Concerning the structures of Lewis base adducts of titanium(IV) hexa­fluoro­iso­pro­pox­ide

The reaction of titanium(IV) chloride with sodium hexa­fluoro­iso­pro­pox­ide, carried out in hexa­fluoro­iso­propanol, produces titanium(IV) hexa­fluoro­iso­pro­pox­ide, which is a liquid at room temperature. Recrystallization from coordinating solvents, such as aceto­nitrile or tetra­hydro­furan, results in the formation of bis-solvate com­plexes. These com­pounds are of inter­est as possible Ziegler–Natta polymerization catalysts. The aceto­nitrile com­plex had been structurally characterized previously and adopts a distorted octahedral structure in which the nitrile ligands adopt a cis configuration, with nitro­gen lone pairs coordinated to the metal. The low-melting tetra­hydro­furan com­plex has not provided crystals suitable for single-crystal X-ray analysis. However, the structure of chlorido­tris­(hexa­fluoro­isopropoxido-κO)bis­(tetra­hydro­furan-κO)titanium(IV), [Ti(C₃HF₆O)₃Cl(C₄H₈O)₂], has been obtained and adopts a distorted octa­hedral coordination geometry, with a facial arrangement of the alkoxide ligands and adjacent tetra­hydro­furan ligands, coordinated by way of metal–oxygen polar coordinate inter­actions.

1. Introduction

Early transition-metal coordination chemistry involving Group IV metals (Ti, Hf, and Zr) has been of inter­est for many years, with applications as Ziegler–Natta (ZN)-type polymerization catalysts (Ziegler et al., 1955). It is generally accepted that effective ZN catalysts involve alkyl­ated and coordinatively unsaturated species that com­plex an olefin monomer, and then allow for insertion into the metal–carbon bond by way of the so-called Cossee–Arlman mechanism (Hartwig, 2010). Theoretical studies predict that the electron densities of the titanium ion play a major role in the effectiveness of the catalyst (Piovano et al., 2021). Previously, the author and co-workers published a description of a series of titanium fluoro­alkoxide com­plexes, obtained primarily by alcohol-exchange reactions. The nature of the products appeared to depend upon the acidity and steric requirements of the fluoro­alcohol and the alkyl groups of the titanium alkoxide starting materials (Campbell et al., 1994; Fisher et al., 1993). In several cases, the products adopted dimeric structures with bridging alkoxide ligands and/or coordinated alcohol ligands to satisfy the coordinative unsaturation of the titanium(IV) ions. In at least one case, a titanium coordination site was filled by the inter­action with an F atom, that wrapped around and formed a weak inter­action. The primary impetus of this work was to use the electron-withdrawing fluoro­alkoxide ligands as pseudohalides to provide significantly more Lewis acidity to the metal ion, yet retain the steric control associated with the alkoxide ligands. Sawamoto & Kamigaito (1996) have described using TiCl₂(OR)₂ com­pounds, where OR represents both alkyl alkoxides and phenoxides, as living polymerization catalysts that are potentially stereospecific. As part of prior work on the related titanium(IV) fluoro­alkoxides, the author and co-workers described the preparation and characterization of two hexa­fluoro­iso­pro­pox­ide com­plexes with the general formula Ti(OR^f)₄L₂, where L represents the coordinating solvents aceto­nitrile (in com­plex 1) and tetra­hydro­furan (THF) (in 2). A single-crystal X-ray structure determination of the aceto­nitrile com­plex indicated a monomeric structure in which the coordination geometry of the titanium was essentially octa­hedral, with cis-nitrile ligands acting as Lewis bases (Fig. 1), coordinating by way of nitro­gen lone pairs. This result was somewhat inter­esting, but not terribly surprising, and consistent with the structures of other similar com­plexes that had been characterized previously (Bradley, 1959; Bradley et al., 1978).

Figure 1 The presumed octa­hedral structure of monomeric bis-Lewis base adducts of titanium(IV) alkoxides.

On the other hand, we did not report the crystal structure of the tetra­hydro­furan com­plex 2. In fact, we attempted to obtain a single-crystal X-ray structure of this com­pound on several occasions, but were unable to obtain crystals of suitable quality to publish the results. However, the diffraction data we did obtain appeared to be most consistent with an autoionization isomer, in which an octa­hedrally coordinated [Ti(OR^f)₂L₄]²⁺ cation and a [Ti(OR^f)₆]²⁻ anion had formed. We have structurally characterized one other example of an octa­hedrally coordinated Ti^IV dianionic hexa­kis­fluoro­phenoxide, Na₂Ti(OC₆F₅)₆(THF)₂, so at least the formation of the dianion is plausible. [We have recently described the X-ray structures of the tetra­kis­(penta­fluoro­phenoxide)bis­(tetra­hydro­furan)­titanium(IV) com­plex and the hexa­kis­(penta­fluoro­phenoxide)titanium(IV) com­plex anion (Van Der Sluys et al., 2018).]

