Tri­bromo(η⁵-1,2,3-tri­methyl­cyclo­penta­dienyl)­titanium(IV)

The crystal structure of the title compound, [TiBr₃(Me₃Cp)], where Me₃Cp is 1,2,3-tri­methyl­cyclo­penta­dienyl (C₈H₁₁), has been determined. The mol­ecule has a typical piano-stool structure in which one η⁵-bonded tri­methyl­cyclo­penta­dienyl ring and three bromide ligands occupy the pseudo-tetrahedral coord­ination sites around the titanium(IV) centre. The Ti–ring distance is 2.0162 (16) Å.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.026
• wR factor = 0.064
• Data-to-parameter ratio = 23.7

checkCIF/PLATON results

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Computing details

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Tribromo(η⁵-1,2,3-trimethylcyclopentadienyl)titanium(IV)

Crystal data

[TiBr3(C8H11)]	Z = 2
Mr = 394.80	F(000) = 372
Triclinic, P1	Dx = 2.239 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8210 (3) Å	Cell parameters from 6322 reflections
b = 8.5280 (3) Å	θ = 1–27.5°
c = 11.0770 (3) Å	µ = 10.91 mm^−1
α = 92.547 (2)°	T = 150 K
β = 95.901 (2)°	Prism, red
γ = 113.3971 (17)°	0.4 × 0.25 × 0.18 mm
V = 585.66 (4) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	2681 independent reflections
Radiation source: fine-focus sealed tube	2362 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 1.9°
φ and ω scans to fill the Ewald sphere	h = −8→8
Absorption correction: integration Gaussian integration (Coppens, 1970)	k = −11→11
Tmin = 0.075, Tmax = 0.301	l = −14→14
9260 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 0.5446P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2681 reflections	Δρmax = 0.80 e Å^−3
113 parameters	Δρmin = −0.70 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0120 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ti1	0.44405 (7)	0.30177 (6)	0.28270 (4)	0.01755 (12)
Br1	0.35027 (5)	0.54335 (4)	0.28845 (3)	0.03004 (10)
Br2	0.25134 (5)	0.14453 (5)	0.09349 (3)	0.03379 (11)
Br3	0.23922 (5)	0.12820 (4)	0.42712 (3)	0.03421 (11)
C1	0.7383 (5)	0.2831 (4)	0.3942 (2)	0.0229 (6)
H1	0.7206	0.2276	0.4652	0.028*
C2	0.7850 (5)	0.4577 (4)	0.3859 (3)	0.0239 (6)
H2	0.8023	0.5373	0.4507	0.029*
C3	0.8012 (4)	0.4928 (4)	0.2634 (3)	0.0216 (6)
C4	0.7620 (4)	0.3361 (4)	0.1947 (2)	0.0195 (5)
C5	0.7228 (4)	0.2062 (4)	0.2759 (2)	0.0210 (6)
C6	0.8657 (5)	0.6657 (4)	0.2161 (3)	0.0360 (8)
H6A	0.8519	0.7446	0.2758	0.054*
H6B	0.7739	0.6569	0.1421	0.054*
H6C	1.0126	0.7064	0.2001	0.054*
C7	0.7807 (5)	0.3157 (4)	0.0623 (3)	0.0303 (7)
H7A	0.7368	0.3947	0.0200	0.045*
H7B	0.6897	0.2004	0.0293	0.045*
H7C	0.9275	0.3389	0.0523	0.045*
C8	0.6782 (5)	0.0226 (4)	0.2423 (3)	0.0304 (7)
H8A	0.8112	0.0120	0.2335	0.046*
H8B	0.5838	−0.0168	0.1667	0.046*
H8C	0.6112	−0.0455	0.3051	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0143 (2)	0.0189 (3)	0.0173 (2)	0.0051 (2)	0.00061 (18)	−0.00115 (18)
Br1	0.02342 (17)	0.02703 (18)	0.04276 (19)	0.01416 (13)	0.00262 (13)	0.00020 (13)
Br2	0.02421 (17)	0.0442 (2)	0.02602 (16)	0.01067 (15)	−0.00666 (12)	−0.01377 (14)
Br3	0.02570 (17)	0.0375 (2)	0.03206 (17)	0.00306 (14)	0.00868 (13)	0.01062 (14)
C1	0.0207 (14)	0.0282 (16)	0.0202 (13)	0.0109 (12)	−0.0002 (11)	0.0024 (12)
C2	0.0172 (13)	0.0252 (15)	0.0253 (13)	0.0072 (12)	−0.0046 (11)	−0.0082 (12)
C3	0.0141 (13)	0.0188 (14)	0.0312 (14)	0.0061 (11)	0.0021 (11)	0.0017 (11)
C4	0.0146 (12)	0.0202 (14)	0.0237 (13)	0.0071 (11)	0.0027 (10)	0.0017 (11)
C5	0.0165 (13)	0.0215 (15)	0.0254 (13)	0.0087 (11)	0.0004 (10)	0.0015 (11)
C6	0.0276 (17)	0.0201 (16)	0.060 (2)	0.0085 (14)	0.0095 (15)	0.0080 (15)
C7	0.0297 (16)	0.0355 (18)	0.0272 (15)	0.0135 (15)	0.0092 (12)	0.0029 (13)
C8	0.0292 (16)	0.0211 (16)	0.0413 (17)	0.0116 (13)	0.0020 (13)	0.0010 (13)

