supplementary materials


bv2226 scheme

Acta Cryst. (2013). E69, m673-m674    [ doi:10.1107/S1600536813030249 ]

[6,6'-Bis(1,1-di­methyl­eth­yl)-4,4'-dimethyl-2,2'-methyl­enediphenolato-[kappa]2O,O']di­chlorido­(9H-fluoren-9-ol-[kappa]O)titanium(IV)-fluorene-diethyl ether (1/0.5/1)

A. J. Nielson, C. Shen and J. M. Waters

Abstract top

The title adduct, [TiCl2(C23H30O2)(C13H10O]·0.5C13H10·C4H10O, is a monomer with a trigonal-bypyramidal coordination sphere of the TiIV atom in which the ligand O atoms of the bidentate diphenolate anion are located in both apical and equatorial positions. Chloride ligands occupy the remaining two equatorial sites of the trigonal bypyramid with the fluoren-9-ol O atom occupying the other apical site. The hy­droxy group H atom of this latter group is hydrogen bonded to an O atom of a non-coordinating diethyl ether mol­ecule. The title compound also contains a further fluorene solvent mol­ecule, which lies across a centre of symmetry and which is equally disordered over an inversion centre.

Comment top

Titanium complexes containing the 2,2-methylenebis-(6-tert-butyl-4-methylphenolato) ligand (OAr)2 are well known and have been used as catalysts for olefin polymerization reactions. These catalysts are normally based on the dichloro complex [TiCl2{(OAr)2}] for which the X-ray crystal structures of this type of molecule shows a monomeric molecule with a distorted tetrahedral geometry (Toscano et al. 1998). This type of molecule is apparently coordinatively unsaturated since there are two reports of X-ray structures which show a fifth ligand can be added (Okuda et al. 1995; Gielens et al. 1999). During reactions of [TiCl2{(OAr)2}] in which we were attempting to replace one of the chloro ligands with a fluorene ligand C13H9, (Fl), the lithiated salt of fluorene was reacted with the titanium precursor and the resulting solution was stood for several months at -20° in an attempt to form crystals of the expected [TiCl(Fl){(OAr)2}] product. Over the extended crystallization period a small quantity of crystals was obtained and these were found to be the fluoren-9-ol adduct of the original [TiCl2{(OAr)2}] starting material with solvate molecules of diethyl ether and fluorene included. The fluoren-9-ol ligand apparently resulted from the lithiated fluorene undergoing hydrolysis as a result of slow moisture ingress into the reaction flask over the crystallization period and the resulting alcohol molecule coordinating to unreacted [TiCl2{(OAr)2}]. The small amount of crystalline material obtained supports this hypothesis. The fluorene molecule found in the unit cell apparently arises from the initial reaction of fluorene with n-butyl lithium not reaching completion.

The overall coordination geometry of the molecule is that of a distorted trigonal bipyramid with the oxygen atom of one side of the bidentate bis-phenolato ligand in one apical position and the oxygen atom of the fluoren-9-ol ligand in the other apical site. This positioning is similar to that of the two other 5-coordinate molecules characterized by X-ray crystallography (Okuda et al. 1995; Gielens et al.1999). The second oxygen atom of the bidentate bis-phenolato ligand occupies one of the equatorial sites with the remaining equatorial positions being taken up by chloro ligands. The largest distortion of the trigonal bipyramid essentially arises from the positioning of the tert-butyl group in the 2-position of the benzene ring of the phenolato ligand that lies in the apical position. This group lies over the top of Cl(1) which apparently causes the O(2)—Ti—Cl(1) bond angle to open out to 98.5 (1)°. In comparison Cl(2) is not in close proximity to the tert-butyl group and the O(2)—Ti—Cl(2) bond angle is smaller at 91.9 (1)°. The O(2)—Ti—O(1) bond angle which involves the bidentate bis-phenolato ligand is 95.6 (1)°. On the opposite side of the molecule where the fluorene-9-ol ligand resides the O(4)—Ti-ligand angles are all somewhat compressed with values ranging from 82.3 (1) to 87.1 (1)°. The angles associated with the equatorial sites of the trigonal bipyramid [range 117.46 (4) to 121.8 (1) °] show little, if any, compression effects. In this case the tert-butyl group in the 2-position of the phenolato ligand attached to the equatorial site, O(1) is well away from Cl(1), Cl(2) and O(4).