There are a limited number of examples of cationic titanium(IV) alkoxides which also include cyclo­pentadienyl ligands (Fandos et al., 2007). Perhaps the most relevant example that we are aware of is a cyclo­penta­dienyl titanium(IV) trication, in which there are coordinated aceto­nitrile ligands and three SbCl₆⁻ anions that act as counter-ions (Willey et al., 1994). Our spectroscopic evidence for autoionization, based on NMR and IR spectroscopic and conductivity measurements, was inconclusive at best and we were unsure if the ionization isomer represented a minor com­ponent or was representative of the bulk of the material. While ionization isomers for metal com­plexes are known (Barbier et al., 1972), we were unwilling to publish our speculative results. More recent results concerning the autoionization of metal coordination com­pounds (Tebbe & Muetterties, 1967; Kamata et al., 2012; Giesbrecht et al., 2004; Xie et al., 1996; Niemeyer, 2001) has encouraged a revisit of this work. Described herein are the most recent efforts, including the X-ray crystal structure of a mixed chloride/fluoro­alkoxide com­plex, which adopts a structure similar to that of the neutral aceto­nitrile com­plex.

2. Experimental

2.1. Synthesis

All synthetic procedures were carried out using standard Schlenk techniques or in a purified nitro­gen atmosphere using a Braun UNIlab glove-box. Solvents were purified by distillation from a sodium benzo­phenone ketal solution and stored in glass containers fitted with solvent seal fittings. IR spectra were recorded as KBr pellets, by grinding small portions of the sample with dried potassium bromide using an agate mortar and pestle in the glove-box. The Fourier transform IR (FT–IR) spectra were recorded on a ThermoScientific Nicolet iS10 FT–IR spectrometer. A background spectrum was subtracted to produce the percent transmittance spectrum of the sample. Residual gaseous carbon dioxide asymmetric vibrations were sometimes ob­served in the 2400 cm⁻¹ region, due to incom­plete background subtraction, and calibration was checked regularly using a film of polystyrene. NMR spectra were collected using a Bruker DPX 300 MHz spectrometer. Deuterated solvents, such as benzene-d₆ (≥99.6 atom% D) and di­chloro­methane-d₂ (≥99.9 atom% D) were purchased from Aldrich and degassed using a freeze–pump–thaw (FPT) method, and stored in the glove-box over mol­ecular sieves.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The selected crystal was twinned by non-merohedry. The twinning in intensity data was effectively removed by the integration and absorption correction programs. The positions of the H atoms were initially determined by geometry and were refined using a riding model. H-atom displacement parameters were set at 1.2 times the isotropic equivalent displacement parameters of the bonded atoms.

Table 1
Experimental details

Crystal data
Chemical formula	[Ti(C3HF6O)3Cl(C4H8O)2]
Mr	728.67
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	14.050 (4), 10.701 (3), 18.692 (5)
β (°)	108.450 (3)
V (Å^3)	2665.9 (13)
Z	4
Radiation type	Mo Kα
μ (mm^−1)	0.58
Crystal size (mm)	0.26 × 0.18 × 0.18
Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan [TWINABS (Sheldrick, 2015c) and SADABS (Krause et al., 2015)]
Tmin, Tmax	0.864, 0.904
No. of measured, independent and ob­served [I > 2σ(I)] reflections	67346, 4968, 3934
Rint	0.058
(sin θ/λ)max (Å^−1)	0.610
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.042, 0.123, 0.98
No. of reflections	4968
No. of parameters	379
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å^−3)	0.56, −0.71
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXT (Sheldrick, 2015a), SHELXL2018 (Sheldrick, 2015b), and Mercury (Macrae et al., 2020).

3. Results and discussion

3.1. Synthesis

Mazdiyasni et al. (1971) described the synthesis of a series of hexa­fluoro­iso­pro­pox­ides of the Group IV elements by way of a metathesis approach, in which the metal chlorides were reacted with four equivalents of sodium hexa­fluoro­iso­pro­pox­ide, with the corresponding alcohol as solvent (Scheme 1). The titanium(IV) com­pound is a colorless liquid that can be obtained in high yield by distillation. Mazdiyasni reported that these com­pounds could be recrystallized from a variety of solvents, including benzene, acetone, diethyl ether, and tetra­hydro­furan (THF), and indicated that the ethers reacted to form solvate com­plexes, but did not provide structural characterization data for these solvate com­plexes.

In our laboratory, we first prepared the sodium hexa­fluoro­iso­pro­pox­ide in situ by reacting sodium hydride with excess hexa­fluoro­iso­propanol and, after the evolution of hydrogen stopped, titanium(IV) chloride was added slowly while stirring. The product was recovered by first removing the excess hexa­fluoro­alcohol in vacuo and then gently heating the somewhat less volatile titanium(IV) hexa­fluoro­iso­pro­pox­ide and condensing the liquid product in a liquid-nitro­gen-cooled trap, which usually resulted in excellent yields. We typically accessed the purity of the product based on NMR spectroscopy, but we suspect that there is rapid ligand exchange on the NMR time scale at room temperature between various species that might be present in solution. Borden & Hammer (1970) also ob­served rapid ligand exchange at room temperature for a mixture of TiCl₄ and TiF₄ in THF solution. At −60 °C, exchange was slowed sufficiently to observe several species in solution. The ¹⁹F NMR data were most easily inter­preted as having resulted from a com­plex mixture of com­pounds in which cis-TiF₄(THF)₂ was present, but also that there were additional com­pounds having both chloride and fluoride coordinated to monomeric octa­hedrally coordinated titanium(IV) species with two THF mol­ecules occupying cis, but not trans, positions. While their inter­pretation of the data is very well reasoned, it is not totally clear that these data eliminate the possible presence of ionic species as well, such as TiF₅(THF)⁻, TiF₆²⁻, TiF₃(THF)₃⁺, and TiF₂(THF)₄²⁺, as additional com­ponents in solution.

