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Volume 68 
Part 11 
Page m1425  
November 2012  

Received 11 October 2012
Accepted 24 October 2012
Online 31 October 2012

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.003 Å
Disorder in main residue
R = 0.027
wR = 0.072
Data-to-parameter ratio = 19.8
Details
Open access

Di-[mu]-sulfido-bis{[rac-1,2-bis([eta]5-4,5,6,7-tetrahydroinden-1-yl)ethane]zirconium(IV)} toluene monosolvate

aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
Correspondence e-mail: martin.haehnel@catalysis.de

The title dimeric zirconium complex, [Zr2(C20H24)2S2]·C7H8, was obtained from the reaction of (ebthi)Zr([eta]2-Me3Si-C2-SiMe3) [ebthi is rac-1,2-bis([eta]5-4,5,6,7-tetrahydroinden-1-yl)ethane] and S=C=N-ada (ada = adamantan-1-yl) along with the formation of the isonitrile C[triple bond]N-ada. Each ZrIV atom is coordinated by the sterically hindered ebthi ligand and two [mu]-sulfide ligands in a strongly distorted tetrahedral geometry. The [ZrS]2 unit is almost planar (mean deviation from the best plane of the four atoms = 0.025 Å). A -CH2-CH2- group in one ebthi ligand was disordered over two sites, with refined occupancy factors of 0.551 (6) and 0.449 (6). The asymmetric unit also contains a toluene solvent molecule.

Related literature

For [mu]-sulfide-bridged [Cp2M([mu]-S)]2 metallocenes (Cp = C5H5), see: for M = Zr, Bottomley et al. (1986[Bottomley, F., Drummond, D. F., Egharevba, G. O. & White, P. S. (1986). Organometallics, 5, 1620-1625.]); Hey et al. (1987[Hey, E., Lappert, M. F., Atwood, J. L. & Bott, S. G. (1987). Chem. Commun. pp. 421-422.]); for M = Nb, Skripkin et al. (1984[Skripkin, Y. V., Eremenko, I. L., Pasynskii, A. A., Struchkov, Y. T. & Shklover, V. E. (1984). J. Organomet. Chem. 267, 285-292.]). Furthermore, for [Cp'2Th([mu]-S)]2 (Cp' = 1,2,4-tri-tert-butylcyclopentadienyl), see: Ren et al. (2011[Ren, W., Zi, G., Fang, D. & Walter, M. D. (2011). J. Am. Chem. Soc. 133, 13183-13196.]); for [Cp'2Ta([mu]-S)]2 (Cp' = C5H4Me), see: Winkler et al. (1998[Winkler, U., Khan, M. A. & Nicholas, K. M. (1998). Inorg. Chem. Commun. 1, 317-319.]). The starting alkyne complex (ebthi)Zr([eta]2-Me3Si-C2-SiMe3) was described by Lefeber et al. (1996[Lefeber, C., Baumann, W., Tillack, A., Kempe, R., Görls, H. & Rosenthal, U. (1996). Organometallics, 15, 3486-3490.]). For [mu]-sulfide complexes with a further bridged ligand Cp'M([mu]-S)2LMCp', L = [mu]2-[eta]10-fulvalene, Cp' = Cp, M = Zr, see: Wielstra et al. (1990[Wielstra, Y., Gambarotta, S., Spek, A. L. & Smeets, W. J. J. (1990). Organometallics, 9, 2142-2148.]), L = [mu]2-bis([eta]5-cyclopentadienyl)dimethylsilane, Cp' = Cp, M = Zr, see: Cacciola et al. (1992[Cacciola, J., Reddy, K. P. & Petersen, J. L. (1992). Organometallics, 11, 665-672.]), L = [mu]2-bis([eta]5-cyclopentadienyl)dimethylsilane, Cp' = Cp* (C5Me5), M = Zr, see: Burstynowicz & Petersen (1995[Burstynowicz, L. M. & Petersen, J. L. (1995). J. Cluster Sci. 6, 93-106.]).

[Scheme 1]

Experimental

Crystal data
  • [Zr2(C20H24)2S2]·C7H8

  • Mr = 867.48

  • Monoclinic, P 21 /n

  • a = 12.6436 (3) Å

  • b = 20.9735 (4) Å

  • c = 14.8855 (3) Å

  • [beta] = 105.092 (2)°

  • V = 3811.20 (14) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.69 mm-1

  • T = 150 K

  • 0.60 × 0.30 × 0.25 mm

Data collection
  • Stoe IPDS II diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005[Stoe & Cie (2005). X-SHAPE, X-RED32 and X-AREA. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.777, Tmax = 0.854

  • 65438 measured reflections

  • 9109 independent reflections

  • 7869 reflections with I > 2[sigma](I)

  • Rint = 0.036

Refinement
  • R[F2 > 2[sigma](F2)] = 0.027

  • wR(F2) = 0.072

  • S = 1.05

  • 9109 reflections

  • 460 parameters

  • 15 restraints

  • H-atom parameters constrained

  • [Delta][rho]max = 1.30 e Å-3

  • [Delta][rho]min = -0.89 e Å-3

Data collection: X-AREA (Stoe & Cie, 2005[Stoe & Cie (2005). X-SHAPE, X-RED32 and X-AREA. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2450 ).


References

Bottomley, F., Drummond, D. F., Egharevba, G. O. & White, P. S. (1986). Organometallics, 5, 1620-1625.  [CrossRef] [ChemPort]
Burstynowicz, L. M. & Petersen, J. L. (1995). J. Cluster Sci. 6, 93-106.  [CrossRef] [ChemPort]
Cacciola, J., Reddy, K. P. & Petersen, J. L. (1992). Organometallics, 11, 665-672.  [CrossRef] [ChemPort]
Hey, E., Lappert, M. F., Atwood, J. L. & Bott, S. G. (1987). Chem. Commun. pp. 421-422.
Lefeber, C., Baumann, W., Tillack, A., Kempe, R., Görls, H. & Rosenthal, U. (1996). Organometallics, 15, 3486-3490.  [CrossRef] [ChemPort]
Ren, W., Zi, G., Fang, D. & Walter, M. D. (2011). J. Am. Chem. Soc. 133, 13183-13196.  [CrossRef] [ChemPort] [PubMed]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Skripkin, Y. V., Eremenko, I. L., Pasynskii, A. A., Struchkov, Y. T. & Shklover, V. E. (1984). J. Organomet. Chem. 267, 285-292.  [CrossRef] [ChemPort]
Stoe & Cie (2005). X-SHAPE, X-RED32 and X-AREA. Stoe & Cie, Darmstadt, Germany.
Wielstra, Y., Gambarotta, S., Spek, A. L. & Smeets, W. J. J. (1990). Organometallics, 9, 2142-2148.  [CrossRef] [ChemPort]
Winkler, U., Khan, M. A. & Nicholas, K. M. (1998). Inorg. Chem. Commun. 1, 317-319.  [CrossRef] [ChemPort]


Acta Cryst (2012). E68, m1425  [ doi:10.1107/S1600536812044121 ]

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