supplementary materials


gg2122 scheme

Acta Cryst. (2013). E69, m554-m555    [ doi:10.1107/S1600536813025634 ]

Di-[mu]-methanolato-bis[(2-tert-butyl-6-methylphenolato-[kappa]O)methyltitanium(IV)]

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

Abstract top

The molecule of the title compound, [Ti2(CH3)2(CH3O)2(C11H15O)4] or {[Ti(Me)([mu]-OCH3)(OC6H3CMe3-2-Me-6)]2}, has a centrosymmetric, dimeric structure with a distorted square pyramidal array about each titanium atom. The methoxide ligands form an asymmetric bridge between the two TiIV atoms [Ti-O bond lengths of 1.9794 (12) and 2.0603 (12) Å] with the two phenolato ligands occupying the remaining basal sites [Ti-O 1.8218 (11) and 1.8135 (11) Å]. The Ti-O-C phenolato bond angles are similar at 161.24 (10) and 160.66 (11)°. The methyl ligand attached to the metal atom has a Ti-C bond length of 2.0878 (17) Å.

Comment top

Titanium complexes containing phenolato ligands (OAr) or alkoxo ligands (OR) as well as an alkyl ligand have been described (Janas et al. 2005; Janas et al. 2004; Zhang 2007a,b; Kobylka et al. 2007) but complexes containing both oxygen ligand sets and an alkyl ligand are not known. The chemistry of phenolato and alkylato complexes has been known for many years (Bradley et al. 1978) and in particular alkoxy bridged bis-phenolato dititanium complexes have been prepared (Ejfler et al. 2004). Several examples of X-ray crystal structures for titanium complexes containing terminal and bridging phenolato ligands have been reported (Gowda et al. 2009; Nielson et al. 2006; Svetich & Voge, 1972). During attempts to form bis-dimethyl bis-phenolato complexes of titanium for testing as olefin oligomerization and polymerization catalysts, in one case we reacted [TiCl2(OC6H3CMe3-2-Me-6)2] (Nielson et al. 2005; Santora et al. 1999) with two equivalents of methylmagnesium iodide and recrystallized the resulting product from petroleum spirit at low temperatures for a period of several months. A nice crystalline red coloured product was formed which was expected to be the bis-dimethyl complex [Ti(Me)2(OC6H3CMe3-2-Me-6)2]. However the X-ray crystal structural analysis showed it was the dimeric methoxy bridged complex [{Ti(Me)(µ-OMe)(OC6H3CMe3-2-Me-6)2}2] (1). Alkyl complexes of transition metal complexes are usually air sensitive and it was expected that the methoxo ligand had resulted from moist air entering the crystallization flask adventiciously and either water or oxygen inserting into a Ti–CH3 bond. A reaction where oxygen inserts into a Ti–CH3 bond has been reported (Zhang et al., 2007a).

The structure of (1) is centrosymmetric and consists of an asymmetric, methoxy bridged dimer in which each Ti centre has two terminal phenolato ligands and a methyl ligand attached (Fig. 1). Each titanium atom has a distorted square pyramidal geometry in which the base of the square pyramid is made up by the oxygen atoms of the two cis-related terminal phenolato ligands and the oxygen atoms of the methoxy bridging system. A similar distorted square pyramidal structure is found in [{(tbop)Ti(Me)}2(µ-OMe)2] (tbop = 2,2-thiobis{4-(1,1,3,3- tetramethylbutyl)phenol} (Janas et al. 2005). The distortion in (1) is such that the O atom of one phenolato ligand and the trans-related oxygen of the methoxy bridge has a nearly linear disposition with the O(1)–Ti–O3i bond angle at 162.64 (5)°. The other phenolato ligand oxygen and its trans-related methoxy ligand oxygen form a much more bent system where the O(2)–Ti–O(3) bond angle is 138.00 (5)°.

The two Ti atoms and the methoxide ligand oxygen atoms of the oxygen bridges (O3, O3i) are coplanar with O1 and O1i lying on either side of the plane with displacements of 0.0234 (2) Å. The remaining oxygen of the square pyramidal base is displaced by -1.134 (2) Å.

