research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structures of titanium–aluminium and –gallium complexes bearing two μ2-CH3 units

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aInstitut für Chemie, Fakultät für Mathematik und Naturwissenschaften, Carl von Ossietzky Universität Oldenburg, 26129 Oldenburg, Germany
*Correspondence e-mail: ruediger.beckhaus@uni-oldenburg.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 March 2017; accepted 28 March 2017; online 13 April 2017)

The isotypic crystal structures of two titanocene complexes containing an EMe3 unit (E = Al, Ga; Me = meth­yl) with two μ2-coordinating methyl groups, namely [μ-1(η5)-(adamantan-1-yl-2κC1)cycylo­penta­dien­yl]di-μ2-methyl-methyl-2κC-[1(η5)-penta­methyl­cyclo­penta­dien­yl]aluminiumtitanium(III), [AlTi(CH3)3(C10H15)(C15H18)], and [μ-1(η5)-(adamantan-1-yl-2κC1)cycylo­penta­dien­yl]di-μ2-methyl-methyl-2κC-[1(η5)-penta­methyl­cyclo­penta­dien­yl]galliumtitanium(III), [GaTi(CH3)3(C10H15)(C15H18)], are reported. Reacting a dinuclear nitro­gen-bridged low-valent titanium(III) complex with the Lewis acids AlMe3 or GaMe3 results in the loss of mol­ecular di­nitro­gen and the formation of two monomeric titanocene(III) fragments bearing two μ2-bridging methyl groups. Single crystal X-ray diffraction reveals the formation of a new E—C bond involving the penta­fulvene ligand while the bridging and terminal methyl groups remain intact.

1. Chemical context

Tri­methyl­aluminium, AlMe3, is of great inter­est because of its use in the synthesis of methyl­aluminoxane as co-catalyst in olefin polymerization (Wang, 2006[Wang, B. (2006). Coord. Chem. Rev. 250, 242-258.]; Janiak, 2006[Janiak, C. (2006). Coord. Chem. Rev. 250, 66-94.]). In organometallic chemistry, many reactions involving tri­methyl­aluminium have been investigated, e.g. the Tebbe reagent Cp2ZrCl(CH2Al(CH3)2) (Cp = cyclo­penta­dien­yl), which can be used for methyl­ation reactions (Tebbe et al., 1978[Tebbe, F. N., Parshall, G. W. & Reddy, G. S. (1978). J. Am. Chem. Soc. 100, 3611-3613.]; Thompson et al., 2014[Thompson, R., Nakamaru-Ogiso, E., Chen, C.-H., Pink, M. & Mindiola, D. J. (2014). Organometallics, 33, 429-432.]). Employing multiple C—H activation reactions, the formation of zirconium- or hafnium-containing clusters [(Cp*M)3Al6Me8(CH2)2(CH)5] (M = Zr, Hf) have been described (Herzog et al., 1996[Herzog, A., Roesky, H. W., Jäger, F., Steiner, A. & Noltemeyer, M. (1996). Organometallics, 15, 909-917.]). In a similar manner, the formation of [TiAl(C)CH3] or [TiAl(CH2)2] metallacycles have been reported (Kickham et al., 2002[Kickham, J. E., Guérin, F. & Stephan, D. W. (2002). J. Am. Chem. Soc. 124, 11486-11494.]; Stephan, 2005[Stephan, D. W. (2005). Organometallics, 24, 2548-2560.]). It is noteworthy that all these complexes result from C—H activation reactions. Since bond activation reactions employing penta­fulvene-substituted metal complexes have been of great inter­est in our work group (Oswald et al., 2016[Oswald, T., Beermann, T., Saak, W. & Beckhaus, R. (2016). Z. Kristallogr. New Cryst. Struct. 232, 143-145.]; Manssen et al., 2015[Manssen, M., Lauterbach, N., Dörfler, J., Schmidtmann, M., Saak, W., Doye, S. & Beckhaus, R. (2015). Angew. Chem. Int. Ed. 54, 4383-4387.]; Ebert et al., 2014[Ebert, H., Timmermann, V., Oswald, T., Saak, W., Schmidtmann, M., Friedemann, M., Haase, D. & Beckhaus, R. (2014). Organomet­allics, 33, 1440-1452.]), we therefore investigated the reactivity of a dinuclear nitro­gen-bridged penta­fulvene titanium complex towards AlMe3 and its heavier analogue GaMe3. Here we report on syntheses and crystal structures of the resulting title compounds, 1 and 2.

2. Structural commentary

Figs. 1[link] and 2[link] show the mol­ecular structures of 1 and isotypic 2, respectively. Both complexes show the formation of a titanium tri­methyl­aluminium or -gallium metallacycle, in which the EMe3 units are still intact and exhibit a μ2-bridging mode of the methyl groups. Additionally, a new C—Al/Ga bond is formed and the former double bond C11—C16 of the penta­fulvene ligand is repealed and at 1.509 (2) Å (1), or 1.507 (2) Å (2) is within the range of a single bond (1.53 Å; March, 2007[March, J. (2007). Advanced Organic Chemistry, 6th ed. New York: John Wiley & Sons.]). As a result of this coordination, the tetra­valent aluminium and gallium atoms differ from the ideal tetra­hedral conformation.

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of complex 1. Displacement ellipsoids correspond to the 50% probability level. H atoms have been omitted for clarity except for those of methyl groups C26, C27 and C28.
[Figure 2]
Figure 2
The mol­ecular structure of complex 2. Displacement ellipsoids correspond to the 50% probability level. H atoms have been omitted for clarity except for those of methyl groups C26, C27 and C28.

The bond lengths Al1—C26 [2.028 (2) Å] and Al1—C27 [2.047 (2) Å] in 1 are significantly elongated in comparison with that to the terminal methyl group [1.969 (2) Å], but are in good agreement with those of the free Al2Me6 mol­ecule (Vranka & Amma, 1967[Vranka, R. G. & Amma, E. L. (1967). J. Am. Chem. Soc. 89, 3121-3126.]). The same behaviour can be observed in 2 where the Ga1—C26 and Ga1—C27 distances [2.056 (2) and 2.099 (2) Å, respectively] are elongated compared to the Ga1—C28 bond length of 1.987 (2) Å [1.966 (2) Å in GaMe3; Beagley & Schmidling, 1974[Beagley, B. & Schmidling, D. G. (1974). J. Mol. Struct. 21, 437-444.]]. The Ti—C26 [2.546 (2) Å] and Ti—C27 [2.507 (2) Å] distances in 1 are significantly longer than terminal Ti—CH3 distances, e.g. Cp2TiMe2 (ca 2.16 Å; Thewalt & Wöhrle, 1994[Thewalt, U. & Wöhrle, T. (1994). J. Organomet. Chem. 464, C17-C19.]) or bridging Ti—CH3 distances such as in [Ti(NtBu)(Me3[9]aneN3)(μ-Me)2AlMe2]+ (ca 2.3 Å; Bolton et al., 2005[Bolton, P. D., Clot, E., Cowley, A. R. & Mountford, P. (2005). Chem. Comm. pp. 3313-3315.]).

3. Supra­molecular features

For both complexes, no significant supra­molecular features are observed. The crystal packing (Fig. 3[link]) appears to be dominated by van der Waals inter­actions.

[Figure 3]
Figure 3
A view along the c axis showing the packing of mol­ecules in the crystal structure of compound 1. No significant supra­molecular features can be observed. Colour code: C grey, H white, Al pink, Ti turquoise spheres.

4. Synthesis and crystallization

All reactions were carried out under a dry nitro­gen atmosphere using Schlenk techniques or in a glove box. The starting titanium complex was prepared according to a published procedure (Scherer et al., 2005[Scherer, A., Kollak, K., Lützen, A., Friedemann, M., Haase, D., Saak, W. & Beckhaus, R. (2005). Eur. J. Inorg. Chem. pp. 1003-1010.]). AlMe3 and GaMe3 solutions were purchased from Sigma Aldrich and used as received. Solvents were dried according to standard procedures over Na/K alloy with benzo­phenone as indicator and distilled under a nitro­gen atmosphere.

