Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029868/ng2285sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029868/ng2285Isup2.hkl |
CCDC reference: 657600
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.
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.
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.
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).
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).
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. |
[HfCl2(C6H7)2] | F(000) = 768 |
Mr = 407.62 | Dx = 2.203 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 7628 reflections |
a = 12.1368 (5) Å | θ = 2.1–32.3° |
b = 15.4218 (6) Å | µ = 8.89 mm−1 |
c = 6.5656 (4) Å | T = 120 K |
V = 1228.89 (10) Å3 | Prism, colourless |
Z = 4 | 0.16 × 0.14 × 0.1 mm |
Oxford Diffraction KM-4 CCD diffractometer | 1132 independent reflections |
Graphite monochromator | 1096 reflections with I > 2σ(I) |
Detector resolution: 8.1883 pixels mm-1 | Rint = 0.028 |
0.75° ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2005) | h = −14→14 |
Tmin = 0.36, Tmax = 0.469 | k = −10→18 |
5507 measured reflections | l = −7→7 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-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 parameters | Δρmax = 2.01 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[HfCl2(C6H7)2] | V = 1228.89 (10) Å3 |
Mr = 407.62 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.1368 (5) Å | µ = 8.89 mm−1 |
b = 15.4218 (6) Å | T = 120 K |
c = 6.5656 (4) Å | 0.16 × 0.14 × 0.1 mm |
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 = 0.469 | Rint = 0.028 |
5507 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.11 | Δρmax = 2.01 e Å−3 |
1132 reflections | Δρmin = −0.66 e Å−3 |
74 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Hf1 | 0.080494 (13) | 0.25 | 0.90179 (3) | 0.01576 (14) | |
Cl1 | 0.27234 (9) | 0.25 | 1.01196 (18) | 0.0244 (3) | |
Cl2 | 0.12988 (9) | 0.25 | 0.5433 (2) | 0.0231 (3) | |
C1 | −0.0143 (3) | 0.1133 (2) | 0.7926 (5) | 0.0254 (7) | |
H1 | −0.0367 | 0.1071 | 0.6547 | 0.031* | |
C2 | −0.0770 (2) | 0.1505 (3) | 0.9496 (8) | 0.0265 (9) | |
H2 | −0.1494 | 0.1732 | 0.9367 | 0.032* | |
C3 | −0.0140 (3) | 0.1482 (2) | 1.1292 (6) | 0.0266 (8) | |
H3 | −0.0358 | 0.1699 | 1.2585 | 0.032* | |
C4 | 0.0869 (3) | 0.1082 (4) | 1.0834 (7) | 0.0270 (12) | |
H4 | 0.1448 | 0.0974 | 1.1775 | 0.032* | |
C5 | 0.0882 (3) | 0.0865 (3) | 0.8746 (8) | 0.0277 (11) | |
C6 | 0.1786 (3) | 0.0414 (3) | 0.7601 (6) | 0.0409 (11) | |
H6A | 0.2498 | 0.0554 | 0.8222 | 0.061* | |
H6B | 0.1782 | 0.0606 | 0.6178 | 0.061* | |
H6C | 0.1668 | −0.0215 | 0.7655 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hf1 | 0.01493 (18) | 0.01262 (19) | 0.01974 (19) | 0 | −0.00026 (5) | 0 |