For the Ti—O bond distances associated with the bidentate bis-phenolato ligand, the Ti—O(2) bond length [1.776 (1) Å] which involves the oxygen in the apical position of the trigonal bipyramid is significantly shorter than the Ti—O(1) bond length [1.804 (1) Å] which involves the equatorial position. The shorter bond to O(2) is related to a greater degree of π-donation from oxygen lone pairs to the metal. Features associated with this aspect are that O(2) lies trans to the datively bonded O(4) atom which means there is minimal competition for π-orbitals on the metal. In addition the Ti—O(2)—C(13) bond angle [155.3 (1)°] approaches linearity which allows a maximum donation of the oxygen atom p orbitals. For the longer Ti—O(1) bond, the Ti—O(1)—C(1) bond angle is 140.5 (1)° which allows less donation of this type from the oxygen. The bidentate ligand is positioned with the carbon atom that forms the bridge between the two phenyl rings (C14) pointing towards the back of the molecule and it is this arrangement that places the tert-butyl group at the 2-postion of the apical phenolato ligand phenyl group over Cl(1).

The fluoren-9-ol ligand coordinates to the metal centre via a dative bond involving a lone pair of electrons from the alcohol oxygen O(4). Since the bond does not have a π-donor component the Ti—O(4) bond length [2.149 (2) Å] is much longer than the bis-phenolato ligand Ti—O bond lengths. The Ti—O(4)—C(25) bond angle is 130.8 (1)° which is larger than the normal bent angle and reflects the push-back effect oxygen lone pairs have on this type of molecule. With this angle there is no clash between the C(25) hydrogen and the nearby Cl(1) atom.

The alcohol hydrogen (H4) is hydrogen bonded to the oxygen atom of a non-coordinated diethyl ether molecule at a distance of 1.76 (3) Å in a linear arrangement [O(4)—H(4)···O(3) bond angle 180 (3)°]. The diethyl ether C(38)—O(3)—C(40) bond angle is 115.3 (2)°.

The crystal structure also shows that there is also a half-weighted fluorene molecule, C13H10 contained in the unit cell which is not coordinated to the metal. This lies across a centre of symmetry.

Related literature top

For monomeric 4-coordinate structures of titanium complexes containing the 2,2'-methylene-bis-(4-methyl-6-tert-butylphenolato) ligand, see: Toscano et al. (1998). For the two other structures with a five-coordinate metal atom containing this type of ligand, see: Okuda et al. (1995); Gielens et al. (1999).

Experimental top

Using normal bench-top techniques for air-sensitive compounds, n-butyl lithium (3.8 ml of a 1.6 mol/L solution, 6.02 mmol) was added dropwise to a solution of fluorene (1.00 g, 6.02 mmol) in diethyl ether (30 ml) cooled to 78°C and the mixture was warmed to room temperature and stirred for a further 2 h. The solution was added dropwise to a solution of [TiCl2{(OAr)2}] (2.83 g, 6.02 mmol) in diethyl ether (50 ml), chilled to 0°C and the mixture allowed to warm to room temperature and the stirring continued overnight. The solution was filtered, the volume reduced to ca 20 ml and the solution stood at -20° C for several months whereupon a small quantity of colourless crystals was formed. A crystal was chosen from the mass and the X-ray crystal structure obtained.

Refinement top

All H atoms, except H4, were included in calculated positions and refined using a riding model [U(H)eq = 1.2UCeq for aromatic CH and U(H) = 1.5U(C) for methyl H atoms]. C—H distances of 0.96 Å and 0.93 Å were assumed for aromatic and methyl groups respectively. For H4, the atom involved in the H-bonding, the positional parameters were refined but the thermal parameter was held constant at 0.08.