Synthesis of 1:

Bis[(η5-penta­methyl­cyclo­penta­dien­yl)(η5:η1-adamantylidene­penta­fulvene)titanium]-μ2,η1,η1-di­nitro­gen (500 mg, 0.632 mmol) was dissolved in toluene and AlMe3 (2 M solution in toluene, 0.65 ml, 1.3 mmol) was added. The colour of the solution changed from blue to green, after 48 h the volume had reduced to 5 ml and another 5 ml of n-hexane were added. Crystals suitable for X-ray diffraction separated after 48 h directly from the mother liquor.

Synthesis of 2:

Bis[(η5-penta­methyl­cyclo­penta­dien­yl)(η5:η1-adamantylidene­penta­fulvene)titanium]-μ2,η1,η1-di­nitro­gen (100 mg, 0.13 mmol) was dissolved in toluene and GaMe3 (1.7 M solution in toluene, 0.15 ml, 0.25 mmol) was added. The former blue solution turned brown and was stored at 233 K. After 10 days, brown–green crystals suitable for X-ray diffraction separated from the mother liquor.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. Hydrogen atoms bonded to C atoms were located from difference-Fourier maps but were subsequently fixed to idealized positions using appropriate riding models with Uiso(H) = 1.2Ueq(C); H atoms of all methyl groups were refined freely.

Table 1
Experimental details

  1 2
Crystal data
Chemical formula [AlTi(CH3)3(C10H15)(C15H18)] [GaTi(CH3)3(C10H15)(C15H18)]
Mr 453.49 496.23
Crystal system, space group Monoclinic, P21/c Monoclinic, P21/c
Temperature (K) 153 153
a, b, c (Å) 12.1618 (5), 19.8355 (8), 10.0403 (6) 12.1445 (8), 19.9196 (7), 10.0350 (4)
β (°) 91.417 (6) 91.400 (7)
V3) 2421.3 (2) 2426.9 (2)
Z 4 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.40 1.45
Crystal size (mm) 0.55 × 0.18 × 0.11 0.50 × 0.30 × 0.29
 
Data collection
Diffractometer Stoe IPDS Stoe IPDS
Absorption correction Numerical (X-RED; Stoe, 1999[Stoe (1999). IPDS and X-RED. Stoe & Cie, Darmstadt, Germany.])
Tmin, Tmax 0.571, 0.717
No. of measured, independent and observed [I > 2σ(I)] reflections 24801, 4572, 3201 28356, 5895, 4830
Rint 0.068 0.042
(sin θ/λ)max−1) 0.617 0.668
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.068, 0.87 0.026, 0.065, 0.94
No. of reflections 4572 5895
No. of parameters 295 295
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.38, −0.22 0.57, −0.32
Computer programs: IPDS and X-RED (Stoe, 1999[Stoe (1999). IPDS and X-RED. Stoe & Cie, Darmstadt, Germany.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/7 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg & Putz, 2006[Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Computing details top

For both compounds, data collection: IPDS (Stoe, 1999); cell refinement: IPDS (Stoe, 1999); data reduction: X-RED (Stoe, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