When the titanium(IV) hexfluoro­iso­pro­pox­ide is recrystallized from coordinating solvents, such as aceto­nitrile or THF, the bis-solvate com­plexes, Ti(OR^f)₄L₂, are formed based on combustion elemental analysis and spectroscopic techniques, such as NMR and IR (Campbell et al., 1994; Fisher et al., 1993). The aceto­nitrile com­plex is a very stable crystalline solid that can be sublimed intact to form large nearly cubic crystals. The THF com­plex is extremely soluble in THF and has a relatively low melting point, which is slightly above room temperature (Campbell et al., 1994). Unfortunately, it has not been possible to produce single crystals of com­pound 2 of suitable quality for a convincing single-crystal X-ray analysis. However, on at least one occasion, recrystallization from a mixture of hexane and THF at −20 °C, produced a small number of crystals which were suitable for X-ray analysis. It appears that this higher-melting crystalline material was a minor com­ponent, with the formula TiCl[OCH(CF₃)₂]₃(THF)₂ (3), resulting from incom­plete substitution of chlorides for fluoro­alkoxides in the metathesis reaction.

3.2. Crystal structure

The mol­ecular structue of 3 shown in Fig. 2 emphasizes the nearly octa­hedral coordination geometry of the Ti atom. The fluoro­alkoxide ligands form a facial arrangement, with the chloride and two THF ligands on opposing sides. Table 2 provides relevant bond length and angle data. Fractional coordinates and other crystallographic data can be found in the supporting information.

Table 2
Selected geometric parameters (Å, °)

Ti1—O1	1.8386 (17)	Ti1—O4	2.1043 (17)
Ti1—O2	1.8426 (17)	Ti1—O5	2.1593 (17)
Ti1—O3	1.8679 (17)	Ti1—Cl1	2.3399 (9)
O1—Ti1—O2	100.14 (8)	O2—Ti1—Cl1	90.52 (5)
O1—Ti1—O3	94.69 (7)	O3—Ti1—Cl1	172.19 (6)
O2—Ti1—O3	92.72 (7)	O4—Ti1—Cl1	90.02 (5)
O1—Ti1—O4	88.84 (7)	O5—Ti1—Cl1	85.92 (5)
O2—Ti1—O4	170.98 (7)	C2—O1—Ti1	140.75 (15)
O3—Ti1—O4	85.68 (7)	C5—O2—Ti1	142.97 (15)
O1—Ti1—O5	167.56 (7)	C8—O3—Ti1	130.80 (15)
O2—Ti1—O5	92.10 (7)	C13—O4—Ti1	129.17 (14)
O3—Ti1—O5	86.87 (7)	C10—O4—Ti1	120.92 (13)
O4—Ti1—O5	78.95 (6)	C14—O5—Ti1	129.22 (14)
O1—Ti1—Cl1	91.72 (6)	C17—O5—Ti1	121.54 (13)

Figure 2 The mol­ecular structure of com­pound 3, showing the numbering scheme used. Displacement ellipsoids are drawn at the 50% probability level.

The coordination geometry of 3 is best described as distorted octa­hedral. The average fluoro­alkoxide Ti—O bond length [1.85 (1) Å] com­pares very well with the average fluoro­alkoxide Ti—O bond lengths reported previously for com­pound 1 [1.84 (1) Å]. Not surprisingly, the longest metal–ligand bond length is the bond between the titanium and chloride [2.3399 (9) Å], which is similar to the terminal Ti—Cl distances ob­served in other octa­hedrally coordinated titanium com­pounds (Sarsfield et al., 1999; McCarthy et al., 2020; Nielson et al., 2001; Wright & Williams, 1968). There appears to be a slight but significant trans influence (Burdett & Albright, 1979) in the Ti—OR^f bond lengths, with the Ti—O3 bond length, which is trans to the chloride ligand, being slightly longer than the Ti—O1/O2 bond lengths, which are trans to the coordinated THF ligands. The Ti—O bond lengths for the coordinated THF ligands are significantly longer than the alkoxide bond lengths [average 2.13 (1) Å], consistent with the weaker polar coordinate inter­actions of these ligands. The trans influence is due to the weakly coordinating neutral THF ligands that allow the trans-fluoro­alkoxides to bond more strongly to titanium than the alkoxide that is trans to the formally anionic chloride ligand.

The large Ti—O—C angles of the fluoro­alkoxides are also com­parable to those ob­served in com­pound 1 and consistent with other structurally characterized Ti^IV alkoxide com­plexes (Schubert et al., 2020). These angles are best inter­preted as resulting from significant oxygen-to-titanium pπ→dπ bonding. Titanium(IV) has a 3d⁰ electronic configuration and therefore in an octa­hedral ligand field, the empty t_2g set (d_xy, d_xz, and d_yz) of d orbitals can accept electrons from π-donor ligands, such as alkoxides. Presumably this is tempered somewhat in fluoro­alkoxide ligands due to the electron-withdrawing nature of the –CF₃ groups, as com­pared with alkyl­alkoxide ligands, making the Ti—OR^f inter­actions more halide-like in nature. The presumed order of π-bonding is proposed to be OR^f > Cl > THF, consistent with the trans-influence effects that we observe in 3 and consistent with the order of F > Cl > THF used by Borden & Hammer (1970) to justify their proposed stereochemical inter­pretation of the ¹⁹F solution NMR data for the TiF₄/TiCl₄/THF system. Perhaps even more straightforward, the trans influence in these com­pounds can be inter­preted based on hard–soft Lewis acid–base theory (Pearson, 1963; Jolly, 1984).