The non H-bonded solvent molecule was half-weighted since it lay across the centre of symmetry and its two six-membered rings were refined as rigid groups.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS90 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Diagram of title compound showing atom labeling and with atomic displacement parameters drawnn at the 50% probability level. Hydrogen atoms are omitted for clarity.
[6,6'-Bis(1,1-dimethylethyl)-4,4'-dimethyl-2,2'-methylenediphenolato-κ2O,O']dichlorido(9H-fluoren-9-ol-κO)titanium(IV)–fluorene–diethyl ether (1/0.5/1) top
Crystal data top
[TiCl2(C23H30O2)(C13H10O)]·C4H10O·0.5C13H10Z = 2
Mr = 796.71F(000) = 844
Triclinic, P1Dx = 1.248 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.710 (3) ÅCell parameters from 5551 reflections
b = 13.227 (3) Åθ = 2–25°
c = 14.431 (3) ŵ = 0.37 mm1
α = 110.28 (3)°T = 203 K
β = 109.22 (3)°Irregular fragment, red
γ = 91.72 (3)°0.28 × 0.22 × 0.08 mm
V = 2120.2 (7) Å3
Data collection top
Siemens SMART
diffractometer
7432 independent reflections
Radiation source: fine-focus sealed tube6033 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Area detector ω scansθmax = 25.1°, θmin = 1.6°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1514
Tmin = 0.904, Tmax = 0.971k = 1514
18146 measured reflectionsl = 017
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086 w = 1/[σ2(Fo2) + (0.0268P)2 + 1.2664P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
7432 reflectionsΔρmax = 0.35 e Å3
531 parametersΔρmin = 0.37 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.0008 (3)
Primary atom site location: structure-invariant direct methods
Crystal data top
[TiCl2(C23H30O2)(C13H10O)]·C4H10O·0.5C13H10γ = 91.72 (3)°
Mr = 796.71V = 2120.2 (7) Å3
Triclinic, P1Z = 2
a = 12.710 (3) ÅMo Kα radiation
b = 13.227 (3) ŵ = 0.37 mm1
c = 14.431 (3) ÅT = 203 K
α = 110.28 (3)°0.28 × 0.22 × 0.08 mm
β = 109.22 (3)°
Data collection top
Siemens SMART
diffractometer
7432 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
6033 reflections with I > 2σ(I)
Tmin = 0.904, Tmax = 0.971Rint = 0.025
18146 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086Δρmax = 0.35 e Å3
S = 1.07Δρmin = 0.37 e Å3
7432 reflectionsAbsolute structure: ?
531 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ti0.59181 (3)0.73459 (3)0.24921 (3)0.01990 (10)
Cl10.66189 (4)0.84629 (4)0.42383 (4)0.03050 (13)
Cl20.64541 (5)0.56538 (4)0.20349 (4)0.03257 (14)
O40.46553 (12)0.65866 (11)0.28390 (11)0.0232 (3)
O10.46954 (11)0.76509 (11)0.16236 (10)0.0218 (3)
O20.69091 (11)0.78731 (11)0.20806 (10)0.0215 (3)
O30.26771 (12)0.56947 (13)0.12867 (11)0.0341 (4)
C10.44084 (16)0.81060 (16)0.08647 (15)0.0210 (4)
C20.37136 (16)0.89285 (16)0.09469 (16)0.0230 (4)
C30.34059 (17)0.93113 (17)0.01229 (17)0.0275 (5)
H30.29420.98530.01540.033*
C40.37470 (17)0.89349 (18)0.07426 (16)0.0278 (5)
C50.44411 (17)0.81449 (17)0.07777 (16)0.0267 (5)
H50.46870.78880.13520.032*
C60.47851 (16)0.77200 (16)0.00151 (15)0.0221 (4)