The methyl group (C24) of the complex occupies the apical site of the square plane as similarly found in [{(tbop)Ti(Me}2(µ-OMe)2] (Janas et al. 2005). The distortion away from the square plane is also shown by the various C24–Ti– bond angles. The C24–Ti–O(3i) bond angle which involves the oxygen of the methoxy bridge is 90.33 (6)° whereas for the trans-related oxygen, O(1), which involves the phenolato ligand, the angle is 97.38 (7)° indicating that this oxygen pushes slightly closer to the methyl group than does the bridging oxygen. For the other bridging methoxy ligand the C(24)–Ti–O(3) bond angle is 112.91 (6) ° and the C(24)–Ti–O(2) bond angle involving the phenolato ligand oxygen is 104.51 (7) ° indicating that this oxygen pushes slightly closer to the methyl group than the bridging oxygen. The angles associated with the C(24)–Ti–O system thus show that for the methoxy bridge the C(24)–Ti–O(3) bond angle [112.91 (6) °] opens out considerably more than does the C(24)–Ti–O(3i) bond angle [90.33 (6) °]. The C(24)–Ti–O angles associated with the phenolato ligand are also very different with the C(24)–Ti–O(2) bond angle [104.51 (7) °] opened out more than the C(24)–Ti–O(1) bond angle [97.38 (7) °].

The methoxy bridging system has a Ti–O–Tii bond angle of 109.03 (5) °, an O(3)–Ti–O(3i) bond angle of 70.97 (5) ° with Ti–O(3)–C(23) and Ti–O(3)–C(23i) bond angles of 129.10 (10) and 121.77 (10) ° respectively which are similar to those found in other alkoxy bridged titanium dimers (Janas et al. 2005, 2004) The separation between the phenolato ligands is shown by the O(1)–Ti–O(2) angle of 102.02 (5) ° which is much wider than the O(3)–Ti–O(3i) angle associated with the methoxy bridge [70.97 (5) °] which means that the bridging system is compressed in comparison to the terminal phenolato ligands. This no doubt occurs since there is significant repulsion between the aromatic rings. However the two terminal phenolato ligand O atoms push away from the cis-related methoxo bridge O atoms to nearly equal extents [O(1)–Tii–O(3) and O(2)–Tii–O(3i) bond angles 91.68 (5) and 90.97 (5) ° respectively].

The aromatic rings of the cis-related phenolato ligands are rotated away from each other with the Ti–O(1)–C(1) and Ti–O(2)–C(12) bond angles being nearly equal [161.24 (10) and 160.66 (11)°]. In comparison, the related bridging tris-phenolato complex [{TiCl(OC6H3Me2-2,4)2(µ-OC6H3Me2-2,4)}2] has one terminal phenolato ligand Ti–O–C bond angle nearly linear [171.4 (1)°] and the other much more bent [Ti–O–C bond angle 138.8 (1)°] (Nielson et al. 2006). Although these angles are essentially the same in (1), one phenyl ring is rotated so that its face points inwards towards the other but slightly down and the other ring is rotated so that it points away from and slightly down from the former. The rotation is such that the tert-butyl substituents in the 2-position of the phenyl ring lie adjacent to each other, as do the two methyl substituents on the phenyl ring 6-position. For the two adjacent tert-butyl substituents the methyl carbons are related by a geared disposition which apparently allows a further gearing across the two substituents of the attached hydrogen atoms. Two methyl groups of both tert-butyl substituents also have a geared disposition with the adjacent carbon atom [C(24)] of the Ti methyl group.