(1) [µ-1(η5)-(Adamantan-1-yl-2κC1)cycylopentadienyl]di-µ2-methyl-methyl-2κC-[1(η5)-pentamethylcyclopentadienyl]-aluminiumtitanium(III) top
Crystal data top
[AlTi(CH3)3(C10H15)(C15H18)]F(000) = 980
Mr = 453.49Dx = 1.244 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.1618 (5) ÅCell parameters from 7286 reflections
b = 19.8355 (8) Åθ = 2.4–26.0°
c = 10.0403 (6) ŵ = 0.40 mm1
β = 91.417 (6)°T = 153 K
V = 2421.3 (2) Å3Block, yellow
Z = 40.55 × 0.18 × 0.11 mm
Data collection top
Stoe IPDS
diffractometer
Rint = 0.068
Radiation source: sealed tubeθmax = 26.0°, θmin = 2.3°
ω scansh = 1414
24801 measured reflectionsk = 2424
4572 independent reflectionsl = 1212
3201 reflections with I > 2σ(I)
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068 w = 1/[σ2(Fo2) + (0.035P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.87(Δ/σ)max = 0.002
4572 reflectionsΔρmax = 0.38 e Å3
295 parametersΔρmin = 0.22 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ti10.26484 (3)0.59327 (2)0.23454 (3)0.01418 (9)
Al10.24338 (5)0.45093 (3)0.21686 (5)0.01685 (13)
C10.26433 (17)0.62640 (9)0.00582 (17)0.0194 (4)
C20.35839 (16)0.65709 (9)0.06987 (16)0.0174 (4)
C30.31849 (17)0.70394 (9)0.16359 (17)0.0190 (4)
C40.20285 (17)0.70296 (9)0.15852 (17)0.0208 (4)
C50.16835 (17)0.65619 (10)0.05950 (18)0.0225 (4)
C60.2660 (2)0.57896 (10)0.11059 (18)0.0307 (5)
H6A0.33880.55810.11550.046*
H6B0.24980.60400.19290.046*
H6C0.21040.54380.09930.046*
C70.47622 (18)0.64859 (10)0.03299 (19)0.0267 (5)
H7A0.52290.64820.11400.040*
H7B0.49800.68610.02430.040*
H7C0.48490.60590.01480.040*
C80.3886 (2)0.75391 (10)0.2411 (2)0.0310 (5)
H8A0.39390.79590.19030.047*
H8B0.46240.73510.25630.047*
H8C0.35510.76310.32690.047*
C90.1279 (2)0.75006 (11)0.2308 (2)0.0346 (5)
H9A0.06320.72520.26020.052*
H9B0.10450.78660.17090.052*
H9C0.16720.76900.30850.052*
C100.05177 (19)0.64766 (12)0.0111 (2)0.0343 (5)
H10A0.02880.68770.03970.051*
H10B0.00400.64200.08750.051*
H10C0.04620.60780.04630.051*
C110.26346 (16)0.52506 (9)0.43500 (15)0.0159 (4)
C120.18257 (18)0.57674 (9)0.44326 (17)0.0201 (4)
H120.10540.56980.44660.024*
C130.2357 (2)0.63998 (9)0.44565 (17)0.0261 (5)
H130.20070.68260.45130.031*
C140.34920 (19)0.62892 (10)0.43818 (18)0.0267 (5)
H140.40460.66270.43780.032*
C150.36642 (17)0.55903 (10)0.43137 (17)0.0208 (4)
H150.43610.53770.42530.025*
C160.24577 (16)0.45016 (9)0.41903 (16)0.0157 (4)
C170.34159 (16)0.40901 (10)0.48341 (16)0.0194 (4)
H170.41240.42290.44300.023*
C180.32207 (19)0.33371 (10)0.45734 (19)0.0265 (5)
H18A0.31840.32530.36020.032*
H18B0.38410.30730.49590.032*
C190.2146 (2)0.31122 (10)0.5197 (2)0.0297 (5)
H190.20220.26220.50140.036*
C200.11873 (19)0.35226 (10)0.4600 (2)0.0277 (5)
H20A0.11230.34390.36290.033*
H20B0.04910.33810.50080.033*
C210.13831 (17)0.42731 (9)0.48584 (17)0.0205 (4)
H210.07500.45370.44740.025*
C220.34877 (18)0.42069 (10)0.63524 (17)0.0253 (5)
H22A0.41120.39480.67430.030*
H22B0.36150.46910.65390.030*
C230.2225 (2)0.32297 (11)0.6709 (2)0.0338 (5)
H23A0.15360.30820.71260.041*
H23B0.28400.29630.71010.041*
C240.14558 (18)0.43886 (11)0.63770 (18)0.0267 (5)
H24A0.15680.48740.65660.032*
H24B0.07600.42470.67840.032*
C250.24165 (19)0.39807 (11)0.69803 (18)0.0286 (5)
H250.24640.40590.79640.034*
C260.11305 (18)0.51058 (10)0.1682 (2)0.0223 (4)
H26A0.091 (2)0.5577 (12)0.195 (2)0.033*
H26B0.100 (2)0.5063 (11)0.073 (2)0.033*
H26C0.060 (2)0.4816 (12)0.212 (2)0.033*
C270.38455 (18)0.49812 (10)0.1606 (2)0.0218 (4)
H27A0.4231 (19)0.5418 (12)0.172 (2)0.033*
H27B0.3890 (19)0.4872 (11)0.066 (2)0.033*
H27C0.433 (2)0.4675 (12)0.206 (2)0.033*
C280.2331 (2)0.36873 (10)0.10736 (18)0.0268 (5)
H28A0.17240.34070.13800.040*
H28B0.30220.34350.11570.040*
H28C0.21960.38110.01390.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.0176 (2)0.01180 (14)0.01316 (15)0.00042 (14)0.00005 (11)0.00074 (12)
Al10.0228 (4)0.0132 (2)0.0145 (2)0.0004 (2)0.0004 (2)0.0011 (2)
C10.0285 (13)0.0163 (9)0.0133 (8)0.0009 (8)0.0002 (7)0.0028 (7)
C20.0200 (12)0.0147 (9)0.0177 (9)0.0001 (7)0.0013 (7)0.0045 (7)
C30.0279 (13)0.0111 (8)0.0180 (8)0.0006 (8)0.0004 (7)0.0022 (7)
C40.0272 (13)0.0150 (9)0.0203 (9)0.0032 (8)0.0042 (8)0.0048 (7)
C50.0214 (13)0.0234 (10)0.0226 (9)0.0009 (8)0.0024 (8)0.0099 (8)
C60.0501 (16)0.0239 (11)0.0180 (9)0.0048 (9)0.0025 (9)0.0018 (7)
C70.0246 (13)0.0269 (10)0.0289 (10)0.0031 (9)0.0052 (8)0.0084 (8)
C80.0463 (16)0.0196 (10)0.0271 (11)0.0093 (10)0.0032 (9)0.0005 (8)
C90.0413 (16)0.0280 (12)0.0352 (12)0.0151 (10)0.0105 (10)0.0058 (9)
C100.0266 (14)0.0356 (12)0.0401 (12)0.0044 (10)0.0100 (9)0.0184 (10)
C110.0201 (12)0.0187 (9)0.0089 (8)0.0006 (8)0.0007 (7)0.0004 (7)
C120.0237 (12)0.0222 (10)0.0145 (8)0.0032 (8)0.0041 (7)0.0005 (7)
C130.0468 (16)0.0156 (10)0.0158 (9)0.0031 (9)0.0015 (8)0.0042 (7)
C140.0397 (16)0.0217 (10)0.0183 (9)0.0113 (9)0.0076 (8)0.0006 (7)
C150.0232 (13)0.0231 (10)0.0158 (9)0.0044 (8)0.0061 (8)0.0027 (7)
C160.0159 (11)0.0142 (8)0.0170 (8)0.0014 (7)0.0010 (7)0.0001 (7)
C170.0192 (11)0.0207 (9)0.0182 (8)0.0003 (8)0.0007 (7)0.0037 (7)