C80.68002 (17)0.73915 (16)0.03058 (15)0.0219 (4)
C90.73235 (17)0.73767 (17)0.04085 (16)0.0250 (4)
H90.69060.70560.11400.030*
C100.84534 (18)0.78286 (17)0.00581 (16)0.0260 (5)
C110.90583 (17)0.83031 (17)0.10316 (16)0.0265 (5)
H110.98210.86100.12670.032*
C120.85864 (16)0.83449 (16)0.17901 (15)0.0220 (4)
C130.74406 (16)0.78770 (16)0.13949 (15)0.0205 (4)
C140.55725 (16)0.68790 (16)0.00806 (15)0.0235 (4)
H14A0.55030.64440.03310.028*
H14B0.53390.63830.08240.028*
C150.3383 (2)0.9391 (2)0.16034 (18)0.0376 (6)
H15A0.39960.99220.15010.056*
H15B0.27290.97410.15730.056*
H15C0.31910.88020.22890.056*
C160.33479 (18)0.94173 (17)0.19089 (17)0.0271 (5)
C170.4393 (2)1.00425 (19)0.29056 (18)0.0367 (5)
H17A0.41591.03730.35040.055*
H17B0.47731.06080.27900.055*
H17C0.49040.95400.30510.055*
C180.2532 (2)1.02337 (19)0.17562 (19)0.0363 (5)
H18A0.18740.98720.11170.054*
H18B0.29101.08420.16950.054*
H18C0.22961.05020.23610.054*
C190.2731 (2)0.85313 (19)0.2091 (2)0.0356 (5)
H19A0.25590.88590.27270.053*
H19B0.32080.79860.21720.053*
H19C0.20340.81880.14880.053*
C200.90321 (19)0.7785 (2)0.08351 (18)0.0347 (5)
H20A0.93700.85180.06890.052*
H20B0.84810.74790.15520.052*
H20C0.96150.73310.07610.052*
C210.92739 (16)0.88579 (17)0.29859 (15)0.0239 (4)
C221.04921 (18)0.9323 (2)0.32137 (18)0.0347 (5)
H22A1.08690.87360.29180.052*
H22B1.08910.96680.39740.052*
H22C1.04880.98580.28930.052*
C230.87372 (18)0.98044 (17)0.35278 (16)0.0277 (5)
H23A0.87651.03760.32550.042*
H23B0.91511.00950.42870.042*
H23C0.79570.95390.33830.042*
C240.93313 (18)0.79741 (18)0.34662 (17)0.0297 (5)
H24A0.85730.76780.33570.045*
H24B0.97720.82960.42200.045*
H24C0.96850.73930.31230.045*
C250.47153 (17)0.63855 (16)0.37816 (15)0.0237 (4)
H250.54810.66910.43250.080*
C260.38535 (17)0.69044 (17)0.42380 (15)0.0242 (4)
C270.37082 (18)0.79872 (18)0.45693 (16)0.0293 (5)
H270.41590.85160.45040.035*
C280.2877 (2)0.8277 (2)0.50039 (17)0.0362 (5)
H280.27630.90080.52330.043*
C290.2217 (2)0.7490 (2)0.50998 (18)0.0391 (6)
H290.16640.76960.53980.047*
C300.23619 (19)0.6406 (2)0.47630 (18)0.0357 (5)
H300.19080.58780.48270.043*
C310.31854 (18)0.61101 (17)0.43305 (16)0.0275 (5)
C320.35526 (18)0.50511 (17)0.39458 (16)0.0279 (5)
C330.3197 (2)0.40365 (18)0.39237 (17)0.0355 (5)
H330.25890.39340.41340.043*
C340.3756 (2)0.31783 (18)0.35860 (17)0.0390 (6)
H340.35220.24890.35690.047*
C350.4651 (2)0.33196 (18)0.32742 (17)0.0374 (6)
H350.50260.27300.30600.045*
C360.5004 (2)0.43296 (18)0.32745 (16)0.0313 (5)
H360.56050.44250.30540.038*
C370.44433 (17)0.51884 (16)0.36079 (15)0.0248 (4)
C380.2640 (2)0.53601 (19)0.02120 (17)0.0347 (5)
H38A0.23900.45690.01450.042*
H38B0.34040.55170.02240.042*
C390.1865 (2)0.5920 (2)0.04151 (18)0.0425 (6)
H39A0.11070.57700.04310.064*
H39B0.18600.56510.11330.064*
H39C0.21290.67020.00860.064*
C400.1719 (2)0.52214 (19)0.14099 (19)0.0368 (5)
H40A0.19800.48280.18860.044*
H40B0.12140.46950.07200.044*
C410.1082 (2)0.6081 (2)0.1853 (2)0.0448 (6)
H41A0.16000.66480.24940.067*