The methoxy bridging system is asymmetric with the Ti–O(3) bond length [1.9794 (12) Å] significantly shorter than the Ti–O(3i) bond length [2.0603 (12) Å]. For the Ti–O bond lengths associated with the phenolato ligands the Ti–O1 and Ti–O2 bond lengths [1.8218 (11) and 1.8135 (11) Å respectively] differ only slightly from one another but are significantly shorter than the methoxy bridge system Ti–O bond lengths. These shorter bond lengths indicate that the phenolato ligands are the better π-donors to the metal and this is supported by the nearly linear Ti–O–C bond angles associated with them. In comparison the related bridging tris-phenolato complex [{TiCl(OC6H3Me2-2,4)2(µ-OC6H3Me2-2,4)}2] has one short Ti–O phenolato ligand bond length [1.757 (1) Å] which is related to the near linear Ti–O–C bond angle [171.4 (1)°] and thus is the stronger π-donor and one longer Ti–O phenolato ligand bond length [1.794 (2) Å] related to the more bent Ti–O–C bond angle [138.8 (1)°] and the poorer π-donor (Nielson et al.. 2006). The Ti–O–C bond angles associated with the asymmetric methoxy bridging system are much reduced in comparison [129.10 (10) and 121.77 (10)°] indicating the reduced π-donor ability in this coordination mode. Terminal alkoxo ligands have much shorter bond lengths and larger Ti–O–C bond angles and are usually stronger π-donor ligands than phenolato ligands which have the ability for competitive π-back-donation to the aromatic ring. However in all cases involving phenolato and alkoxo ligands there is a subtle interplay of the π-donor properties depending on coordination mode and geometry. The Ti–C bond length for the Ti—CH3 ligand [2.0878 (17) Å] is similar to the Ti–C bond length [2.078 (4) Å] found in [{(tbop)Ti(Me)}2(µ-OMe)2] (Janas et al. 2005).

Related literature top

For other methoxy-bridged dialkyl or diphenyl bis-phenolate dititanium complexes, see: Janas et al. (2004, 2005); Zhang (2007a,b); Kobylka et al. (2007). For other alkoxy-bridged bis-phenolato dititanium complexes, see: Ejfler et al. (2004). For insertion of oxygen into a terminal Ti—Me bond to give a µ-methoxy ligand, see: Zhang (2007a). For general phenolato and alkylato complexes, see; Bradley et al. (1978). For bis-phenolato complexes of titanium containing 2-(1,1-dimethylethyl) and 6-methyl subsituents, see: Nielson et al. (2005); Santora et al. (1999). For some crystal structures of titanium complexes containing terminal and bridging phenolato ligands, see: Gowda et al. (2009); Nielson et al. (2006); Svetich & Voge (1972).

Experimental top

Methyl magnesium iodide (11.8 ml of a 1.076 mol/l solution, 12.7 mmole) in diethyl ether was added dropwise to a stirred suspension of [TiCl2(OC6H3CMe3-2-Me-6)2] (2.41 g, 5.79 mmole) in petroleum spirit (boiling point 40–60°) cooled in a dry-ice bath. The dry-ice bath was removed and the mixture stirred overnight. The solution was filtered, solvent removed and the residue extracted with hot petroleum spirit to give an orange-red solution. Reduction of the solvent volume and standing at -20° C gave a small quantity of the product as orange-red crystals. Found: C, 68.24; H, 9.10. C48H72O6Ti2 requires C, 68.56; H, 8.63. A crystal was chosen and the X-ray single crystal structure obtained.