C180.0325 (14)0.0193 (10)0.0276 (10)0.0056 (9)0.0014 (9)0.0034 (8)
C190.0385 (15)0.0186 (10)0.0321 (11)0.0045 (9)0.0011 (9)0.0077 (8)
C200.0263 (14)0.0265 (11)0.0303 (11)0.0111 (9)0.0004 (8)0.0062 (8)
C210.0174 (12)0.0229 (10)0.0211 (9)0.0014 (8)0.0010 (7)0.0048 (7)
C220.0258 (13)0.0292 (11)0.0205 (9)0.0000 (9)0.0070 (8)0.0052 (7)
C230.0365 (15)0.0327 (12)0.0321 (11)0.0028 (10)0.0006 (10)0.0170 (9)
C240.0252 (13)0.0344 (12)0.0210 (10)0.0021 (9)0.0081 (8)0.0028 (8)
C250.0344 (14)0.0350 (11)0.0166 (9)0.0024 (10)0.0006 (8)0.0078 (8)
C260.0227 (13)0.0239 (11)0.0202 (10)0.0013 (8)0.0014 (8)0.0035 (8)
C270.0259 (13)0.0185 (9)0.0213 (10)0.0031 (8)0.0051 (8)0.0015 (7)
C280.0371 (14)0.0214 (10)0.0220 (10)0.0022 (9)0.0001 (8)0.0044 (8)
Geometric parameters (Å, º) top
Ti1—C132.3481 (18)C11—C121.425 (3)
Ti1—C122.3673 (18)C11—C161.509 (2)
Ti1—C142.3726 (18)C12—C131.411 (3)
Ti1—C12.3884 (17)C12—H120.9500
Ti1—C22.3923 (17)C13—C141.401 (3)
Ti1—C152.4025 (18)C13—H130.9500
Ti1—C32.4032 (18)C14—C151.404 (3)
Ti1—C42.4199 (18)C14—H140.9500
Ti1—C112.4255 (16)C15—H150.9500
Ti1—C52.4334 (18)C16—C171.551 (3)
Ti1—C272.507 (2)C16—C211.551 (3)
Ti1—C262.546 (2)C17—C181.534 (3)
Ti1—Al12.8406 (6)C17—C221.542 (2)
Ti1—H26A2.26 (2)C17—H171.0000
Al1—C281.9687 (19)C18—C191.530 (3)
Al1—C262.028 (2)C18—H18A0.9900
Al1—C162.0294 (17)C18—H18B0.9900
Al1—C272.047 (2)C19—C201.532 (3)
C1—C51.426 (3)C19—C231.537 (3)
C1—C21.434 (3)C19—H191.0000
C1—C61.501 (3)C20—C211.529 (3)
C2—C31.417 (3)C20—H20A0.9900
C2—C71.499 (3)C20—H20B0.9900
C3—C41.406 (3)C21—C241.542 (3)
C3—C81.511 (3)C21—H211.0000
C4—C51.416 (3)C22—C251.529 (3)
C4—C91.504 (3)C22—H22A0.9900
C5—C101.497 (3)C22—H22B0.9900
C6—H6A0.9800C23—C251.531 (3)
C6—H6B0.9800C23—H23A0.9900
C6—H6C0.9800C23—H23B0.9900
C7—H7A0.9800C24—C251.533 (3)
C7—H7B0.9800C24—H24A0.9900
C7—H7C0.9800C24—H24B0.9900
C8—H8A0.9800C25—H251.0000
C8—H8B0.9800C26—H26A1.01 (2)
C8—H8C0.9800C26—H26B0.97 (2)
C9—H9A0.9800C26—H26C0.98 (2)
C9—H9B0.9800C27—H27A0.99 (2)
C9—H9C0.9800C27—H27B0.98 (2)
C10—H10A0.9800C27—H27C0.95 (2)
C10—H10B0.9800C28—H28A0.9800
C10—H10C0.9800C28—H28B0.9800
C11—C151.423 (3)C28—H28C0.9800
C13—Ti1—C1234.82 (7)H7A—C7—H7B109.5
C13—Ti1—C1434.53 (8)C2—C7—H7C109.5
C12—Ti1—C1457.43 (7)H7A—C7—H7C109.5
C13—Ti1—C1139.68 (7)H7B—C7—H7C109.5
C12—Ti1—C1153.91 (7)C3—C8—H8A109.5
C14—Ti1—C1137.51 (7)C3—C8—H8B109.5
C13—Ti1—C2120.00 (7)H8A—C8—H8B109.5
C12—Ti1—C2154.65 (6)C3—C8—H8C109.5
C14—Ti1—C2103.59 (7)H8A—C8—H8C109.5
C1—Ti1—C234.91 (7)H8B—C8—H8C109.5
C13—Ti1—C1556.98 (7)C4—C9—H9A109.5
C12—Ti1—C1556.82 (7)C4—C9—H9B109.5
C14—Ti1—C1534.19 (6)H9A—C9—H9B109.5
C1—Ti1—C15149.06 (7)C4—C9—H9C109.5
C2—Ti1—C15118.32 (7)H9A—C9—H9C109.5
C13—Ti1—C387.44 (6)H9B—C9—H9C109.5
C12—Ti1—C3120.84 (6)C5—C10—H10A109.5
C14—Ti1—C382.44 (6)C5—C10—H10B109.5
C1—Ti1—C357.18 (6)H10A—C10—H10B109.5
C2—Ti1—C334.37 (6)C5—C10—H10C109.5
C15—Ti1—C3111.36 (6)H10A—C10—H10C109.5
C13—Ti1—C482.94 (6)H10B—C10—H10C109.5
C12—Ti1—C4105.57 (6)C15—C11—C12105.67 (17)
C14—Ti1—C497.39 (7)C15—C11—C16125.91 (17)
C1—Ti1—C457.04 (6)C12—C11—C16128.15 (18)
C2—Ti1—C457.05 (6)C15—C11—Ti171.98 (10)
C15—Ti1—C4131.56 (7)C12—C11—Ti170.48 (10)
C3—Ti1—C433.90 (7)C16—C11—Ti1117.70 (10)
C13—Ti1—C1157.78 (6)C13—C12—C11108.90 (19)
C12—Ti1—C1134.56 (6)C13—C12—Ti171.85 (10)
C14—Ti1—C1157.51 (6)C11—C12—Ti174.96 (10)
C1—Ti1—C11162.06 (6)C13—C12—H12125.6
C2—Ti1—C11151.86 (7)C11—C12—H12125.6
C15—Ti1—C1134.28 (6)Ti1—C12—H12119.4
C3—Ti1—C11139.73 (6)C14—C13—C12108.14 (18)
C4—Ti1—C11139.00 (6)C14—C13—Ti173.69 (11)
C13—Ti1—C5111.64 (7)C12—C13—Ti173.33 (10)
C12—Ti1—C5120.23 (7)C14—C13—H13125.9
C14—Ti1—C5131.30 (7)C12—C13—H13125.9
C1—Ti1—C534.39 (7)Ti1—C13—H13118.9
C2—Ti1—C557.22 (7)C13—C14—C15107.78 (18)
C15—Ti1—C5165.47 (7)C13—C14—Ti171.78 (11)
C3—Ti1—C556.43 (7)C15—C14—Ti174.07 (11)
C4—Ti1—C533.92 (7)C13—C14—H14126.1
C11—Ti1—C5150.72 (7)C15—C14—H14126.1
C13—Ti1—C27131.75 (7)Ti1—C14—H14119.9
C12—Ti1—C27114.77 (6)C14—C15—C11109.50 (19)
C14—Ti1—C27103.74 (8)C14—C15—Ti171.74 (11)
C1—Ti1—C2784.85 (7)C11—C15—Ti173.74 (10)
C2—Ti1—C2784.51 (6)C14—C15—H15125.2
C15—Ti1—C2774.94 (7)C11—C15—H15125.2
C3—Ti1—C27115.85 (7)Ti1—C15—H15120.9
C4—Ti1—C27139.65 (6)C11—C16—C17111.73 (15)
C11—Ti1—C2780.89 (6)C11—C16—C21111.17 (15)
C5—Ti1—C27116.46 (7)C17—C16—C21107.36 (14)
C13—Ti1—C26111.45 (7)C11—C16—Al195.59 (10)
C12—Ti1—C2679.78 (7)C17—C16—Al1114.39 (12)
C14—Ti1—C26135.46 (7)C21—C16—Al1116.31 (12)
C1—Ti1—C2686.63 (7)C18—C17—C22108.65 (15)
C2—Ti1—C26120.95 (6)C18—C17—C16109.26 (15)
C15—Ti1—C26112.82 (6)C22—C17—C16110.88 (15)
C3—Ti1—C26135.35 (7)C18—C17—H17109.3
C4—Ti1—C26106.17 (7)C22—C17—H17109.3
C11—Ti1—C2680.66 (6)C16—C17—H17109.3
C5—Ti1—C2678.93 (7)C19—C18—C17110.13 (16)
C27—Ti1—C2681.97 (7)C19—C18—H18A109.6
C13—Ti1—Al1115.65 (5)C17—C18—H18A109.6
C12—Ti1—Al182.96 (5)C19—C18—H18B109.6
C14—Ti1—Al1112.78 (5)C17—C18—H18B109.6
C1—Ti1—Al1102.43 (5)H18A—C18—H18B108.1
C2—Ti1—Al1121.82 (5)C18—C19—C20109.55 (16)
C15—Ti1—Al179.34 (5)C18—C19—C23109.08 (18)
C3—Ti1—Al1156.15 (5)C20—C19—C23109.54 (18)