H41B0.05060.57540.20150.067*
H41C0.07280.63970.13350.067*
C511.0508 (6)0.5759 (4)0.6109 (5)0.049 (2)0.50
C521.0701 (6)0.6721 (5)0.6982 (4)0.068 (3)0.50
H521.12420.68050.76430.082*0.50
C531.0092 (8)0.7557 (5)0.6880 (5)0.059 (7)0.50
H531.02230.82070.74700.071*0.50
C540.9291 (6)0.7431 (4)0.5903 (5)0.051 (2)0.50
H540.88800.79970.58340.062*0.50
C550.9098 (5)0.6470 (5)0.5030 (4)0.0468 (16)0.50
H550.85560.63850.43700.056*0.50
C560.9706 (6)0.5634 (4)0.5133 (4)0.044 (2)0.50
C570.9651 (6)0.4566 (3)0.4346 (5)0.0395 (19)0.50
C580.8984 (5)0.4057 (5)0.3278 (5)0.0487 (15)0.50
H580.84490.44200.29470.058*0.50
C590.9108 (7)0.3012 (5)0.2699 (4)0.058 (2)0.50
H590.86570.26680.19770.070*0.50
C600.9899 (8)0.2476 (5)0.3188 (6)0.072 (9)0.50
H600.99820.17700.27970.086*0.50
C611.0565 (6)0.2986 (5)0.4256 (6)0.065 (3)0.50
H611.11000.26230.45860.078*0.50
C621.0441 (5)0.4030 (5)0.4835 (4)0.0428 (19)0.50
C631.1025 (5)0.4738 (5)0.5994 (5)0.0620 (17)0.50
H63A1.08800.43850.64450.074*0.50
H63B1.18430.48970.61770.074*0.50
H40.399 (3)0.629 (3)0.232 (3)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti0.01863 (19)0.0224 (2)0.01971 (19)0.00279 (14)0.00761 (15)0.00857 (15)
Cl10.0317 (3)0.0332 (3)0.0217 (3)0.0040 (2)0.0094 (2)0.0055 (2)
Cl20.0367 (3)0.0276 (3)0.0404 (3)0.0119 (2)0.0207 (3)0.0142 (2)
O40.0222 (7)0.0301 (8)0.0208 (7)0.0024 (6)0.0077 (6)0.0137 (6)
O10.0198 (7)0.0254 (7)0.0237 (7)0.0056 (6)0.0090 (6)0.0123 (6)
O20.0202 (7)0.0250 (7)0.0196 (7)0.0020 (6)0.0082 (6)0.0079 (6)
O30.0273 (8)0.0429 (9)0.0268 (8)0.0019 (7)0.0076 (7)0.0096 (7)
C10.0167 (10)0.0234 (11)0.0213 (10)0.0009 (8)0.0032 (8)0.0105 (9)
C20.0189 (10)0.0220 (10)0.0278 (11)0.0016 (8)0.0075 (9)0.0102 (9)
C30.0228 (11)0.0257 (11)0.0347 (12)0.0050 (9)0.0066 (9)0.0159 (10)
C40.0228 (11)0.0332 (12)0.0285 (11)0.0016 (9)0.0053 (9)0.0168 (10)
C50.0241 (11)0.0334 (12)0.0215 (10)0.0023 (9)0.0068 (9)0.0104 (9)
C60.0172 (10)0.0233 (11)0.0225 (10)0.0005 (8)0.0041 (8)0.0079 (9)
C80.0229 (11)0.0218 (10)0.0229 (10)0.0074 (8)0.0094 (9)0.0095 (9)
C90.0274 (11)0.0278 (11)0.0203 (10)0.0086 (9)0.0096 (9)0.0083 (9)
C100.0303 (12)0.0292 (11)0.0261 (11)0.0116 (9)0.0158 (9)0.0135 (9)
C110.0208 (11)0.0310 (12)0.0318 (12)0.0060 (9)0.0120 (9)0.0143 (10)
C120.0206 (10)0.0226 (10)0.0245 (10)0.0054 (8)0.0098 (8)0.0094 (9)
C130.0227 (10)0.0216 (10)0.0224 (10)0.0080 (8)0.0119 (8)0.0104 (9)
C140.0219 (11)0.0258 (11)0.0188 (10)0.0025 (9)0.0056 (8)0.0056 (9)
C150.0375 (14)0.0453 (14)0.0352 (13)0.0098 (11)0.0094 (11)0.0246 (12)
C160.0263 (11)0.0241 (11)0.0321 (12)0.0072 (9)0.0123 (9)0.0102 (9)
C170.0372 (13)0.0336 (13)0.0334 (13)0.0069 (11)0.0117 (11)0.0067 (11)
C180.0384 (14)0.0314 (13)0.0435 (14)0.0137 (11)0.0202 (11)0.0134 (11)
C190.0369 (13)0.0354 (13)0.0495 (14)0.0129 (11)0.0292 (12)0.0203 (12)
C200.0336 (13)0.0469 (14)0.0334 (12)0.0111 (11)0.0195 (11)0.0193 (11)
C210.0180 (10)0.0303 (11)0.0218 (10)0.0023 (9)0.0067 (8)0.0087 (9)
C220.0225 (11)0.0491 (15)0.0306 (12)0.0006 (10)0.0085 (10)0.0142 (11)