Refinement top

All H atoms 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.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS93 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP diagram of molecule, at the 50% probability level, showing the numbering system.
Di-µ-methanolato-bis[(2-tert-butyl-6-methylphenolato-κO)methyltitanium(IV)] top
Crystal data top
[Ti2(CH3)2(CH3O)2(C11H15O)4]F(000) = 904
Mr = 840.80V = 2386.4(8)
Monoclinic, P21/cDx = 1.170 Mg m3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 15.127 (3) ÅCell parameters from 10380 reflections
b = 11.067 (2) Åθ = 2–26°
c = 15.821 (3) ŵ = 0.38 mm1
β = 115.71 (3)°T = 150 K
V = 2386.4 (8) Å3Needle, yellow
Z = 20.48 × 0.20 × 0.18 mm
Data collection top
Siemens SMART
diffractometer
4844 independent reflections
Radiation source: fine-focus sealed tube4113 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Area detector ω scansθmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan
(Blessing, 1995)
h = 918
Tmin = 0.834, Tmax = 0.953k = 1313
13277 measured reflectionsl = 1918
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)] = 0.034H-atom parameters constrained
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.0371P)2 + 1.0664P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
4844 reflectionsΔρmax = 0.30 e Å3
263 parametersΔρmin = 0.30 e Å3
0 restraintsAbsolute structure: structure is centrosymmetric
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ti2(CH3)2(CH3O)2(C11H15O)4]V = 2386.4 (8) Å3
Mr = 840.80Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.127 (3) ŵ = 0.38 mm1
b = 11.067 (2) ÅT = 150 K
c = 15.821 (3) Å0.48 × 0.20 × 0.18 mm
β = 115.71 (3)°
Data collection top
Siemens SMART
diffractometer
4844 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
4113 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.953Rint = 0.022
13277 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.089Δρmax = 0.30 e Å3
S = 1.04Δρmin = 0.30 e Å3
4844 reflectionsAbsolute structure: structure is centrosymmetric
263 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*/Ueq
Ti0.113050 (19)0.99514 (2)1.010663 (18)0.02326 (9)
O10.20285 (8)0.87453 (10)1.06042 (7)0.0265 (2)
O20.13233 (8)1.04040 (10)0.90976 (7)0.0273 (2)
O30.01427 (8)0.90487 (9)1.03621 (8)0.0275 (2)
C10.25027 (11)0.76640 (14)1.07086 (11)0.0266 (3)
C20.21767 (12)0.69000 (15)0.99229 (12)0.0306 (3)
C30.26384 (14)0.57900 (16)0.99989 (14)0.0404 (4)
H30.24190.52700.94870.048*
C40.34152 (16)0.54566 (18)1.08239 (15)0.0488 (5)
H40.37300.47221.08650.059*
C50.37277 (14)0.62199 (18)1.15939 (14)0.0437 (5)
H50.42520.59791.21480.052*
C60.32879 (12)0.73322 (15)1.15704 (12)0.0312 (4)
C70.13366 (13)0.72806 (16)0.90185 (12)0.0356 (4)