C4—Ti1—Al1147.83 (5)C18—C19—H19109.6
C11—Ti1—Al159.66 (4)C20—C19—H19109.6
C5—Ti1—Al1115.01 (5)C23—C19—H19109.6
C27—Ti1—Al144.47 (5)C21—C20—C19109.71 (17)
C26—Ti1—Al143.81 (5)C21—C20—H20A109.7
C13—Ti1—H26A97.0 (6)C19—C20—H20A109.7
C12—Ti1—H26A72.5 (5)C21—C20—H20B109.7
C14—Ti1—H26A129.0 (5)C19—C20—H20B109.7
C1—Ti1—H26A86.3 (5)H20A—C20—H20B108.2
C2—Ti1—H26A120.2 (5)C20—C21—C24108.50 (15)
C15—Ti1—H26A121.2 (6)C20—C21—C16109.91 (15)
C3—Ti1—H26A119.5 (6)C24—C21—C16110.84 (16)
C4—Ti1—H26A86.6 (6)C20—C21—H21109.2
C11—Ti1—H26A87.0 (6)C24—C21—H21109.2
C5—Ti1—H26A66.3 (6)C16—C21—H21109.2
C27—Ti1—H26A105.1 (6)C25—C22—C17109.61 (16)
C26—Ti1—H26A23.3 (6)C25—C22—H22A109.7
Al1—Ti1—H26A66.1 (6)C17—C22—H22A109.7
C28—Al1—C26108.08 (9)C25—C22—H22B109.7
C28—Al1—C16123.47 (8)C17—C22—H22B109.7
C26—Al1—C16103.71 (8)H22A—C22—H22B108.2
C28—Al1—C27105.47 (9)C25—C23—C19109.20 (15)
C26—Al1—C27108.83 (9)C25—C23—H23A109.8
C16—Al1—C27106.73 (8)C19—C23—H23A109.8
C28—Al1—Ti1149.60 (6)C25—C23—H23B109.8
C26—Al1—Ti160.34 (6)C19—C23—H23B109.8
C16—Al1—Ti186.90 (5)H23A—C23—H23B108.3
C27—Al1—Ti159.09 (6)C25—C24—C21109.67 (16)
C5—C1—C2107.81 (16)C25—C24—H24A109.7
C5—C1—C6125.52 (18)C21—C24—H24A109.7
C2—C1—C6126.12 (19)C25—C24—H24B109.7
C5—C1—Ti174.54 (10)C21—C24—H24B109.7
C2—C1—Ti172.70 (10)H24A—C24—H24B108.2
C6—C1—Ti1125.20 (12)C22—C25—C23109.86 (18)
C3—C2—C1107.09 (17)C22—C25—C24109.33 (16)
C3—C2—C7125.68 (18)C23—C25—C24109.38 (18)
C1—C2—C7126.77 (17)C22—C25—H25109.4
C3—C2—Ti173.24 (10)C23—C25—H25109.4
C1—C2—Ti172.40 (10)C24—C25—H25109.4
C7—C2—Ti1125.83 (12)Al1—C26—Ti175.85 (7)
C4—C3—C2109.00 (16)Al1—C26—H26A133.6 (13)
C4—C3—C8125.40 (18)Ti1—C26—H26A62.1 (14)
C2—C3—C8125.0 (2)Al1—C26—H26B107.4 (14)
C4—C3—Ti173.70 (10)Ti1—C26—H26B114.7 (14)
C2—C3—Ti172.40 (10)H26A—C26—H26B107.4 (18)
C8—C3—Ti1126.91 (12)Al1—C26—H26C94.0 (14)
C3—C4—C5108.26 (16)Ti1—C26—H26C138.2 (13)
C3—C4—C9126.24 (18)H26A—C26—H26C104.1 (18)
C5—C4—C9125.0 (2)H26B—C26—H26C107.1 (19)
C3—C4—Ti172.40 (10)Al1—C27—Ti176.44 (7)
C5—C4—Ti173.56 (11)Al1—C27—H27A140.1 (13)
C9—C4—Ti1126.44 (13)Ti1—C27—H27A65.5 (14)
C4—C5—C1107.81 (18)Al1—C27—H27B103.6 (14)
C4—C5—C10124.33 (19)Ti1—C27—H27B120.1 (13)
C1—C5—C10127.44 (18)H27A—C27—H27B105.4 (18)
C4—C5—Ti172.52 (10)Al1—C27—H27C94.9 (14)
C1—C5—Ti171.08 (10)Ti1—C27—H27C133.8 (13)
C10—C5—Ti1127.77 (13)H27A—C27—H27C102.7 (19)
C1—C6—H6A109.5H27B—C27—H27C106.2 (19)
C1—C6—H6B109.5Al1—C28—H28A109.5
H6A—C6—H6B109.5Al1—C28—H28B109.5
C1—C6—H6C109.5H28A—C28—H28B109.5
H6A—C6—H6C109.5Al1—C28—H28C109.5
H6B—C6—H6C109.5H28A—C28—H28C109.5
C2—C7—H7A109.5H28B—C28—H28C109.5
C2—C7—H7B109.5
C5—C1—C2—C31.29 (19)C12—C13—C14—Ti165.77 (12)
C6—C1—C2—C3173.12 (17)C13—C14—C15—C110.2 (2)
Ti1—C1—C2—C365.54 (12)Ti1—C14—C15—C1164.56 (12)
C5—C1—C2—C7171.20 (17)C13—C14—C15—Ti164.34 (13)
C6—C1—C2—C70.6 (3)C12—C11—C15—C140.43 (19)
Ti1—C1—C2—C7121.97 (18)C16—C11—C15—C14174.87 (15)
C5—C1—C2—Ti166.83 (12)Ti1—C11—C15—C1463.28 (13)
C6—C1—C2—Ti1121.34 (18)C12—C11—C15—Ti162.86 (11)
C1—C2—C3—C40.15 (19)C16—C11—C15—Ti1111.59 (15)
C7—C2—C3—C4172.44 (16)C15—C11—C16—C1735.8 (2)
Ti1—C2—C3—C465.13 (12)C12—C11—C16—C17150.96 (16)
C1—C2—C3—C8171.86 (16)Ti1—C11—C16—C17122.91 (13)
C7—C2—C3—C80.7 (3)C15—C11—C16—C21155.76 (16)
Ti1—C2—C3—C8123.17 (18)C12—C11—C16—C2131.0 (2)
C1—C2—C3—Ti164.97 (12)Ti1—C11—C16—C21117.17 (14)
C7—C2—C3—Ti1122.43 (17)C15—C11—C16—Al183.21 (17)
C2—C3—C4—C51.1 (2)C12—C11—C16—Al189.99 (17)
C8—C3—C4—C5170.61 (17)Ti1—C11—C16—Al13.86 (14)
Ti1—C3—C4—C565.34 (13)C11—C16—C17—C18176.93 (14)
C2—C3—C4—C9173.03 (17)C21—C16—C17—C1860.94 (18)
C8—C3—C4—C91.4 (3)Al1—C16—C17—C1869.73 (17)
Ti1—C3—C4—C9122.69 (18)C11—C16—C17—C2263.35 (19)
C2—C3—C4—Ti164.29 (12)C21—C16—C17—C2258.78 (19)
C8—C3—C4—Ti1124.05 (18)Al1—C16—C17—C22170.55 (13)
C3—C4—C5—C11.8 (2)C22—C17—C18—C1960.1 (2)
C9—C4—C5—C1173.95 (17)C16—C17—C18—C1960.95 (19)
Ti1—C4—C5—C162.73 (12)C17—C18—C19—C2059.2 (2)
C3—C4—C5—C10171.19 (17)C17—C18—C19—C2360.7 (2)
C9—C4—C5—C100.9 (3)C18—C19—C20—C2158.9 (2)
Ti1—C4—C5—C10124.23 (18)C23—C19—C20—C2160.7 (2)
C3—C4—C5—Ti164.57 (12)C19—C20—C21—C2460.5 (2)
C9—C4—C5—Ti1123.32 (18)C19—C20—C21—C1660.8 (2)
C2—C1—C5—C41.9 (2)C11—C16—C21—C20176.23 (15)
C6—C1—C5—C4173.83 (17)C17—C16—C21—C2061.29 (19)
Ti1—C1—C5—C463.66 (12)Al1—C16—C21—C2068.30 (18)
C2—C1—C5—C10170.82 (17)C11—C16—C21—C2463.84 (19)
C6—C1—C5—C101.1 (3)C17—C16—C21—C2458.64 (19)
Ti1—C1—C5—C10123.58 (19)Al1—C16—C21—C24171.78 (13)
C2—C1—C5—Ti165.60 (12)C18—C17—C22—C2559.5 (2)
C6—C1—C5—Ti1122.50 (18)C16—C17—C22—C2560.6 (2)
C15—C11—C12—C130.48 (18)C18—C19—C23—C2560.0 (2)
C16—C11—C12—C13174.75 (15)C20—C19—C23—C2559.9 (2)
Ti1—C11—C12—C1364.34 (12)C20—C21—C24—C2560.5 (2)
C15—C11—C12—Ti163.87 (11)C16—C21—C24—C2560.3 (2)
C16—C11—C12—Ti1110.41 (16)C17—C22—C25—C2360.2 (2)
C11—C12—C13—C140.4 (2)C17—C22—C25—C2459.9 (2)
Ti1—C12—C13—C1466.01 (13)C19—C23—C25—C2260.2 (2)
C11—C12—C13—Ti166.37 (12)C19—C23—C25—C2459.8 (2)
C12—C13—C14—C150.1 (2)C21—C24—C25—C2259.8 (2)
Ti1—C13—C14—C1565.86 (13)C21—C24—C25—C2360.5 (2)
