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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.
Supporting information
CCDC reference: 248756
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- R factor = 0.026
- wR factor = 0.064
- Data-to-parameter ratio = 23.7
checkCIF/PLATON results
No syntax errors found
No errors found in this datablock
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)
top
Crystal data top
[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) Å3 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0276P)2 + 0.5446P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0120 (8) |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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 |
Selected geometric parameters (Å, °). topTi1-Cg | 2.0162 (16) | Ti1-Br2 | 2.3880 (6) |
Ti1-Br1 | 2.3877 (6) | Ti1-Br3 | 2.3937 (6) |
| | | |
Cg-Ti1-Br1 | 116.04 (5) | Br1-Ti1-Br2 | 102.71 (2) |
Cg-Ti1-Br2 | 114.32 (4) | Br2-Ti1-Br3 | 101.87 (2) |
Cg-Ti1-Br3 | 116.61 (4) | Br3-Ti1-Br1 | 103.30 (2) |
| | | |
Pr-C3-C6 | 3.9 (2) | Pr-C4-C7 | 4.5 (2) |
Pr-C5-C8 | 0.8 (2) | | |
a) Cg is the centroid of the cyclopentadienyl ring.
b) Pr is the ring plane defined by atoms C1-C5. |
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