H7A0.12040.66570.85570.053*
H7B0.15060.80140.87990.053*
H7C0.07640.74140.91220.053*
C80.36418 (12)0.81365 (17)1.24508 (12)0.0364 (4)
C90.27979 (14)0.8334 (2)1.27289 (13)0.0468 (5)
H9A0.22700.87491.22320.070*
H9B0.30270.88101.32910.070*
H9C0.25690.75661.28370.070*
C100.44889 (16)0.7549 (2)1.32983 (14)0.0556 (6)
H10A0.42810.67781.34250.083*
H10B0.46710.80611.38370.083*
H10C0.50420.74401.31600.083*
C110.40205 (13)0.93433 (18)1.22650 (13)0.0414 (4)
H11A0.45910.92041.21590.062*
H11B0.41890.98641.27980.062*
H11C0.35190.97191.17210.062*
C120.13202 (12)1.03778 (14)0.82316 (11)0.0272 (3)
C130.04673 (13)0.99423 (14)0.74772 (11)0.0307 (3)
C140.04534 (15)0.99010 (16)0.65910 (12)0.0381 (4)
H140.01080.96330.60810.046*
C150.12567 (16)1.02501 (17)0.64586 (13)0.0437 (5)
H150.12431.01970.58660.052*
C160.20860 (15)1.06815 (17)0.72079 (13)0.0399 (4)
H160.26201.09220.71040.048*
C170.21512 (12)1.07692 (15)0.81156 (12)0.0312 (4)
C180.04102 (13)0.95336 (18)0.76132 (13)0.0381 (4)
H18A0.02240.88800.80560.057*
H18B0.09150.92660.70240.057*
H18C0.06521.01940.78460.057*
C190.30757 (13)1.12730 (16)0.89323 (13)0.0365 (4)
C200.28073 (14)1.24147 (17)0.93236 (14)0.0442 (5)
H20A0.25691.30240.88440.066*
H20B0.33781.27100.98490.066*
H20C0.23071.22230.95220.066*
C210.38714 (16)1.1638 (2)0.86143 (17)0.0560 (6)
H21A0.40561.09450.83630.084*
H21B0.44361.19440.91420.084*
H21C0.36171.22530.81410.084*
C220.35367 (14)1.03064 (18)0.97023 (14)0.0423 (4)
H22A0.30731.00780.99380.063*
H22B0.41151.06291.02050.063*
H22C0.37090.96100.94440.063*
C230.02098 (13)0.78584 (15)1.07531 (13)0.0343 (4)
H23A0.01710.73031.02640.051*
H23B0.00380.78751.12180.051*
H23C0.08830.76031.10380.051*
C240.18633 (13)1.12601 (16)1.11211 (12)0.0358 (4)
H24A0.24861.14331.11230.054*
H24B0.19651.09651.17270.054*
H24C0.14761.19841.09800.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti0.02042 (14)0.02367 (15)0.02448 (14)0.00311 (11)0.00862 (11)0.00058 (11)
O10.0221 (5)0.0268 (5)0.0287 (6)0.0042 (4)0.0091 (4)0.0002 (4)
O20.0261 (6)0.0295 (6)0.0265 (5)0.0006 (5)0.0117 (5)0.0002 (4)
O30.0250 (6)0.0233 (5)0.0343 (6)0.0042 (4)0.0130 (5)0.0042 (5)
C10.0221 (7)0.0264 (8)0.0340 (8)0.0035 (6)0.0146 (7)0.0029 (6)
C20.0318 (8)0.0275 (8)0.0361 (9)0.0025 (7)0.0181 (7)0.0019 (7)
C30.0483 (11)0.0311 (9)0.0466 (10)0.0047 (8)0.0250 (9)0.0019 (8)
C40.0524 (12)0.0351 (10)0.0623 (13)0.0200 (9)0.0279 (11)0.0086 (9)
C50.0361 (10)0.0461 (11)0.0458 (11)0.0163 (8)0.0147 (8)0.0141 (9)
C60.0247 (8)0.0353 (9)0.0349 (9)0.0040 (7)0.0142 (7)0.0066 (7)
C70.0389 (10)0.0303 (8)0.0335 (9)0.0005 (7)0.0120 (8)0.0061 (7)
C80.0253 (8)0.0495 (11)0.0296 (8)0.0038 (8)0.0075 (7)0.0053 (8)
C90.0407 (10)0.0690 (14)0.0337 (9)0.0009 (10)0.0189 (8)0.0020 (9)
C100.0438 (12)0.0709 (15)0.0378 (10)0.0110 (11)0.0044 (9)0.0101 (10)
