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Acta Cryst. (2007). E63, m2174    [ doi:10.1107/S1600536807029868 ]

Dichloridobis([eta]5-methylcyclopentadienyl)hafnium(IV)

A. Wisniewska, K. Baranowska and J. Pikies

Abstract top

The title compound, [HfCl2(C6H7)2], has the Hf atom in a distorted pseudo-tetrahedral geometry. The molecule lies about a mirror plane.

Comment top

The discrete molecule has the Hf atom in a pseudotetrahedral geometry. The bond dimensions involving the metal atom are similar to those in [(η5-C5H5)2HfCl2] (Soloveichik et al., 1988) and [(η5-C2H5C5H4)2HfCl2] (Dong et al., 1982). The molecule lies about a mirror plane defined by the Hf—Cl1—Cl2 atoms.

Related literature top

For dichloridobis(η5-cyclopentadienyl)hafnium(IV), see Soloveichik et al. (1988), and for dichloridobis(η5-ethylcyclopentadienyl)hafnium(IV), see Dong et al. (1982).

For related literature, see: Lappert et al. (1981).

Experimental top

The compound was been obtained as a white powder in the reaction of (CH3C5H4)Li with HfCl4 in THF (Lappert et al., 1981). Slow crystallization from THF at 203 K yielded colourless crystals.

