ?
C3 C4 C5 119.9(7) . . ?
C4 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C7 C6 H6A 109.5 . . ?
C7 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C7 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
O3 C7 C8 122.6(6) . . ?
O3 C7 C6 117.1(7) . . ?
C8 C7 C6 120.3(7) . . ?
C9 C8 C7 123.0(6) . . ?
C9 C8 H8 118.5 . . ?
C7 C8 H8 118.5 . . ?
O4 C9 C8 121.9(6) . . ?
O4 C9 C10 117.0(7) . . ?
C8 C9 C10 121.1(7) . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C2 O1 Ti1 134.2(5) . . ?
C4 O2 Ti1 133.2(5) . . ?
C7 O3 Ti1 132.7(4) . . ?
C9 O4 Ti1 135.9(5) . . ?
F1 Ti1 F2 96.3(2) . . ?
F1 Ti1 O4 90.64(19) . . ?
F2 Ti1 O4 97.9(2) . . ?
F1 Ti1 O1 97.1(2) . . ?
F2 Ti1 O1 88.0(2) . . ?
O4 Ti1 O1 169.7(2) . . ?
F1 Ti1 O3 171.7(2) . . ?
F2 Ti1 O3 90.2(2) . . ?
O4 Ti1 O3 83.4(2) . . ?
O1 Ti1 O3 88.2(2) . . ?
F1 Ti1 O2 89.9(2) . . ?
F2 Ti1 O2 170.1(2) . . ?
O4 Ti1 O2 89.6(2) . . ?
O1 Ti1 O2 83.6(2) . . ?
O3 Ti1 O2 84.2(2) . . ?
C30 C30 Cl1 109.9(13) 3_755 . ?
C30 C30 H30A 109.7 3_755 . ?
Cl1 C30 H30A 109.7 . . ?
C30 C30 H30B 109.7 3_755 . ?
Cl1 C30 H30B 109.7 . . ?
H30A C30 H30B 108.2 . . ?

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
O1 C2 C3 C4 0.3(12) . . . . ?
C1 C2 C3 C4 -177.7(7) . . . . ?
C2 C3 C4 O2 0.1(13) . . . . ?
C2 C3 C4 C5 -178.3(8) . . . . ?
O3 C7 C8 C9 1.7(13) . . . . ?
C6 C7 C8 C9 -176.1(8) . . . . ?
C7 C8 C9 O4 -3.6(12) . . . . ?
C7 C8 C9 C10 176.1(8) . . . . ?
C3 C2 O1 Ti1 -1.3(11) . . . . ?
C1 C2 O1 Ti1 176.8(5) . . . . ?
C3 C4 O2 Ti1 0.5(11) . . . . ?
C5 C4 O2 Ti1 178.9(5) . . . . ?
C8 C7 O3 Ti1 5.5(11) . . . . ?
C6 C7 O3 Ti1 -176.7(6) . . . . ?
C8 C9 O4 Ti1 -1.9(11) . . . . ?
C10 C9 O4 Ti1 178.4(5) . . . . ?
C9 O4 Ti1 F1 -168.4(7) . . . . ?
C9 O4 Ti1 F2 95.1(7) . . . . ?
C9 O4 Ti1 O1 -29.5(16) . . . . ?
C9 O4 Ti1 O3 5.8(7) . . . . ?
C9 O4 Ti1 O2 -78.5(7) . . . . ?
C2 O1 Ti1 F1 90.5(6) . . . . ?
C2 O1 Ti1 F2 -173.3(6) . . . . ?
C2 O1 Ti1 O4 -48.0(15) . . . . ?
C2 O1 Ti1 O3 -83.0(6) . . . . ?
C2 O1 Ti1 O2 1.4(6) . . . . ?
C7 O3 Ti1 F1 37.0(17) . . . . ?
C7 O3 Ti1 F2 -105.4(6) . . . . ?
C7 O3 Ti1 O4 -7.5(6) . . . . ?
C7 O3 Ti1 O1 166.5(7) . . . . ?
C7 O3 Ti1 O2 82.7(6) . . . . ?
C4 O2 Ti1 F1 -98.1(6) . . . . ?
C4 O2 Ti1 F2 31.7(15) . . . . ?
C4 O2 Ti1 O4 171.3(6) . . . . ?
C4 O2 Ti1 O1 -0.9(6) . . . . ?
C4 O2 Ti1 O3 87.9(6) . . . . ?

_diffrn_measured_fraction_theta_max 0.990
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.990
_refine_diff_density_max         1.432
_refine_diff_density_min         -1.209
_refine_diff_density_rms         0.157


_database_code_depnum_ccdc_archive 'CCDC 782632'