4. Conclusions

While the crystal structure of com­pound 3 reported here clearly indicates a monomeric mol­ecular coordination com­pound and not an ionization isomer, as speculated for com­pound 2, it is not totally clear if replacing the final chloride ligand would tip the scale in favor of such a structure. There may be a subtle balance between the steric factors of the coordinated ligands, the degree of covalency or ionic inter­actions associated with the metal cation and the ligands, as well as inter­molecular forces of attraction between the coordination com­plex and the solvent. The initial hypothesis suggested that an increase in the ionic nature of the alkoxide ligands would produce favorable properties that would facilitate polymerization catalysis. Coordinately unsaturated cationic transition-metal species are particularly promising in this regard. We note that the ionic radius of the titanium(IV) ion (0.745 Å), is smaller than the highly ionic lanthanide ions (1.00–1.17 Å) (Shannon, 1976), with the latter producing autoionization in certain cases (Fandos et al., 2007). It is also not clear if there are several structural possibilities that might exist in solution, all of which are rapidly exchanging, and that crystallization of a solid does not necessarily indicate what species are present in solution. It is hoped that the solvent mol­ecules are labile enough to provide open coordination sites and that alkyl­ation of these com­pounds will produce effective olefin polymerization catalysts. Further studies are currently in progress.

Supporting information

Computing details

Chloridotris(hexafluoroisopropoxido-κO)bis(tetrahydrofuran-κO)titanium(IV)

Crystal data

[Ti(C3HF6O)3Cl(C4H8O)2]	F(000) = 1448
Mr = 728.67	Dx = 1.816 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.050 (4) Å	Cell parameters from 9958 reflections
b = 10.701 (3) Å	θ = 2.2–24.3°
c = 18.692 (5) Å	µ = 0.57 mm^−1
β = 108.450 (3)°	T = 100 K
V = 2665.9 (13) Å^3	Block, colourless
Z = 4	0.26 × 0.18 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer	3934 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.058
Absorption correction: multi-scan [TWINABS (Sheldrick, 2015c) and SADABS (Krause et al. (2015)]	θmax = 25.7°, θmin = 2.2°
Tmin = 0.864, Tmax = 0.904	h = −16→16
67346 measured reflections	k = 0→13
4968 independent reflections	l = 0→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.090P)^2 + 0.4P] where P = (Fo^2 + 2Fc^2)/3
4968 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.71 e Å^−3

Special details

Geometry. 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.

Refinement. A colorless block-shaped crystal of dimensions 0.180 × 0.182 × 0.262 mm was selected for structural analysis. Intensity data for this compound were collected using a diffractometer with a Bruker APEX CCD area detector and graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The sample was cooled to 100(±2) K. Cell parameters were determined from a least-squares fit of 9958 peaks in the range 2.22 < q < 24.29°. A total of 67346 data were measured in the range 2.223 < q < 25.677° using w oscillation frames. The data were corrected for absorption by the empirical method giving minimum and maximum transmission factors of 0.864 and 0.904 (Krause et al., 2015).

The displacement ellipsoids were drawn at the 50% probability level. The data were merged to form a set of 4968 independent data with R(int) = 0.0582 and a coverage of 99.6%. The monoclinic space group P21/c was determined by systematic absences and statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by full-matrix least-squares methods on F².