Cl1 | 0.0182 (5) | 0.0260 (6) | 0.0289 (7) | 0 | −0.0023 (5) | 0 |
Cl2 | 0.0238 (6) | 0.0233 (6) | 0.0223 (5) | 0 | 0.0005 (5) | 0 |
C1 | 0.0314 (16) | 0.0187 (17) | 0.0262 (18) | −0.0100 (13) | −0.0001 (14) | 0.0005 (14) |
C2 | 0.019 (2) | 0.017 (2) | 0.043 (2) | −0.0055 (11) | 0.0028 (14) | 0.003 (2) |
C3 | 0.0326 (19) | 0.0187 (17) | 0.0285 (18) | −0.0076 (15) | 0.0119 (15) | −0.0009 (14) |
C4 | 0.023 (2) | 0.020 (3) | 0.038 (3) | −0.0034 (13) | −0.0037 (12) | 0.0115 (17) |
C5 | 0.029 (2) | 0.012 (2) | 0.042 (3) | −0.0026 (13) | 0.0113 (14) | 0.0025 (17) |
C6 | 0.042 (2) | 0.016 (2) | 0.065 (3) | 0.0017 (14) | 0.023 (2) | 0.0012 (14) |
Hf1—Cl2 | 2.4286 (13) | C2—C3 | 1.406 (7) |
Hf1—Cl1 | 2.4381 (11) | C2—H2 | 0.95 |
Hf1—C3i | 2.451 (4) | C3—C4 | 1.404 (6) |
Hf1—C2i | 2.472 (4) | C3—H3 | 0.95 |
Hf1—C4i | 2.492 (5) | C4—C5 | 1.411 (6) |
Hf1—C1i | 2.507 (3) | C4—H4 | 0.95 |
Hf1—C5i | 2.529 (5) | C5—C6 | 1.502 (6) |
C1—C2 | 1.404 (6) | C6—H6A | 0.98 |
C1—C5 | 1.416 (5) | C6—H6B | 0.98 |
C1—H1 | 0.95 | C6—H6C | 0.98 |
Cl2—Hf1—Cl1 | 92.97 (4) | C2—C1—C5 | 108.4 (4) |
Cl2—Hf1—C3i | 134.90 (9) | C2—C1—H1 | 125.8 |
Cl1—Hf1—C3i | 105.43 (10) | C5—C1—H1 | 125.8 |
Cl2—Hf1—C2i | 108.30 (13) | C1—C2—C3 | 108.1 (3) |
Cl1—Hf1—C2i | 134.50 (11) | C1—C2—H2 | 125.9 |
C3i—Hf1—C2i | 33.18 (16) | C3—C2—H2 | 125.9 |
Cl2—Hf1—C4i | 117.13 (12) | C4—C3—C2 | 107.8 (4) |
Cl1—Hf1—C4i | 80.11 (8) | C4—C3—H3 | 126.1 |
C3i—Hf1—C4i | 32.99 (13) | C2—C3—H3 | 126.1 |
C2i—Hf1—C4i | 54.43 (13) | C3—C4—C5 | 108.8 (3) |
Cl2—Hf1—C1i | 80.56 (8) | C3—C4—H4 | 125.6 |
Cl1—Hf1—C1i | 121.53 (8) | C5—C4—H4 | 125.6 |
C3i—Hf1—C1i | 54.62 (11) | C4—C5—C1 | 106.9 (4) |
C2i—Hf1—C1i | 32.76 (14) | C4—C5—C6 | 127.2 (4) |
C4i—Hf1—C1i | 54.05 (13) | C1—C5—C6 | 125.9 (4) |
Cl2—Hf1—C5i | 85.55 (11) | C5—C6—H6A | 109.5 |
Cl1—Hf1—C5i | 89.19 (9) | C5—C6—H6B | 109.5 |
C3i—Hf1—C5i | 54.69 (14) | H6A—C6—H6B | 109.5 |
C2i—Hf1—C5i | 54.44 (13) | C5—C6—H6C | 109.5 |
C4i—Hf1—C5i | 32.63 (15) | H6A—C6—H6C | 109.5 |
C1i—Hf1—C5i | 32.66 (12) | H6B—C6—H6C | 109.5 |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [HfCl2(C6H7)2] |
Mr | 407.62 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 120 |
a, b, c (Å) | 12.1368 (5), 15.4218 (6), 6.5656 (4) |
V (Å3) | 1228.89 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.89 |
Crystal size (mm) | 0.16 × 0.14 × 0.1 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4 CCD |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2005) |
Tmin, Tmax | 0.36, 0.469 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5507, 1132, 1096 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.064, 1.11 |
No. of reflections | 1132 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.01, −0.66 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
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.