C110.0283 (9)0.0491 (11)0.0393 (10)0.0033 (8)0.0076 (8)0.0040 (8)
C120.0317 (8)0.0230 (7)0.0278 (8)0.0060 (6)0.0137 (7)0.0018 (6)
C130.0353 (9)0.0247 (8)0.0296 (8)0.0047 (7)0.0117 (7)0.0012 (6)
C140.0492 (11)0.0313 (9)0.0288 (8)0.0057 (8)0.0121 (8)0.0025 (7)
C150.0651 (13)0.0401 (10)0.0325 (9)0.0075 (9)0.0273 (9)0.0009 (8)
C160.0498 (11)0.0369 (10)0.0440 (10)0.0055 (8)0.0304 (9)0.0063 (8)
C170.0353 (9)0.0256 (8)0.0360 (9)0.0060 (7)0.0185 (7)0.0038 (7)
C180.0306 (9)0.0422 (10)0.0332 (9)0.0020 (8)0.0059 (7)0.0002 (8)
C190.0291 (9)0.0380 (9)0.0453 (10)0.0012 (7)0.0188 (8)0.0004 (8)
C200.0377 (10)0.0362 (10)0.0555 (12)0.0072 (8)0.0172 (9)0.0090 (9)
C210.0419 (11)0.0667 (14)0.0670 (14)0.0070 (10)0.0308 (11)0.0053 (11)
C220.0286 (9)0.0492 (11)0.0478 (11)0.0050 (8)0.0154 (8)0.0035 (9)
C230.0310 (9)0.0265 (8)0.0450 (10)0.0044 (7)0.0160 (8)0.0091 (7)
C240.0334 (9)0.0330 (9)0.0364 (9)0.0003 (7)0.0107 (7)0.0080 (7)
Geometric parameters (Å, º) top
Ti—O11.8218 (11)C7—H7A0.9600
Ti—O21.8135 (11)C7—H7B0.9600
Ti—O31.9794 (12)C7—H7C0.9600
Ti—O3i2.0603 (12)C3—C41.375 (3)
Ti—C242.0878 (17)C3—H30.9300
Ti—Tii3.2897 (9)C5—C41.386 (3)
O3—Tii2.0603 (12)C5—H50.9300
O1—C11.3678 (18)C11—H11A0.9600
O2—C121.3683 (18)C11—H11B0.9600
O3—C231.4401 (19)C11—H11C0.9600
C1—C21.404 (2)C22—H22A0.9600
C1—C61.414 (2)C22—H22B0.9600
C17—C161.400 (2)C22—H22C0.9600
C17—C121.415 (2)C24—H24A0.9600
C17—C191.539 (3)C24—H24B0.9600
C19—C201.537 (3)C24—H24C0.9600
C19—C221.542 (3)C13—C141.394 (2)
C19—C211.546 (2)C20—H20A0.9600
C12—C131.409 (2)C20—H20B0.9600
C6—C51.392 (2)C20—H20C0.9600
C6—C81.540 (2)C15—C141.375 (3)
C18—C131.504 (2)C15—H150.9300
C18—H18A0.9600C4—H40.9300
C18—H18B0.9600C10—H10A0.9600
C8—C111.531 (3)C10—H10B0.9600
C8—C91.536 (2)C10—H10C0.9600
C8—C101.540 (3)C14—H140.9300
C23—H23A0.9600C9—H9A0.9600
C23—H23B0.9600C9—H9B0.9600
C23—H23C0.9600C9—H9C0.9600
C2—C31.392 (2)C21—H21A0.9600
C2—C71.504 (2)C21—H21B0.9600
C16—C151.384 (3)C21—H21C0.9600
C16—H160.9300
O1—Ti—O2102.02 (5)H7A—C7—H7B109.5
O1—Ti—O391.68 (5)C2—C7—H7C109.5
O2—Ti—O3138.00 (5)H7A—C7—H7C109.5
O1—Ti—O3i162.64 (5)H7B—C7—H7C109.5
O2—Ti—O3i90.97 (5)C4—C3—C2120.59 (18)
O3—Ti—O3i70.97 (5)C4—C3—H3119.7
O1—Ti—C2497.38 (7)C2—C3—H3119.7
O2—Ti—C24104.51 (7)C4—C5—C6122.60 (17)
O3—Ti—C24112.91 (6)C4—C5—H5118.7
O3i—Ti—C2490.33 (6)C6—C5—H5118.7
O1—Ti—Tii127.98 (4)C8—C11—H11A109.5
O2—Ti—Tii117.24 (5)C8—C11—H11B109.5
O3—Ti—Tii36.30 (3)H11A—C11—H11B109.5
O3i—Ti—Tii34.67 (3)C8—C11—H11C109.5
C24—Ti—Tii103.76 (6)H11A—C11—H11C109.5
C23—O3—Ti129.10 (10)H11B—C11—H11C109.5
C23—O3—Tii121.77 (10)C19—C22—H22A109.5
Ti—O3—Tii109.03 (5)C19—C22—H22B109.5
C1—O1—Ti161.24 (10)H22A—C22—H22B109.5
C12—O2—Ti160.66 (11)C19—C22—H22C109.5
O1—C1—C2117.10 (14)H22A—C22—H22C109.5