A total of 379 parameters were refined against 4968 data to give wR(F²) = 0.1229 and S = 0.984 for weights of w = 1/[s² (F²) + (0.0900 P)² + 0.4000 P], where P = [F_o² + 2F_c²]/3. The final R(F) was 0.0420 for the 3934 observed, [F > 4 s (F)], data. The largest shift/s.u. was 0.001 in the final refinement cycle. The final difference map had maxima and minima of 0.564 and -0.707 e Å^-3, respectively. The X-ray crystallographic data has been submitted to the Cambridge Structural Database.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ti1	0.23757 (3)	0.27877 (4)	0.52659 (2)	0.01242 (14)
Cl1	0.08372 (4)	0.29034 (6)	0.54994 (3)	0.01954 (17)
F1	0.00839 (14)	0.35382 (17)	0.35953 (10)	0.0471 (5)
F2	−0.04629 (13)	0.20602 (18)	0.27930 (10)	0.0453 (5)
F3	0.09556 (14)	0.29234 (17)	0.29047 (10)	0.0440 (5)
F4	0.01723 (15)	−0.03175 (17)	0.33302 (11)	0.0519 (5)
F5	0.13441 (15)	0.04539 (17)	0.29625 (10)	0.0468 (5)
F6	0.17015 (15)	−0.03587 (15)	0.40541 (10)	0.0452 (5)
F7	0.11586 (12)	−0.03793 (16)	0.54016 (10)	0.0399 (4)
F8	0.18142 (16)	−0.14042 (17)	0.64284 (12)	0.0559 (6)
F9	0.26588 (13)	−0.11180 (16)	0.56607 (10)	0.0388 (4)
F10	0.30104 (16)	−0.0130 (2)	0.76008 (10)	0.0593 (6)
F11	0.40387 (12)	−0.02103 (17)	0.69618 (9)	0.0378 (4)
F12	0.36859 (14)	0.15502 (18)	0.73564 (9)	0.0432 (5)
F13	0.35957 (13)	0.19588 (17)	0.37698 (9)	0.0366 (4)
F14	0.50952 (14)	0.12417 (18)	0.42146 (10)	0.0458 (5)
F15	0.48170 (14)	0.32223 (16)	0.42168 (10)	0.0411 (5)
F16	0.59612 (12)	0.12469 (18)	0.57080 (10)	0.0455 (5)
F17	0.57008 (12)	0.32210 (17)	0.57630 (10)	0.0419 (5)
F18	0.51019 (12)	0.19529 (17)	0.63939 (9)	0.0371 (4)
O1	0.17872 (12)	0.20501 (15)	0.43429 (9)	0.0173 (4)
O2	0.27198 (12)	0.13877 (15)	0.58666 (9)	0.0166 (4)
O3	0.36457 (12)	0.29014 (15)	0.51504 (9)	0.0151 (4)
O4	0.21035 (12)	0.45446 (15)	0.47342 (9)	0.0159 (4)
O5	0.29344 (12)	0.40218 (15)	0.62214 (9)	0.0171 (4)
C1	0.0363 (2)	0.2527 (3)	0.32909 (16)	0.0317 (7)
C2	0.08771 (19)	0.1580 (2)	0.39018 (14)	0.0202 (6)
H2	0.044296	0.144049	0.422740	0.024*
C3	0.1030 (2)	0.0337 (3)	0.35594 (15)	0.0288 (6)
C4	0.2017 (2)	−0.0576 (3)	0.59623 (17)	0.0303 (7)
C5	0.24189 (19)	0.0646 (2)	0.63554 (14)	0.0199 (5)
H5	0.186717	0.108028	0.648787	0.024*
C6	0.3300 (2)	0.0457 (3)	0.70725 (15)	0.0313 (7)
C7	0.4460 (2)	0.2102 (3)	0.43168 (16)	0.0273 (6)
C8	0.43050 (18)	0.1979 (2)	0.50863 (14)	0.0175 (5)
H8	0.400039	0.114424	0.511673	0.021*
C9	0.5278 (2)	0.2099 (3)	0.57390 (16)	0.0268 (6)
C10	0.24761 (19)	0.4840 (2)	0.41010 (13)	0.0188 (5)
H10A	0.236777	0.412906	0.374522	0.023*
H10B	0.320045	0.504382	0.428445	0.023*
C11	0.1864 (2)	0.5961 (3)	0.37291 (15)	0.0265 (6)
H11A	0.224154	0.649274	0.347877	0.032*
H11B	0.122329	0.570331	0.335365	0.032*
C12	0.1688 (2)	0.6630 (2)	0.43848 (17)	0.0300 (7)
H12A	0.111163	0.720959	0.421247	0.036*
H12B	0.229079	0.710321	0.467785	0.036*
C13	0.14695 (19)	0.5575 (2)	0.48432 (15)	0.0216 (6)
H13A	0.165042	0.580831	0.538235	0.026*
H13B	0.075085	0.534296	0.465743	0.026*
C14	0.2531 (2)	0.4263 (2)	0.68441 (14)	0.0231 (6)
H14A	0.249614	0.348035	0.711704	0.028*
H14B	0.185126	0.463146	0.665311	0.028*
C15	0.3259 (2)	0.5172 (3)	0.73536 (15)	0.0318 (7)
H15A	0.380907	0.472747	0.773328	0.038*
H15B	0.291513	0.572981	0.761594	0.038*
C16	0.3651 (2)	0.5899 (2)	0.68097 (15)	0.0251 (6)
H16A	0.316295	0.653889	0.653447	0.030*