C230.0264 (11)0.0273 (11)0.0246 (11)0.0004 (9)0.0068 (9)0.0067 (9)
C240.0251 (11)0.0347 (12)0.0279 (11)0.0064 (10)0.0064 (9)0.0130 (10)
C250.0280 (11)0.0259 (11)0.0203 (10)0.0041 (9)0.0093 (9)0.0119 (9)
C260.0248 (11)0.0285 (11)0.0181 (10)0.0035 (9)0.0056 (8)0.0093 (9)
C270.0319 (12)0.0303 (12)0.0245 (11)0.0035 (10)0.0090 (9)0.0102 (10)
C280.0406 (14)0.0370 (13)0.0312 (12)0.0139 (11)0.0149 (11)0.0107 (11)
C290.0345 (13)0.0548 (16)0.0339 (13)0.0140 (12)0.0191 (11)0.0167 (12)
C300.0307 (13)0.0473 (15)0.0375 (13)0.0046 (11)0.0176 (11)0.0210 (12)
C310.0280 (12)0.0315 (12)0.0237 (11)0.0000 (9)0.0084 (9)0.0126 (9)
C320.0324 (12)0.0294 (12)0.0202 (10)0.0014 (9)0.0058 (9)0.0114 (9)
C330.0427 (14)0.0345 (13)0.0270 (11)0.0063 (11)0.0091 (10)0.0134 (10)
C340.0635 (17)0.0238 (12)0.0237 (11)0.0035 (11)0.0078 (11)0.0104 (10)
C350.0616 (17)0.0271 (12)0.0228 (11)0.0115 (11)0.0131 (11)0.0103 (10)
C360.0404 (13)0.0311 (12)0.0231 (11)0.0084 (10)0.0115 (10)0.0107 (10)
C370.0292 (11)0.0254 (11)0.0185 (10)0.0015 (9)0.0046 (9)0.0107 (9)
C380.0379 (13)0.0340 (13)0.0287 (12)0.0079 (10)0.0120 (10)0.0075 (10)
C390.0464 (15)0.0434 (15)0.0320 (13)0.0093 (12)0.0081 (11)0.0133 (11)
C400.0349 (13)0.0348 (13)0.0365 (13)0.0035 (10)0.0115 (11)0.0108 (11)
C410.0367 (14)0.0425 (15)0.0484 (15)0.0002 (12)0.0163 (12)0.0088 (12)
C510.042 (4)0.062 (5)0.049 (6)0.004 (4)0.008 (4)0.039 (5)
C520.080 (6)0.076 (7)0.038 (4)0.023 (6)0.003 (4)0.029 (4)
C530.065 (12)0.065 (14)0.060 (10)0.009 (10)0.027 (9)0.034 (9)
C540.058 (5)0.052 (5)0.062 (5)0.003 (4)0.028 (4)0.037 (4)
C550.045 (4)0.053 (4)0.054 (4)0.003 (3)0.023 (3)0.029 (3)
C560.033 (4)0.059 (5)0.057 (5)0.002 (3)0.020 (4)0.037 (4)
C570.032 (4)0.051 (4)0.046 (5)0.000 (3)0.017 (4)0.029 (4)
C580.050 (4)0.057 (4)0.052 (4)0.010 (3)0.022 (3)0.032 (4)
C590.073 (6)0.050 (4)0.056 (4)0.001 (4)0.029 (4)0.022 (4)
C600.11 (2)0.045 (12)0.088 (14)0.015 (12)0.069 (15)0.031 (10)
C610.058 (5)0.067 (7)0.121 (10)0.031 (5)0.057 (6)0.070 (7)
C620.035 (4)0.053 (4)0.060 (5)0.007 (4)0.018 (3)0.044 (4)
C630.047 (3)0.079 (4)0.076 (4)0.006 (3)0.013 (3)0.058 (4)
Geometric parameters (Å, º) top
Ti—O21.7755 (13)C24—H24B0.9700
Ti—O11.8040 (14)C24—H24C0.9700
Ti—O42.1485 (15)C25—C261.520 (3)
Ti—Cl12.2778 (12)C25—C371.525 (3)
Ti—Cl22.2963 (9)C25—H250.9900
O4—C251.453 (2)C26—C271.383 (3)
O4—H40.89 (3)C26—C311.400 (3)
O1—C11.379 (2)C27—C281.397 (3)
O2—C131.371 (2)C27—H270.9400
O3—C381.442 (3)C28—C291.389 (3)
O3—C401.442 (3)C28—H280.9400
C1—C61.400 (3)C29—C301.384 (3)
C1—C21.419 (3)C29—H290.9400
C2—C31.395 (3)C30—C311.387 (3)
C2—C161.543 (3)C30—H300.9400
C3—C41.391 (3)C31—C321.469 (3)
C3—H30.9400C32—C331.389 (3)
C4—C51.386 (3)C32—C371.402 (3)
C4—C151.509 (3)C33—C341.387 (3)
C5—C61.395 (3)C33—H330.9400
C5—H50.9400C34—C351.384 (3)
C6—C141.520 (3)C34—H340.9400
C8—C91.394 (3)C35—C361.396 (3)
C8—C131.404 (3)C35—H350.9400
C8—C141.519 (3)C36—C371.387 (3)
C9—C101.391 (3)C36—H360.9400
C9—H90.9400C38—C391.504 (3)
C10—C111.396 (3)C38—H38A0.9800
C10—C201.517 (3)C38—H38B0.9800