(2) [µ-1(η5)-(Adamantan-1-yl-2κC1)cycylopentadienyl]di-µ2-methyl-methyl-2κC-[1(η5)-pentamethylcyclopentadienyl]-galliumtitanium(III) top
Crystal data top
[GaTi(CH3)3(C10H15)(C15H18)]F(000) = 1052
Mr = 496.23Dx = 1.358 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.1445 (8) ÅCell parameters from 8000 reflections
b = 19.9196 (7) Åθ = 2.6–28.4°
c = 10.0350 (4) ŵ = 1.45 mm1
β = 91.400 (7)°T = 153 K
V = 2426.9 (2) Å3Block, green
Z = 40.50 × 0.30 × 0.29 mm
Data collection top
Stoe IPDS
diffractometer
4830 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.042
ω–scansθmax = 28.3°, θmin = 2.7°
Absorption correction: numerical
(X-RED; Stoe, 1999)
h = 1616
Tmin = 0.571, Tmax = 0.717k = 2626
28356 measured reflectionsl = 1313
5895 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.065 w = 1/[σ2(Fo2) + (0.045P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.001
5895 reflectionsΔρmax = 0.57 e Å3
295 parametersΔρmin = 0.32 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ti10.26510 (2)0.59328 (2)0.23594 (3)0.01499 (6)
Ga10.24185 (2)0.44945 (2)0.21612 (2)0.01868 (5)
C10.26371 (12)0.62639 (7)0.00683 (16)0.0200 (3)
C20.35740 (11)0.65699 (7)0.07047 (15)0.0187 (3)
C30.31964 (12)0.70397 (7)0.16453 (16)0.0201 (3)
C40.20233 (12)0.70289 (7)0.16042 (16)0.0218 (3)
C50.16791 (12)0.65626 (8)0.06199 (16)0.0220 (3)
C60.26467 (16)0.57887 (8)0.10972 (18)0.0306 (4)
H6A0.33880.56030.11870.046*
H6B0.24340.60310.19140.046*
H6C0.21240.54230.09500.046*
C70.47592 (12)0.64853 (8)0.03272 (18)0.0263 (3)
H7A0.52260.64630.11370.039*
H7B0.49840.68680.02150.039*
H7C0.48390.60700.01850.039*
C80.38924 (15)0.75375 (8)0.24158 (19)0.0305 (4)
H8A0.39620.79510.18940.046*
H8B0.46250.73460.25930.046*
H8C0.35440.76400.32620.046*
C90.12758 (15)0.75012 (9)0.2327 (2)0.0341 (4)
H9A0.06450.72510.26620.051*
H9B0.10140.78520.17130.051*
H9C0.16820.77070.30770.051*
C100.05046 (13)0.64805 (9)0.0134 (2)0.0336 (4)
H10A0.02580.68940.03120.050*
H10B0.00350.63900.08940.050*
H10C0.04560.61050.04950.050*
C110.26365 (12)0.52545 (7)0.43654 (15)0.0169 (3)
C120.18259 (13)0.57730 (8)0.44522 (16)0.0220 (3)
H120.10530.57050.44910.026*
C130.23655 (15)0.64068 (8)0.44711 (17)0.0276 (3)
H130.20180.68330.45280.033*
C140.35007 (15)0.62917 (8)0.43912 (17)0.0275 (3)
H140.40590.66260.43820.033*
C150.36680 (12)0.55911 (7)0.43266 (16)0.0211 (3)
H150.43640.53770.42660.025*
C160.24577 (11)0.45104 (7)0.41968 (15)0.0160 (3)
C170.34130 (11)0.40929 (7)0.48259 (16)0.0199 (3)
H170.41230.42340.44270.024*
C180.32215 (14)0.33399 (8)0.45491 (19)0.0268 (3)
H18A0.31880.32600.35750.032*
H18B0.38420.30760.49340.032*
C190.21393 (15)0.31129 (8)0.51680 (19)0.0307 (4)
H190.20130.26260.49750.037*
C200.11816 (13)0.35279 (8)0.45715 (19)0.0279 (3)
H20A0.04820.33850.49710.033*
H20B0.11220.34510.35980.033*
C210.13800 (12)0.42791 (8)0.48504 (16)0.0211 (3)
H210.07480.45450.44700.025*
C220.34832 (13)0.41990 (8)0.63446 (17)0.0256 (3)
H22A0.41070.39380.67290.031*
H22B0.36150.46800.65430.031*
C230.22157 (16)0.32224 (9)0.6678 (2)0.0360 (4)
H23A0.28310.29540.70650.043*
H23B0.15250.30730.70890.043*
C240.14504 (14)0.43846 (9)0.63692 (18)0.0283 (3)
H24A0.15650.48670.65690.034*
H24B0.07510.42430.67710.034*
C250.24086 (14)0.39729 (9)0.69729 (18)0.0300 (4)
H250.24550.40460.79590.036*
C260.10953 (13)0.50957 (8)0.16647 (18)0.0233 (3)
H26A0.0920 (18)0.5522 (11)0.194 (2)0.035*
H26B0.0986 (18)0.5057 (11)0.077 (3)0.035*
H26C0.0531 (19)0.4848 (11)0.206 (2)0.035*
C270.38617 (12)0.49823 (8)0.15818 (17)0.0185 (3)
H27A0.4057 (18)0.5323 (11)0.169 (2)0.028*
H27B0.3895 (16)0.4900 (10)0.076 (2)0.028*
H27C0.4357 (17)0.4692 (10)0.206 (2)0.028*
C280.23418 (15)0.36701 (8)0.10482 (19)0.0298 (4)
H28A0.17620.33740.13740.045*
H28B0.30510.34360.11010.045*
H28C0.21740.37930.01200.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ti10.01601 (11)0.01426 (11)0.01467 (14)0.00026 (8)0.00024 (9)0.00099 (9)
Ga10.02268 (8)0.01700 (8)0.01628 (9)0.00069 (6)0.00110 (6)0.00145 (6)
C10.0237 (7)0.0198 (7)0.0162 (8)0.0006 (5)0.0012 (6)0.0024 (5)
C20.0195 (6)0.0185 (6)0.0181 (8)0.0002 (5)0.0019 (5)0.0040 (5)
C30.0240 (7)0.0166 (6)0.0196 (8)0.0012 (5)0.0001 (6)0.0022 (5)
C40.0236 (7)0.0189 (7)0.0230 (8)0.0044 (5)0.0040 (6)0.0051 (6)
C50.0198 (7)0.0234 (7)0.0228 (9)0.0001 (5)0.0017 (6)0.0079 (6)
C60.0467 (10)0.0263 (8)0.0186 (9)0.0027 (7)0.0031 (7)0.0022 (6)
C70.0210 (7)0.0296 (8)0.0285 (9)0.0032 (6)0.0057 (6)0.0071 (6)
C80.0410 (9)0.0209 (7)0.0293 (10)0.0085 (7)0.0037 (7)0.0007 (6)
C90.0379 (9)0.0302 (8)0.0347 (11)0.0139 (7)0.0106 (8)0.0035 (7)
C100.0214 (7)0.0389 (9)0.0400 (11)0.0047 (6)0.0089 (7)0.0157 (8)
C110.0198 (6)0.0186 (6)0.0124 (7)0.0002 (5)0.0010 (5)0.0001 (5)
C120.0253 (7)0.0241 (7)0.0168 (8)0.0039 (6)0.0035 (6)0.0015 (6)
C130.0475 (10)0.0183 (7)0.0170 (8)0.0036 (6)0.0006 (7)0.0036 (6)
C140.0392 (9)0.0219 (7)0.0210 (9)0.0097 (6)0.0083 (7)0.0007 (6)
C150.0225 (7)0.0226 (7)0.0180 (8)0.0048 (5)0.0057 (6)0.0017 (5)
C160.0150 (6)0.0165 (6)0.0167 (7)0.0006 (5)0.0007 (5)0.0012 (5)
C170.0173 (6)0.0213 (7)0.0210 (8)0.0012 (5)0.0020 (5)0.0041 (6)