H16B	0.429902	0.630870	0.707385	0.030*
C17	0.3776 (2)	0.4884 (2)	0.62865 (15)	0.0232 (6)
H17A	0.373852	0.523353	0.578781	0.028*
H17B	0.442781	0.445263	0.650081	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0111 (2)	0.0140 (2)	0.0132 (2)	−0.00076 (17)	0.00517 (17)	−0.00024 (16)
Cl1	0.0143 (3)	0.0214 (3)	0.0259 (3)	0.0006 (2)	0.0107 (2)	0.0000 (2)
F1	0.0429 (11)	0.0381 (11)	0.0425 (11)	0.0130 (9)	−0.0119 (8)	−0.0046 (8)
F2	0.0299 (10)	0.0628 (13)	0.0295 (10)	−0.0096 (9)	−0.0101 (8)	−0.0069 (8)
F3	0.0456 (11)	0.0488 (11)	0.0298 (10)	−0.0120 (9)	0.0006 (8)	0.0149 (8)
F4	0.0522 (12)	0.0423 (11)	0.0631 (13)	−0.0302 (9)	0.0209 (10)	−0.0288 (10)
F5	0.0657 (13)	0.0502 (11)	0.0363 (10)	−0.0055 (10)	0.0330 (10)	−0.0131 (8)
F6	0.0642 (13)	0.0223 (9)	0.0449 (11)	0.0018 (9)	0.0112 (10)	−0.0043 (8)
F7	0.0256 (9)	0.0321 (9)	0.0574 (12)	−0.0083 (7)	0.0067 (8)	−0.0050 (8)
F8	0.0612 (14)	0.0343 (11)	0.0819 (15)	−0.0082 (9)	0.0363 (12)	0.0256 (10)
F9	0.0375 (10)	0.0265 (9)	0.0547 (11)	0.0036 (8)	0.0179 (9)	−0.0098 (8)
F10	0.0682 (14)	0.0882 (16)	0.0290 (10)	0.0156 (12)	0.0262 (10)	0.0328 (10)
F11	0.0312 (9)	0.0471 (10)	0.0331 (9)	0.0189 (8)	0.0075 (7)	0.0064 (8)
F12	0.0429 (11)	0.0536 (12)	0.0249 (9)	0.0086 (9)	−0.0010 (8)	−0.0104 (8)
F13	0.0334 (10)	0.0552 (11)	0.0233 (9)	0.0023 (8)	0.0119 (7)	−0.0096 (7)
F14	0.0409 (11)	0.0554 (12)	0.0523 (11)	0.0145 (9)	0.0308 (9)	−0.0093 (9)
F15	0.0510 (11)	0.0441 (10)	0.0401 (10)	−0.0119 (9)	0.0312 (9)	0.0063 (8)
F16	0.0226 (9)	0.0588 (12)	0.0538 (11)	0.0240 (9)	0.0105 (8)	0.0113 (9)
F17	0.0224 (9)	0.0459 (11)	0.0508 (11)	−0.0150 (8)	0.0020 (8)	0.0025 (8)
F18	0.0258 (9)	0.0573 (11)	0.0252 (9)	0.0060 (8)	0.0038 (7)	0.0129 (8)
O1	0.0151 (9)	0.0205 (9)	0.0149 (9)	−0.0023 (7)	0.0026 (7)	−0.0015 (7)
O2	0.0160 (9)	0.0189 (9)	0.0182 (9)	−0.0005 (7)	0.0100 (7)	0.0025 (7)
O3	0.0145 (9)	0.0159 (9)	0.0154 (9)	0.0019 (7)	0.0055 (7)	0.0002 (6)
O4	0.0179 (9)	0.0159 (9)	0.0165 (9)	0.0024 (7)	0.0089 (7)	0.0015 (7)
O5	0.0179 (9)	0.0212 (9)	0.0150 (8)	−0.0067 (7)	0.0089 (7)	−0.0047 (7)
C1	0.0273 (16)	0.0362 (16)	0.0238 (15)	−0.0039 (13)	−0.0030 (12)	−0.0035 (13)
C2	0.0185 (13)	0.0249 (14)	0.0170 (13)	−0.0078 (11)	0.0051 (10)	−0.0052 (10)
C3	0.0326 (16)	0.0287 (15)	0.0253 (15)	−0.0100 (13)	0.0093 (12)	−0.0051 (12)
C4	0.0306 (16)	0.0211 (14)	0.0435 (17)	−0.0014 (12)	0.0180 (14)	0.0070 (12)
C5	0.0215 (13)	0.0213 (13)	0.0224 (13)	0.0044 (11)	0.0147 (11)	0.0066 (10)
C6	0.0379 (17)	0.0380 (17)	0.0222 (14)	0.0124 (14)	0.0156 (13)	0.0098 (13)
C7	0.0248 (15)	0.0317 (16)	0.0315 (16)	0.0007 (12)	0.0176 (13)	−0.0045 (12)
C8	0.0142 (12)	0.0157 (12)	0.0255 (14)	0.0006 (10)	0.0106 (10)	0.0026 (10)
C9	0.0193 (14)	0.0307 (16)	0.0317 (16)	0.0046 (12)	0.0099 (12)	0.0060 (12)
C10	0.0212 (13)	0.0208 (13)	0.0183 (13)	−0.0003 (11)	0.0115 (10)	0.0060 (10)
C11	0.0253 (15)	0.0259 (14)	0.0288 (15)	0.0022 (12)	0.0092 (12)	0.0108 (11)
C12	0.0298 (16)	0.0181 (14)	0.0465 (18)	0.0029 (12)	0.0184 (14)	0.0063 (12)
C13	0.0228 (14)	0.0155 (13)	0.0301 (14)	0.0068 (11)	0.0133 (11)	0.0009 (10)
C14	0.0289 (15)	0.0278 (14)	0.0179 (13)	−0.0037 (12)	0.0150 (11)	−0.0047 (11)
C15	0.0375 (17)	0.0373 (17)	0.0227 (14)	−0.0121 (14)	0.0123 (13)	−0.0117 (12)
C16	0.0271 (15)	0.0220 (14)	0.0247 (14)	−0.0065 (12)	0.0059 (11)	−0.0053 (11)
C17	0.0223 (14)	0.0260 (14)	0.0235 (14)	−0.0113 (11)	0.0106 (11)	−0.0058 (11)