Refinement top

All H atoms were refined as riding on C atoms with aromatic C—H = 0.95 Å, methyl C—H = 0.98 Å, and Uiso(H) = 1.2Ueq(C) for CH groups, 1.5Ueq(C) for CH3 groups. The final difference Fourier map had a large peak at about 1 Å from Hf1.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Symmetry code i: x, 1/2 - y, z.
Dichloridobis(η5-methylcyclopentadienyl)hafnium(IV) top
Crystal data top
[HfCl2(C6H7)2]F(000) = 768
Mr = 407.62Dx = 2.203 Mg m−3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 7628 reflections
a = 12.1368 (5) Åθ = 2.1–32.3°
b = 15.4218 (6) ŵ = 8.89 mm−1
c = 6.5656 (4) ÅT = 120 K
V = 1228.89 (10) Å3Prism, colourless
Z = 40.16 × 0.14 × 0.1 mm
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		1132 independent reflections
graphite1096 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1Rint = 0.028
0.75° ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2005)		h = −14→14
Tmin = 0.36, Tmax = 0.469k = −10→18
5507 measured reflectionsl = −7→7
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.051P)2 + 0.3835P]
where P = (Fo2 + 2Fc2)/3
1132 reflections(Δ/σ)max = 0.001
74 parametersΔρmax = 2.01 e Å−3
0 restraintsΔρmin = −0.66 e Å−3
Crystal data top
[HfCl2(C6H7)2]V = 1228.89 (10) Å3
Mr = 407.62Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 12.1368 (5) ŵ = 8.89 mm−1
b = 15.4218 (6) ÅT = 120 K
c = 6.5656 (4) Å0.16 × 0.14 × 0.1 mm
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		1132 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2005)		1096 reflections with I > 2σ(I)
Tmin = 0.36, Tmax = 0.469Rint = 0.028
5507 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.064Δρmax = 2.01 e Å−3
S = 1.11Δρmin = −0.66 e Å−3
1132 reflectionsAbsolute structure: ?
74 parametersFlack 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
Hf10.080494 (13)0.250.90179 (3)0.01576 (14)
Cl10.27234 (9)0.251.01196 (18)0.0244 (3)
Cl20.12988 (9)0.250.5433 (2)0.0231 (3)
C1−0.0143 (3)0.1133 (2)0.7926 (5)0.0254 (7)
H1−0.03670.10710.65470.031*
C2−0.0770 (2)0.1505 (3)0.9496 (8)0.0265 (9)
H2−0.14940.17320.93670.032*
C3−0.0140 (3)0.1482 (2)1.1292 (6)0.0266 (8)
H3−0.03580.16991.25850.032*
C40.0869 (3)0.1082 (4)1.0834 (7)0.0270 (12)
H40.14480.09741.17750.032*
C50.0882 (3)0.0865 (3)0.8746 (8)0.0277 (11)
C60.1786 (3)0.0414 (3)0.7601 (6)0.0409 (11)
H6A0.24980.05540.82220.061*
H6B0.17820.06060.61780.061*
H6C0.1668−0.02150.76550.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hf10.01493 (18)0.01262 (19)0.01974 (19)0−0.00026 (5)0
Cl10.0182 (5)0.0260 (6)0.0289 (7)0−0.0023 (5)0
Cl20.0238 (6)0.0233 (6)0.0223 (5)00.0005 (5)0
C10.0314 (16)0.0187 (17)0.0262 (18)−0.0100 (13)−0.0001 (14)0.0005 (14)
C20.019 (2)0.017 (2)0.043 (2)−0.0055 (11)0.0028 (14)0.003 (2)
C30.0326 (19)0.0187 (17)0.0285 (18)−0.0076 (15)0.0119 (15)−0.0009 (14)
C40.023 (2)0.020 (3)0.038 (3)−0.0034 (13)−0.0037 (12)0.0115 (17)
C50.029 (2)0.012 (2)0.042 (3)−0.0026 (13)0.0113 (14)0.0025 (17)
C60.042 (2)0.016 (2)0.065 (3)0.0017 (14)0.023 (2)0.0012 (14)
Geometric parameters (Å, °) top
Hf1—Cl22.4286 (13)C2—C31.406 (7)
Hf1—Cl12.4381 (11)C2—H20.95
Hf1—C3i2.451 (4)C3—C41.404 (6)
Hf1—C2i2.472 (4)C3—H30.95
Hf1—C4i2.492 (5)C4—C51.411 (6)
Hf1—C1i2.507 (3)C4—H40.95
Hf1—C5i2.529 (5)C5—C61.502 (6)
C1—C21.404 (6)C6—H6A0.98
C1—C51.416 (5)C6—H6B0.98
C1—H10.95C6—H6C0.98
Cl2—Hf1—Cl192.97 (4)C2—C1—C5108.4 (4)
Cl2—Hf1—C3i134.90 (9)C2—C1—H1125.8
Cl1—Hf1—C3i105.43 (10)C5—C1—H1125.8
Cl2—Hf1—C2i108.30 (13)C1—C2—C3108.1 (3)
Cl1—Hf1—C2i134.50 (11)C1—C2—H2125.9
C3i—Hf1—C2i33.18 (16)C3—C2—H2125.9
Cl2—Hf1—C4i117.13 (12)C4—C3—C2107.8 (4)
Cl1—Hf1—C4i80.11 (8)C4—C3—H3126.1
C3i—Hf1—C4i32.99 (13)C2—C3—H3126.1
C2i—Hf1—C4i54.43 (13)C3—C4—C5108.8 (3)
Cl2—Hf1—C1i80.56 (8)C3—C4—H4125.6
Cl1—Hf1—C1i121.53 (8)C5—C4—H4125.6
C3i—Hf1—C1i54.62 (11)C4—C5—C1106.9 (4)
C2i—Hf1—C1i32.76 (14)C4—C5—C6127.2 (4)
C4i—Hf1—C1i54.05 (13)C1—C5—C6125.9 (4)
Cl2—Hf1—C5i85.55 (11)C5—C6—H6A109.5
Cl1—Hf1—C5i89.19 (9)C5—C6—H6B109.5
C3i—Hf1—C5i54.69 (14)H6A—C6—H6B109.5
C2i—Hf1—C5i54.44 (13)C5—C6—H6C109.5
C4i—Hf1—C5i32.63 (15)H6A—C6—H6C109.5
C1i—Hf1—C5i32.66 (12)H6B—C6—H6C109.5
Symmetry codes: (i) x, −y+1/2, z.
Table 1
Selected geometric parameters (Å, °) top
Hf1—Cl22.4286 (13)Hf1—Cl12.4381 (11)
Cl2—Hf1—Cl192.97 (4)
references
References top

Dong, Y.-C., Wu, S., Zhang, R.-G. & Chen, S.-S. (1982). Kexue Tongbao, 27, 1436–1440.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Lappert, M. F., Pickett, C. J., Riley, P. I. & Yarrow, P. I. W. (1981). J. Chem. Soc. Dalton Trans. pp. 805–812.

Oxford Diffraction, (2005). CrysAlis CCD and CrysAlis RED. Version 1.171.27p5 beta (release 01-04-2005 CrysAlis171.NET). Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Soloveichik, G. L., Arkhireeva, T. M., Belskij, V. K. & Bulychev, B. M. (1988). Metalloorg. Khim. 1, 226–230.