O1—C1—C6121.39 (14)H22B—C22—H22C109.5
C2—C1—C6121.51 (15)Ti—C24—H24A109.5
C16—C17—C12116.15 (16)Ti—C24—H24B109.5
C16—C17—C19121.37 (16)H24A—C24—H24B109.5
C12—C17—C19122.47 (15)Ti—C24—H24C109.5
C20—C19—C17109.47 (14)H24A—C24—H24C109.5
C20—C19—C22111.10 (16)H24B—C24—H24C109.5
C17—C19—C22110.29 (15)C14—C13—C12118.17 (16)
C20—C19—C21107.17 (16)C14—C13—C18120.34 (16)
C17—C19—C21111.94 (16)C12—C13—C18121.49 (15)
C22—C19—C21106.81 (16)C19—C20—H20A109.5
O2—C12—C13117.37 (15)C19—C20—H20B109.5
O2—C12—C17120.40 (15)H20A—C20—H20B109.5
C13—C12—C17122.23 (15)C19—C20—H20C109.5
C5—C6—C1116.56 (16)H20A—C20—H20C109.5
C5—C6—C8120.82 (16)H20B—C20—H20C109.5
C1—C6—C8122.61 (15)C14—C15—C16119.93 (17)
C13—C18—H18A109.5C14—C15—H15120.0
C13—C18—H18B109.5C16—C15—H15120.0
H18A—C18—H18B109.5C3—C4—C5119.73 (17)
C13—C18—H18C109.5C3—C4—H4120.1
H18A—C18—H18C109.5C5—C4—H4120.1
H18B—C18—H18C109.5C8—C10—H10A109.5
C11—C8—C9110.96 (16)C8—C10—H10B109.5
C11—C8—C6110.04 (14)H10A—C10—H10B109.5
C9—C8—C6109.59 (15)C8—C10—H10C109.5
C11—C8—C10107.24 (16)H10A—C10—H10C109.5
C9—C8—C10106.96 (16)H10B—C10—H10C109.5
C6—C8—C10112.00 (16)C15—C14—C13121.02 (18)
O3—C23—H23A109.5C15—C14—H14119.5
O3—C23—H23B109.5C13—C14—H14119.5
H23A—C23—H23B109.5C8—C9—H9A109.5
O3—C23—H23C109.5C8—C9—H9B109.5
H23A—C23—H23C109.5H9A—C9—H9B109.5
H23B—C23—H23C109.5C8—C9—H9C109.5
C3—C2—C1118.98 (16)H9A—C9—H9C109.5
C3—C2—C7120.96 (16)H9B—C9—H9C109.5
C1—C2—C7120.06 (14)C19—C21—H21A109.5
C15—C16—C17122.47 (18)C19—C21—H21B109.5
C15—C16—H16118.8H21A—C21—H21B109.5
C17—C16—H16118.8C19—C21—H21C109.5
C2—C7—H7A109.5H21A—C21—H21C109.5
C2—C7—H7B109.5H21B—C21—H21C109.5
Symmetry code: (i) x, y+2, z+2.

Experimental details

Crystal data
Chemical formula[Ti2(CH3)2(CH3O)2(C11H15O)4]
Mr840.80
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)15.127 (3), 11.067 (2), 15.821 (3)
β (°) 115.71 (3)
V3)2386.4 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.48 × 0.20 × 0.18
Data collection
DiffractometerSiemens SMART
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.834, 0.953
No. of measured, independent and
observed [I > 2σ(I)] reflections
13277, 4844, 4113
Rint0.022
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.089, 1.04
No. of reflections4844
No. of parameters263
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.30
Absolute structureStructure is centrosymmetric

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS93 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

Acknowledgements top

We are grateful to Massey University for the award of a Post-Doctoral Fellowship to CS and to Ms T. Groutso of the University of Auckland for the data collection.

references
References top

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