C180.0313 (8)0.0198 (7)0.0291 (10)0.0052 (6)0.0024 (7)0.0051 (6)
C190.0353 (8)0.0215 (7)0.0351 (10)0.0060 (6)0.0029 (7)0.0089 (7)
C200.0255 (7)0.0250 (8)0.0330 (10)0.0094 (6)0.0007 (6)0.0059 (7)
C210.0161 (6)0.0243 (7)0.0230 (9)0.0027 (5)0.0006 (6)0.0031 (6)
C220.0243 (7)0.0304 (8)0.0217 (9)0.0011 (6)0.0056 (6)0.0044 (6)
C230.0385 (9)0.0350 (9)0.0345 (11)0.0036 (7)0.0007 (8)0.0180 (8)
C240.0265 (8)0.0362 (9)0.0226 (9)0.0013 (6)0.0078 (6)0.0037 (7)
C250.0336 (8)0.0389 (9)0.0176 (9)0.0036 (7)0.0009 (7)0.0086 (7)
C260.0210 (7)0.0271 (8)0.0216 (9)0.0014 (6)0.0019 (6)0.0035 (6)
C270.0180 (6)0.0173 (7)0.0205 (8)0.0001 (5)0.0062 (6)0.0016 (6)
C280.0369 (9)0.0261 (8)0.0264 (10)0.0022 (6)0.0004 (7)0.0091 (7)
Geometric parameters (Å, º) top
Ti1—C132.3533 (17)C11—C121.431 (2)
Ti1—C122.3704 (16)C11—C161.5069 (19)
Ti1—C142.3728 (16)C12—C131.422 (2)
Ti1—C22.3906 (15)C12—H120.9500
Ti1—C12.3916 (16)C13—C141.402 (3)
Ti1—C152.4013 (15)C13—H130.9500
Ti1—C32.4160 (14)C14—C151.412 (2)
Ti1—C112.4248 (15)C14—H140.9500
Ti1—C42.4279 (14)C15—H150.9500
Ti1—C52.4318 (15)C16—C211.5483 (19)
Ti1—C272.5322 (16)C16—C171.5493 (19)
Ti1—C262.6023 (17)C17—C221.539 (2)
Ti1—Ga12.8852 (3)C17—C181.542 (2)
Ti1—H27A2.22 (2)C17—H171.0000
Ga1—C281.9869 (16)C18—C191.535 (2)
Ga1—C162.0423 (15)C18—H18A0.9900
Ga1—C262.0556 (15)C18—H18B0.9900
Ga1—C272.0985 (15)C19—C231.531 (3)
C1—C21.428 (2)C19—C201.536 (2)
C1—C51.430 (2)C19—H191.0000
C1—C61.505 (2)C20—C211.540 (2)
C2—C31.414 (2)C20—H20A0.9900
C2—C71.507 (2)C20—H20B0.9900
C3—C41.424 (2)C21—C241.539 (2)
C3—C81.504 (2)C21—H211.0000
C4—C51.412 (2)C22—C251.531 (2)
C4—C91.506 (2)C22—H22A0.9900
C5—C101.505 (2)C22—H22B0.9900
C6—H6A0.9800C23—C251.541 (3)
C6—H6B0.9800C23—H23A0.9900
C6—H6C0.9800C23—H23B0.9900
C7—H7A0.9800C24—C251.536 (2)
C7—H7B0.9800C24—H24A0.9900
C7—H7C0.9800C24—H24B0.9900
C8—H8A0.9800C25—H251.0000
C8—H8B0.9800C26—H26A0.92 (2)
C8—H8C0.9800C26—H26B0.90 (2)
C9—H9A0.9800C26—H26C0.94 (2)
C9—H9B0.9800C27—H27A0.73 (2)
C9—H9C0.9800C27—H27B0.84 (2)
C10—H10A0.9800C27—H27C0.96 (2)
C10—H10B0.9800C28—H28A0.9800
C10—H10C0.9800C28—H28B0.9800
C11—C151.422 (2)C28—H28C0.9800
C13—Ti1—C1235.05 (6)H7A—C7—H7B109.5
C13—Ti1—C1434.51 (6)C2—C7—H7C109.5
C12—Ti1—C1457.56 (6)H7A—C7—H7C109.5
C13—Ti1—C2119.63 (6)H7B—C7—H7C109.5
C12—Ti1—C2154.45 (5)C3—C8—H8A109.5
C14—Ti1—C2103.62 (6)C3—C8—H8B109.5
C13—Ti1—C1139.23 (5)H8A—C8—H8B109.5
C12—Ti1—C1153.58 (5)C3—C8—H8C109.5
C14—Ti1—C1137.36 (5)H8A—C8—H8C109.5
C2—Ti1—C134.74 (5)H8B—C8—H8C109.5
C13—Ti1—C1557.16 (6)C4—C9—H9A109.5
C12—Ti1—C1556.89 (5)C4—C9—H9B109.5
C14—Ti1—C1534.40 (5)H9A—C9—H9B109.5
C2—Ti1—C15118.75 (5)C4—C9—H9C109.5
C1—Ti1—C15149.30 (5)H9A—C9—H9C109.5
C13—Ti1—C387.04 (6)H9B—C9—H9C109.5
C12—Ti1—C3120.68 (5)C5—C10—H10A109.5
C14—Ti1—C382.14 (5)C5—C10—H10B109.5
C2—Ti1—C334.20 (5)H10A—C10—H10B109.5
C1—Ti1—C357.23 (5)C5—C10—H10C109.5
C15—Ti1—C3111.30 (5)H10A—C10—H10C109.5
C13—Ti1—C1158.12 (5)H10B—C10—H10C109.5
C12—Ti1—C1134.70 (5)C15—C11—C12105.61 (13)
C14—Ti1—C1157.75 (5)C15—C11—C16125.82 (13)
C2—Ti1—C11152.31 (5)C12—C11—C16128.26 (13)
C1—Ti1—C11162.12 (5)C15—C11—Ti171.96 (9)
C15—Ti1—C1134.28 (5)C12—C11—Ti170.57 (9)
C3—Ti1—C11139.68 (5)C16—C11—Ti1117.31 (10)
C13—Ti1—C482.43 (6)C13—C12—C11108.91 (14)
C12—Ti1—C4105.13 (5)C13—C12—Ti171.82 (9)
C14—Ti1—C497.12 (6)C11—C12—Ti174.73 (9)
C2—Ti1—C456.96 (5)C13—C12—H12125.5
C1—Ti1—C457.12 (5)C11—C12—H12125.5
C15—Ti1—C4131.51 (5)Ti1—C12—H12119.7
C3—Ti1—C434.20 (5)C14—C13—C12107.91 (14)
C11—Ti1—C4138.74 (5)C14—C13—Ti173.51 (10)
C13—Ti1—C5111.09 (6)C12—C13—Ti173.13 (9)
C12—Ti1—C5119.80 (5)C14—C13—H13126.0
C14—Ti1—C5130.89 (6)C12—C13—H13126.0
C2—Ti1—C556.98 (5)Ti1—C13—H13119.2
C1—Ti1—C534.49 (5)C13—C14—C15107.89 (14)
C15—Ti1—C5165.29 (5)C13—C14—Ti171.99 (9)
C3—Ti1—C556.50 (5)C15—C14—Ti173.91 (9)
C11—Ti1—C5150.48 (5)C13—C14—H14126.1
C4—Ti1—C533.78 (5)C15—C14—H14126.1
C13—Ti1—C27132.61 (6)Ti1—C14—H14119.9
C12—Ti1—C27115.71 (5)C14—C15—C11109.69 (14)
C14—Ti1—C27104.27 (6)C14—C15—Ti171.69 (9)
C2—Ti1—C2784.10 (5)C11—C15—Ti173.77 (8)
C1—Ti1—C2784.29 (5)C14—C15—H15125.2
C15—Ti1—C2775.55 (6)C11—C15—H15125.2
C3—Ti1—C27115.18 (5)Ti1—C15—H15121.0
C11—Ti1—C2781.67 (5)C11—C16—C21111.47 (12)
C4—Ti1—C27139.16 (5)C11—C16—C17112.20 (11)
C5—Ti1—C27116.09 (6)C21—C16—C17107.46 (12)
C13—Ti1—C26112.11 (6)C11—C16—Ga197.31 (9)
C12—Ti1—C2680.29 (6)C21—C16—Ga1114.82 (10)
C14—Ti1—C26136.13 (6)C17—C16—Ga1113.46 (10)
C2—Ti1—C26120.25 (5)C22—C17—C18108.45 (13)
C1—Ti1—C2686.05 (5)C22—C17—C16110.65 (12)
C15—Ti1—C26113.21 (5)C18—C17—C16109.91 (12)
C3—Ti1—C26135.06 (5)C22—C17—H17109.3
C11—Ti1—C2681.10 (5)C18—C17—H17109.3
C4—Ti1—C26105.80 (5)C16—C17—H17109.3
C5—Ti1—C2678.57 (5)C19—C18—C17109.91 (14)
C27—Ti1—C2682.04 (5)C19—C18—H18A109.7
C13—Ti1—Ga1116.37 (4)C17—C18—H18A109.7
C12—Ti1—Ga183.39 (4)C19—C18—H18B109.7
C14—Ti1—Ga1113.47 (4)C17—C18—H18B109.7
C2—Ti1—Ga1121.73 (4)H18A—C18—H18B108.2
C1—Ti1—Ga1102.07 (4)C23—C19—C18109.06 (15)
C15—Ti1—Ga179.79 (4)C23—C19—C20109.62 (16)
C3—Ti1—Ga1155.90 (4)C18—C19—C20109.35 (13)
C11—Ti1—Ga160.08 (3)C23—C19—H19109.6
C4—Ti1—Ga1147.35 (4)C18—C19—H19109.6