C11—C121.398 (3)C39—H39A0.9700
C11—H110.9400C39—H39B0.9700
C12—C131.408 (3)C39—H39C0.9700
C12—C211.537 (3)C40—C411.499 (3)
C14—H14A0.9800C40—H40A0.9800
C14—H14B0.9800C40—H40B0.9800
C15—H15A0.9700C41—H41A0.9700
C15—H15B0.9700C41—H41B0.9700
C15—H15C0.9700C41—H41C0.9700
C16—C191.533 (3)C51—C521.3900
C16—C171.539 (3)C51—C561.3900
C16—C181.540 (3)C51—C631.502 (8)
C17—H17A0.9700C52—C531.3900
C17—H17B0.9700C52—H520.9400
C17—H17C0.9700C53—C541.3900
C18—H18A0.9700C53—H530.9400
C18—H18B0.9700C54—C551.3900
C18—H18C0.9700C54—H540.9400
C19—H19A0.9700C55—C561.3900
C19—H19B0.9700C55—H550.9400
C19—H19C0.9700C56—C571.455 (5)
C20—H20A0.9700C57—C581.3900
C20—H20B0.9700C57—C621.3900
C20—H20C0.9700C58—C591.3900
C21—C221.533 (3)C58—H580.9400
C21—C231.539 (3)C59—C601.3900
C21—C241.545 (3)C59—H590.9400
C22—H22A0.9700C60—C611.3900
C22—H22B0.9700C60—H600.9400
C22—H22C0.9700C61—C621.3900
C23—H23A0.9700C61—H610.9400
C23—H23B0.9700C62—C631.511 (8)
C23—H23C0.9700C63—H63A0.9800
C24—H24A0.9700C63—H63B0.9800
O2—Ti—O195.60 (6)C21—C23—H23C109.5
O2—Ti—O4174.46 (6)H23A—C23—H23C109.5
O1—Ti—O482.26 (6)H23B—C23—H23C109.5
O2—Ti—Cl198.45 (6)C21—C24—H24A109.5
O1—Ti—Cl1118.21 (6)C21—C24—H24B109.5
O4—Ti—Cl187.05 (5)H24A—C24—H24B109.5
O2—Ti—Cl291.89 (5)C21—C24—H24C109.5
O1—Ti—Cl2121.81 (6)H24A—C24—H24C109.5
O4—Ti—Cl284.95 (5)H24B—C24—H24C109.5
Cl1—Ti—Cl2117.46 (4)O4—C25—C26112.09 (16)
C25—O4—Ti130.83 (12)O4—C25—C37115.09 (16)
C25—O4—H4111 (2)C26—C25—C37102.78 (16)
Ti—O4—H4118 (2)O4—C25—H25108.9
C1—O1—Ti140.46 (12)C26—C25—H25108.9
C13—O2—Ti155.26 (13)C37—C25—H25108.9
C38—O3—C40115.25 (17)C27—C26—C31121.2 (2)
O1—C1—C6118.93 (17)C27—C26—C25128.98 (19)
O1—C1—C2119.33 (17)C31—C26—C25109.77 (18)
C6—C1—C2121.71 (17)C26—C27—C28118.5 (2)
C3—C2—C1116.33 (18)C26—C27—H27120.8
C3—C2—C16120.95 (18)C28—C27—H27120.8
C1—C2—C16122.67 (17)C29—C28—C27120.3 (2)
C4—C3—C2123.62 (19)C29—C28—H28119.8
C4—C3—H3118.2C27—C28—H28119.8
C2—C3—H3118.2C30—C29—C28121.0 (2)
C5—C4—C3117.88 (19)C30—C29—H29119.5
C5—C4—C15121.5 (2)C28—C29—H29119.5
C3—C4—C15120.6 (2)C29—C30—C31119.1 (2)
C4—C5—C6121.94 (19)C29—C30—H30120.5
C4—C5—H5119.0C31—C30—H30120.5
C6—C5—H5119.0C30—C31—C26119.9 (2)
C5—C6—C1118.50 (18)C30—C31—C32131.2 (2)
C5—C6—C14117.93 (18)C26—C31—C32108.92 (18)
C1—C6—C14123.56 (17)C33—C32—C37120.1 (2)
C9—C8—C13118.40 (18)C33—C32—C31130.8 (2)
C9—C8—C14121.00 (18)C37—C32—C31108.98 (18)
C13—C8—C14120.59 (17)C34—C33—C32118.8 (2)
C10—C9—C8121.20 (19)C34—C33—H33120.6
C10—C9—H9119.4C32—C33—H33120.6
C8—C9—H9119.4C35—C34—C33121.1 (2)
C9—C10—C11118.48 (19)C35—C34—H34119.4
C9—C10—C20121.22 (19)C33—C34—H34119.4
C11—C10—C20120.28 (19)C34—C35—C36120.7 (2)
C10—C11—C12123.26 (19)C34—C35—H35119.7
C10—C11—H11118.4C36—C35—H35119.7
C12—C11—H11118.4C37—C36—C35118.3 (2)
C11—C12—C13116.04 (18)C37—C36—H36120.8
C11—C12—C21122.33 (18)C35—C36—H36120.8
C13—C12—C21121.63 (17)C36—C37—C32121.00 (19)
O2—C13—C8117.27 (17)C36—C37—C25129.19 (19)
O2—C13—C12120.12 (17)C32—C37—C25109.54 (18)
C8—C13—C12122.61 (18)O3—C38—C39113.16 (19)