Geometric parameters (Å, º)

Ti1—O1	1.8386 (17)	C1—C2	1.526 (4)
Ti1—O2	1.8426 (17)	C2—C3	1.521 (4)
Ti1—O3	1.8679 (17)	C2—H2	1.0000
Ti1—O4	2.1043 (17)	C4—C5	1.518 (4)
Ti1—O5	2.1593 (17)	C5—C6	1.523 (4)
Ti1—Cl1	2.3399 (9)	C5—H5	1.0000
F1—C1	1.338 (3)	C7—C8	1.527 (4)
F2—C1	1.334 (3)	C8—C9	1.523 (4)
F3—C1	1.332 (4)	C8—H8	1.0000
F4—C3	1.341 (3)	C10—C11	1.511 (4)
F5—C3	1.330 (3)	C10—H10A	0.9900
F6—C3	1.322 (3)	C10—H10B	0.9900
F7—C4	1.341 (3)	C11—C12	1.506 (4)
F8—C4	1.335 (3)	C11—H11A	0.9900
F9—C4	1.338 (3)	C11—H11B	0.9900
F10—C6	1.338 (3)	C12—C13	1.506 (4)
F11—C6	1.329 (3)	C12—H12A	0.9900
F12—C6	1.327 (4)	C12—H12B	0.9900
F13—C7	1.326 (3)	C13—H13A	0.9900
F14—C7	1.337 (3)	C13—H13B	0.9900
F15—C7	1.335 (3)	C14—C15	1.511 (4)
F16—C9	1.338 (3)	C14—H14A	0.9900
F17—C9	1.334 (3)	C14—H14B	0.9900
F18—C9	1.333 (3)	C15—C16	1.515 (4)
O1—C2	1.379 (3)	C15—H15A	0.9900
O2—C5	1.374 (3)	C15—H15B	0.9900
O3—C8	1.384 (3)	C16—C17	1.509 (4)
O4—C13	1.472 (3)	C16—H16A	0.9900
O4—C10	1.472 (3)	C16—H16B	0.9900
O5—C14	1.469 (3)	C17—H17A	0.9900
O5—C17	1.475 (3)	C17—H17B	0.9900
O1—Ti1—O2	100.14 (8)	F13—C7—C8	110.3 (2)
O1—Ti1—O3	94.69 (7)	F15—C7—C8	112.4 (2)
O2—Ti1—O3	92.72 (7)	F14—C7—C8	112.1 (2)
O1—Ti1—O4	88.84 (7)	O3—C8—C9	109.0 (2)
O2—Ti1—O4	170.98 (7)	O3—C8—C7	108.6 (2)
O3—Ti1—O4	85.68 (7)	C9—C8—C7	112.8 (2)
O1—Ti1—O5	167.56 (7)	O3—C8—H8	108.8
O2—Ti1—O5	92.10 (7)	C9—C8—H8	108.8
O3—Ti1—O5	86.87 (7)	C7—C8—H8	108.8
O4—Ti1—O5	78.95 (6)	F18—C9—F17	106.6 (2)
O1—Ti1—Cl1	91.72 (6)	F18—C9—F16	107.7 (2)
O2—Ti1—Cl1	90.52 (5)	F17—C9—F16	107.3 (2)
O3—Ti1—Cl1	172.19 (6)	F18—C9—C8	110.2 (2)
O4—Ti1—Cl1	90.02 (5)	F17—C9—C8	112.3 (2)
O5—Ti1—Cl1	85.92 (5)	F16—C9—C8	112.5 (2)
C2—O1—Ti1	140.75 (15)	O4—C10—C11	104.20 (19)
C5—O2—Ti1	142.97 (15)	O4—C10—H10A	110.9
C8—O3—Ti1	130.80 (15)	C11—C10—H10A	110.9
C13—O4—C10	109.58 (17)	O4—C10—H10B	110.9
C13—O4—Ti1	129.17 (14)	C11—C10—H10B	110.9
C10—O4—Ti1	120.92 (13)	H10A—C10—H10B	108.9
C14—O5—C17	108.95 (17)	C12—C11—C10	102.6 (2)
C14—O5—Ti1	129.22 (14)	C12—C11—H11A	111.2
C17—O5—Ti1	121.54 (13)	C10—C11—H11A	111.2
F3—C1—F2	107.2 (2)	C12—C11—H11B	111.2
F3—C1—F1	106.9 (2)	C10—C11—H11B	111.2
F2—C1—F1	107.0 (2)	H11A—C11—H11B	109.2
F3—C1—C2	112.9 (2)	C11—C12—C13	102.9 (2)
F2—C1—C2	112.0 (2)	C11—C12—H12A	111.2
F1—C1—C2	110.6 (2)	C13—C12—H12A	111.2
O1—C2—C3	110.1 (2)	C11—C12—H12B	111.2
O1—C2—C1	109.6 (2)	C13—C12—H12B	111.2
C3—C2—C1	111.2 (2)	H12A—C12—H12B	109.1
O1—C2—H2	108.6	O4—C13—C12	104.0 (2)
C3—C2—H2	108.6	O4—C13—H13A	111.0
C1—C2—H2	108.6	C12—C13—H13A	111.0
F6—C3—F5	106.6 (2)	O4—C13—H13B	111.0
F6—C3—F4	107.4 (2)	C12—C13—H13B	111.0
F5—C3—F4	106.5 (2)	H13A—C13—H13B	109.0
F6—C3—C2	111.3 (2)	O5—C14—C15	105.0 (2)
F5—C3—C2	113.5 (2)	O5—C14—H14A	110.7
F4—C3—C2	111.1 (2)	C15—C14—H14A	110.7
F9—C4—F8	107.4 (2)	O5—C14—H14B	110.7
F9—C4—F7	107.4 (2)	C15—C14—H14B	110.7
F8—C4—F7	106.8 (2)	H14A—C14—H14B	108.8