C5—Ti1—Ga1114.70 (4)C20—C19—H19109.6
C27—Ti1—Ga145.00 (3)C19—C20—C21109.78 (13)
C26—Ti1—Ga143.62 (3)C19—C20—H20A109.7
C13—Ti1—H27A128.8 (6)C21—C20—H20A109.7
C12—Ti1—H27A122.9 (6)C19—C20—H20B109.7
C14—Ti1—H27A96.0 (6)C21—C20—H20B109.7
C2—Ti1—H27A72.6 (6)H20A—C20—H20B108.2
C1—Ti1—H27A81.1 (6)C24—C21—C20108.49 (13)
C15—Ti1—H27A73.2 (6)C24—C21—C16110.60 (12)
C3—Ti1—H27A101.0 (6)C20—C21—C16110.01 (13)
C11—Ti1—H27A88.2 (6)C24—C21—H21109.2
C4—Ti1—H27A129.5 (6)C20—C21—H21109.2
C5—Ti1—H27A115.4 (6)C16—C21—H21109.2
C27—Ti1—H27A15.8 (6)C25—C22—C17109.89 (13)
C26—Ti1—H27A97.3 (6)C25—C22—H22A109.7
Ga1—Ti1—H27A60.6 (6)C17—C22—H22A109.7
C28—Ga1—C16125.07 (7)C25—C22—H22B109.7
C28—Ga1—C26108.64 (7)C17—C22—H22B109.7
C16—Ga1—C26103.44 (6)H22A—C22—H22B108.2
C28—Ga1—C27104.77 (7)C19—C23—C25109.49 (14)
C16—Ga1—C27105.71 (6)C19—C23—H23A109.8
C26—Ga1—C27108.45 (6)C25—C23—H23A109.8
C28—Ga1—Ti1149.61 (6)C19—C23—H23B109.8
C16—Ga1—Ti185.17 (4)C25—C23—H23B109.8
C26—Ga1—Ti160.85 (5)H23A—C23—H23B108.2
C27—Ga1—Ti158.56 (4)C25—C24—C21109.93 (14)
C2—C1—C5107.23 (13)C25—C24—H24A109.7
C2—C1—C6126.51 (14)C21—C24—H24A109.7
C5—C1—C6125.75 (14)C25—C24—H24B109.7
C2—C1—Ti172.59 (9)C21—C24—H24B109.7
C5—C1—Ti174.30 (9)H24A—C24—H24B108.2
C6—C1—Ti1125.01 (10)C22—C25—C24109.01 (13)
C3—C2—C1108.26 (13)C22—C25—C23109.48 (15)
C3—C2—C7124.70 (14)C24—C25—C23109.39 (15)
C1—C2—C7126.55 (14)C22—C25—H25109.6
C3—C2—Ti173.88 (9)C24—C25—H25109.6
C1—C2—Ti172.67 (8)C23—C25—H25109.6
C7—C2—Ti1125.61 (10)Ga1—C26—Ti175.53 (5)
C2—C3—C4108.13 (13)Ga1—C26—H26A130.7 (14)
C2—C3—C8126.31 (14)Ti1—C26—H26A60.0 (14)
C4—C3—C8125.02 (15)Ga1—C26—H26B106.6 (14)
C2—C3—Ti171.92 (8)Ti1—C26—H26B114.1 (14)
C4—C3—Ti173.36 (8)H26A—C26—H26B110 (2)
C8—C3—Ti1127.13 (11)Ga1—C26—H26C99.6 (13)
C5—C4—C3108.00 (13)Ti1—C26—H26C139.3 (14)
C5—C4—C9125.20 (14)H26A—C26—H26C100.7 (19)
C3—C4—C9126.22 (15)H26B—C26—H26C106.1 (19)
C5—C4—Ti173.26 (8)Ga1—C27—Ti176.45 (5)
C3—C4—Ti172.44 (8)Ga1—C27—H27A131.8 (17)
C9—C4—Ti1126.85 (11)Ti1—C27—H27A56.5 (17)
C4—C5—C1108.35 (13)Ga1—C27—H27B103.9 (14)
C4—C5—C10124.06 (15)Ti1—C27—H27B119.3 (14)
C1—C5—C10127.09 (16)H27A—C27—H27B107 (2)
C4—C5—Ti172.96 (9)Ga1—C27—H27C95.7 (12)
C1—C5—Ti171.22 (8)Ti1—C27—H27C131.1 (13)
C10—C5—Ti1128.02 (11)H27A—C27—H27C107 (2)
C1—C6—H6A109.5H27B—C27—H27C109.4 (18)
C1—C6—H6B109.5Ga1—C28—H28A109.5
H6A—C6—H6B109.5Ga1—C28—H28B109.5
C1—C6—H6C109.5H28A—C28—H28B109.5
H6A—C6—H6C109.5Ga1—C28—H28C109.5
H6B—C6—H6C109.5H28A—C28—H28C109.5
C2—C7—H7A109.5H28B—C28—H28C109.5
C2—C7—H7B109.5
C5—C1—C2—C30.94 (16)C12—C13—C14—Ti165.56 (12)
C6—C1—C2—C3173.10 (15)C13—C14—C15—C110.01 (19)
Ti1—C1—C2—C365.84 (10)Ti1—C14—C15—C1164.46 (11)
C5—C1—C2—C7171.35 (14)C13—C14—C15—Ti164.45 (12)
C6—C1—C2—C70.8 (2)C12—C11—C15—C140.17 (18)
Ti1—C1—C2—C7121.87 (15)C16—C11—C15—C14174.25 (14)
C5—C1—C2—Ti166.78 (10)Ti1—C11—C15—C1463.15 (12)
C6—C1—C2—Ti1121.06 (15)C12—C11—C15—Ti162.98 (11)
C1—C2—C3—C40.13 (17)C16—C11—C15—Ti1111.10 (15)
C7—C2—C3—C4172.59 (14)C15—C11—C16—C21156.47 (15)
Ti1—C2—C3—C464.91 (10)C12—C11—C16—C2130.8 (2)
C1—C2—C3—C8171.72 (15)Ti1—C11—C16—C21116.80 (11)
C7—C2—C3—C80.7 (2)C15—C11—C16—C1735.9 (2)
Ti1—C2—C3—C8123.24 (16)C12—C11—C16—C17151.37 (15)
C1—C2—C3—Ti165.04 (10)Ti1—C11—C16—C17122.62 (11)
C7—C2—C3—Ti1122.49 (15)C15—C11—C16—Ga183.18 (15)
C2—C3—C4—C51.17 (17)C12—C11—C16—Ga189.56 (16)
C8—C3—C4—C5170.82 (15)Ti1—C11—C16—Ga13.55 (10)
Ti1—C3—C4—C565.14 (10)C11—C16—C17—C2263.70 (16)
C2—C3—C4—C9172.80 (15)C21—C16—C17—C2259.17 (15)
C8—C3—C4—C90.8 (3)Ga1—C16—C17—C22172.79 (9)
Ti1—C3—C4—C9123.23 (16)C11—C16—C17—C18176.55 (13)
C2—C3—C4—Ti163.97 (10)C21—C16—C17—C1860.58 (16)
C8—C3—C4—Ti1124.05 (16)Ga1—C16—C17—C1867.47 (14)
C3—C4—C5—C11.75 (17)C22—C17—C18—C1960.40 (16)
C9—C4—C5—C1173.49 (15)C16—C17—C18—C1960.68 (17)
Ti1—C4—C5—C162.84 (10)C17—C18—C19—C2360.83 (17)
C3—C4—C5—C10170.61 (14)C17—C18—C19—C2059.03 (19)
C9—C4—C5—C101.1 (2)C23—C19—C20—C2160.45 (18)
Ti1—C4—C5—C10124.79 (15)C18—C19—C20—C2159.06 (19)
C3—C4—C5—Ti164.60 (10)C19—C20—C21—C2460.25 (17)
C9—C4—C5—Ti1123.66 (16)C19—C20—C21—C1660.87 (18)
C2—C1—C5—C41.67 (17)C11—C16—C21—C2464.24 (16)
C6—C1—C5—C4173.90 (15)C17—C16—C21—C2459.08 (16)
Ti1—C1—C5—C463.97 (11)Ga1—C16—C21—C24173.66 (10)
C2—C1—C5—C10170.41 (15)C11—C16—C21—C20175.92 (12)
C6—C1—C5—C101.8 (3)C17—C16—C21—C2060.76 (16)
Ti1—C1—C5—C10123.96 (15)Ga1—C16—C21—C2066.50 (14)
C2—C1—C5—Ti165.64 (10)C18—C17—C22—C2559.99 (16)
C6—C1—C5—Ti1122.13 (15)C16—C17—C22—C2560.63 (16)
C15—C11—C12—C130.26 (18)C18—C19—C23—C2560.07 (18)
C16—C11—C12—C13174.15 (15)C20—C19—C23—C2559.62 (18)
Ti1—C11—C12—C1364.19 (12)C20—C21—C24—C2560.31 (16)
C15—C11—C12—Ti163.92 (11)C16—C21—C24—C2560.43 (17)
C16—C11—C12—Ti1109.97 (15)C17—C22—C25—C2459.51 (18)
C11—C12—C13—C140.26 (19)C17—C22—C25—C2360.12 (17)
Ti1—C12—C13—C1465.81 (12)C21—C24—C25—C2259.47 (18)
C11—C12—C13—Ti166.08 (11)C21—C24—C25—C2360.21 (18)
C12—C13—C14—C150.16 (19)C19—C23—C25—C2259.94 (18)
Ti1—C13—C14—C1565.72 (12)C19—C23—C25—C2459.45 (19)
 

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