Geometric parameters (Å, º)

Ti1—C1	2.311 (3)	C3—C6	1.498 (4)
Ti1—C2	2.312 (3)	C4—C5	1.418 (4)
Ti1—C5	2.354 (3)	C4—C7	1.494 (4)
Ti1—C3	2.371 (3)	C5—C8	1.493 (4)
Ti1—C4	2.386 (3)	C6—H6A	0.9600
Ti1—Br1	2.3876 (5)	C6—H6B	0.9600
Ti1—Br2	2.3880 (5)	C6—H6C	0.9600
Ti1—Br3	2.3937 (6)	C7—H7A	0.9600
C1—C2	1.403 (4)	C7—H7B	0.9600
C1—C5	1.414 (4)	C7—H7C	0.9600
C1—H1	0.9300	C8—H8A	0.9600
C2—C3	1.408 (4)	C8—H8B	0.9600
C2—H2	0.9300	C8—H8C	0.9600
C3—C4	1.421 (4)
C1—Ti1—C2	35.34 (11)	C3—C2—H2	125.6
C1—Ti1—C5	35.28 (10)	Ti1—C2—H2	119.1
C2—Ti1—C5	58.54 (10)	C2—C3—C4	107.3 (2)
C1—Ti1—C3	58.45 (10)	C2—C3—C6	126.2 (3)
C2—Ti1—C3	34.96 (10)	C4—C3—C6	126.3 (3)
C5—Ti1—C3	58.23 (10)	C2—C3—Ti1	70.23 (16)
C1—Ti1—C4	58.17 (9)	C4—C3—Ti1	73.21 (16)
C2—Ti1—C4	58.00 (10)	C6—C3—Ti1	125.58 (19)
C5—Ti1—C4	34.80 (9)	C5—C4—C3	108.2 (2)
C3—Ti1—C4	34.76 (9)	C5—C4—C7	125.8 (3)
C1—Ti1—Br1	126.22 (8)	C3—C4—C7	125.8 (3)
C2—Ti1—Br1	92.99 (7)	C5—C4—Ti1	71.35 (15)
C5—Ti1—Br1	146.22 (8)	C3—C4—Ti1	72.03 (15)
C3—Ti1—Br1	88.09 (7)	C7—C4—Ti1	126.92 (19)
C4—Ti1—Br1	116.42 (7)	C1—C5—C4	107.5 (2)
C1—Ti1—Br2	127.63 (7)	C1—C5—C8	126.5 (3)
C2—Ti1—Br2	143.81 (8)	C4—C5—C8	126.0 (3)
C5—Ti1—Br2	93.49 (7)	C1—C5—Ti1	70.71 (15)
C3—Ti1—Br2	112.40 (7)	C4—C5—Ti1	73.85 (15)
C4—Ti1—Br2	85.86 (7)	C8—C5—Ti1	122.0 (2)
Br1—Ti1—Br2	102.71 (2)	C3—C6—H6A	109.5
C1—Ti1—Br3	85.45 (8)	C3—C6—H6B	109.5
C2—Ti1—Br3	105.96 (8)	H6A—C6—H6B	109.5
C5—Ti1—Br3	102.05 (7)	C3—C6—H6C	109.5
C3—Ti1—Br3	140.54 (7)	H6A—C6—H6C	109.5
C4—Ti1—Br3	136.84 (7)	H6B—C6—H6C	109.5
Br1—Ti1—Br3	103.30 (2)	C4—C7—H7A	109.5
Br2—Ti1—Br3	101.87 (2)	C4—C7—H7B	109.5
C2—C1—C5	108.1 (2)	H7A—C7—H7B	109.5
C2—C1—Ti1	72.36 (16)	C4—C7—H7C	109.5
C5—C1—Ti1	74.01 (15)	H7A—C7—H7C	109.5
C2—C1—H1	125.9	H7B—C7—H7C	109.5
C5—C1—H1	125.9	C5—C8—H8A	109.5
Ti1—C1—H1	119.5	C5—C8—H8B	109.5
C1—C2—C3	108.9 (2)	H8A—C8—H8B	109.5
C1—C2—Ti1	72.30 (16)	C5—C8—H8C	109.5
C3—C2—Ti1	74.81 (16)	H8A—C8—H8C	109.5
C1—C2—H2	125.6	H8B—C8—H8C	109.5