C8—C14—C6112.87 (16)O3—C38—H38A108.9
C8—C14—H14A109.0C39—C38—H38A108.9
C6—C14—H14A109.0O3—C38—H38B108.9
C8—C14—H14B109.0C39—C38—H38B108.9
C6—C14—H14B109.0H38A—C38—H38B107.8
H14A—C14—H14B107.8C38—C39—H39A109.5
C4—C15—H15A109.5C38—C39—H39B109.5
C4—C15—H15B109.5H39A—C39—H39B109.5
H15A—C15—H15B109.5C38—C39—H39C109.5
C4—C15—H15C109.5H39A—C39—H39C109.5
H15A—C15—H15C109.5H39B—C39—H39C109.5
H15B—C15—H15C109.5O3—C40—C41111.31 (19)
C19—C16—C17109.86 (18)O3—C40—H40A109.4
C19—C16—C18106.62 (17)C41—C40—H40A109.4
C17—C16—C18107.34 (18)O3—C40—H40B109.4
C19—C16—C2111.66 (17)C41—C40—H40B109.4
C17—C16—C2109.51 (17)H40A—C40—H40B108.0
C18—C16—C2111.72 (17)C40—C41—H41A109.5
C16—C17—H17A109.5C40—C41—H41B109.5
C16—C17—H17B109.5H41A—C41—H41B109.5
H17A—C17—H17B109.5C40—C41—H41C109.5
C16—C17—H17C109.5H41A—C41—H41C109.5
H17A—C17—H17C109.5H41B—C41—H41C109.5
H17B—C17—H17C109.5C52—C51—C56120.0
C16—C18—H18A109.5C52—C51—C63131.3 (5)
C16—C18—H18B109.5C56—C51—C63108.7 (5)
H18A—C18—H18B109.5C51—C52—C53120.0
C16—C18—H18C109.5C51—C52—H52120.0
H18A—C18—H18C109.5C53—C52—H52120.0
H18B—C18—H18C109.5C54—C53—C52120.0
C16—C19—H19A109.5C54—C53—H53120.0
C16—C19—H19B109.5C52—C53—H53120.0
H19A—C19—H19B109.5C53—C54—C55120.0
C16—C19—H19C109.5C53—C54—H54120.0
H19A—C19—H19C109.5C55—C54—H54120.0
H19B—C19—H19C109.5C54—C55—C56120.0
C10—C20—H20A109.5C54—C55—H55120.0
C10—C20—H20B109.5C56—C55—H55120.0
H20A—C20—H20B109.5C55—C56—C51120.0
C10—C20—H20C109.5C55—C56—C57129.9 (7)
H20A—C20—H20C109.5C51—C56—C57110.1 (7)
H20B—C20—H20C109.5C58—C57—C62120.0
C22—C21—C12111.68 (17)C58—C57—C56131.9 (7)
C22—C21—C23107.49 (18)C62—C57—C56108.1 (7)
C12—C21—C23110.13 (16)C59—C58—C57120.0
C22—C21—C24107.20 (17)C59—C58—H58120.0
C12—C21—C24109.47 (17)C57—C58—H58120.0
C23—C21—C24110.82 (16)C58—C59—C60120.0
C21—C22—H22A109.5C58—C59—H59120.0
C21—C22—H22B109.5C60—C59—H59120.0
H22A—C22—H22B109.5C57—C62—C63109.7 (5)
C21—C22—H22C109.5C51—C63—C62103.4 (4)
H22A—C22—H22C109.5C51—C63—H63A111.1
H22B—C22—H22C109.5C62—C63—H63A111.1
C21—C23—H23A109.5C51—C63—H63B111.1
C21—C23—H23B109.5C62—C63—H63B111.1
H23A—C23—H23B109.5H63A—C63—H63B109.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O30.89 (3)1.76 (3)2.648 (2)180 (3)
Selected bond lengths (Å) top
Ti—O21.7755 (13)Ti—Cl12.2778 (12)
Ti—O11.8040 (14)Ti—Cl22.2963 (9)
Ti—O42.1485 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O30.89 (3)1.76 (3)2.648 (2)180 (3)
Acknowledgements top

This work was supported by the award of a Massey University Research Fund Post-Doctoral Fellowship to CS. We are grateful to Ms T. Groutso of the University of Auckland for the data collection.

references
References top

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Gielens, E. E. C. G., Dijkstra, T. W., Berno, P., Meetsma, A., Hessen, B. & Teuben, J. H. (1999). J. Organomet. Chem. 591, 88–95.

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Toscano, P. J., James Schermerhorn, E. J., Barren, E., Liu, S. & Zubieta, J. (1998). J. Coord. Chem. 43, 169–185.