F9—C4—C5	112.3 (2)	C14—C15—C16	103.0 (2)
F8—C4—C5	112.3 (2)	C14—C15—H15A	111.2
F7—C4—C5	110.3 (2)	C16—C15—H15A	111.2
O2—C5—C4	108.8 (2)	C14—C15—H15B	111.2
O2—C5—C6	109.0 (2)	C16—C15—H15B	111.2
C4—C5—C6	112.7 (2)	H15A—C15—H15B	109.1
O2—C5—H5	108.8	C17—C16—C15	101.9 (2)
C4—C5—H5	108.8	C17—C16—H16A	111.4
C6—C5—H5	108.8	C15—C16—H16A	111.4
F12—C6—F11	107.2 (2)	C17—C16—H16B	111.4
F12—C6—F10	107.5 (2)	C15—C16—H16B	111.4
F11—C6—F10	107.3 (2)	H16A—C16—H16B	109.2
F12—C6—C5	110.5 (2)	O5—C17—C16	104.4 (2)
F11—C6—C5	113.0 (2)	O5—C17—H17A	110.9
F10—C6—C5	111.1 (2)	C16—C17—H17A	110.9
F13—C7—F15	106.8 (2)	O5—C17—H17B	110.9
F13—C7—F14	107.5 (2)	C16—C17—H17B	110.9
F15—C7—F14	107.5 (2)	H17A—C17—H17B	108.9
O2—Ti1—O1—C2	85.1 (2)	O2—C5—C6—F12	53.2 (3)
O3—Ti1—O1—C2	178.7 (2)	C4—C5—C6—F12	174.1 (2)
O4—Ti1—O1—C2	−95.8 (2)	O2—C5—C6—F11	−67.0 (3)
O5—Ti1—O1—C2	−84.6 (4)	C4—C5—C6—F11	53.9 (3)
Cl1—Ti1—O1—C2	−5.8 (2)	O2—C5—C6—F10	172.4 (2)
O1—Ti1—O2—C5	−99.1 (3)	C4—C5—C6—F10	−66.8 (3)
O3—Ti1—O2—C5	165.7 (3)	Ti1—O3—C8—C9	−119.1 (2)
O5—Ti1—O2—C5	78.7 (3)	Ti1—O3—C8—C7	117.6 (2)
Cl1—Ti1—O2—C5	−7.2 (3)	F13—C7—C8—O3	−60.6 (3)
O1—Ti1—O3—C8	−64.4 (2)	F15—C7—C8—O3	58.5 (3)
O2—Ti1—O3—C8	36.0 (2)	F14—C7—C8—O3	179.7 (2)
O4—Ti1—O3—C8	−152.9 (2)	F13—C7—C8—C9	178.4 (2)
O5—Ti1—O3—C8	128.0 (2)	F15—C7—C8—C9	−62.5 (3)
Ti1—O1—C2—C3	−135.4 (2)	F14—C7—C8—C9	58.7 (3)
Ti1—O1—C2—C1	102.0 (3)	O3—C8—C9—F18	60.8 (3)
F3—C1—C2—O1	51.3 (3)	C7—C8—C9—F18	−178.4 (2)
F2—C1—C2—O1	172.5 (2)	O3—C8—C9—F17	−57.8 (3)
F1—C1—C2—O1	−68.3 (3)	C7—C8—C9—F17	62.9 (3)
F3—C1—C2—C3	−70.6 (3)	O3—C8—C9—F16	−179.0 (2)
F2—C1—C2—C3	50.5 (3)	C7—C8—C9—F16	−58.2 (3)
F1—C1—C2—C3	169.7 (2)	C13—O4—C10—C11	−11.7 (3)
O1—C2—C3—F6	41.1 (3)	Ti1—O4—C10—C11	162.37 (15)
C1—C2—C3—F6	162.8 (2)	O4—C10—C11—C12	32.5 (3)
O1—C2—C3—F5	−79.2 (3)	C10—C11—C12—C13	−41.1 (3)
C1—C2—C3—F5	42.4 (3)	C10—O4—C13—C12	−13.9 (3)
O1—C2—C3—F4	160.8 (2)	Ti1—O4—C13—C12	172.74 (16)
C1—C2—C3—F4	−77.6 (3)	C11—C12—C13—O4	33.9 (3)
Ti1—O2—C5—C4	106.6 (3)	C17—O5—C14—C15	−8.2 (3)
Ti1—O2—C5—C6	−130.1 (2)	Ti1—O5—C14—C15	177.99 (17)
F9—C4—C5—O2	51.7 (3)	O5—C14—C15—C16	30.3 (3)
F8—C4—C5—O2	172.9 (2)	C14—C15—C16—C17	−40.6 (3)
F7—C4—C5—O2	−68.0 (3)	C14—O5—C17—C16	−17.4 (3)
F9—C4—C5—C6	−69.3 (3)	Ti1—O5—C17—C16	157.00 (16)
F8—C4—C5—C6	51.9 (3)	C15—C16—C17—O5	35.7 (3)
F7—C4—C5—C6	171.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1	1.00	2.75	3.321 (3)	117
C5—H5···Cl1	1.00	2.76	3.329 (3)	117
C10—H10A···F3	0.99	2.47	3.278 (3)	139
C10—H10B···F17^i	0.99	2.43	3.243 (3)	139
C11—H11B···F2^ii	0.99	2.53	3.132 (3)	119
C12—H12A···Cl1^iii	0.99	2.96	3.657 (3)	129
C12—H12B···F9^iv	0.99	2.58	3.361 (3)	136
C13—H13B···Cl1^iii	0.99	2.86	3.500 (3)	123
C14—H14A···F12	0.99	2.61	3.315 (3)	129
C17—H17A···F15^i	0.99	2.62	3.174 (3)	116
C17—H17A···O4	0.99	2.61	3.124 (3)	112

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) x, y+1, z.