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Volume 69 
Part 9 
Page m505  
September 2013  

Received 2 May 2013
Accepted 13 August 2013
Online 21 August 2013

Key indicators
Single-crystal X-ray study
T = 173 K
Mean [sigma](C-C) = 0.006 Å
R = 0.029
wR = 0.068
Data-to-parameter ratio = 21.6
Details
Open access

Trichlorido{methyl[4-(methylimino)pent-2-en-2-yl]azanido-[kappa]2N,N'}hafnium(IV)

aDepartment of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
Correspondence e-mail: masuda.hideki@nitech.ac.jp

The title complex, [Hf(C29H41N2)Cl3], was synthesized from HfCl4 and HC[C(Me)N(iPr2C6H3)]2Li(Et2O) in toluene. The structure is isotypic with those of TiIV and ZrIV complexes reported previously [Nikiforov et al. (2007[Nikiforov, G. B., Roesky, H. W., Jones, P. G., Oswald, R. B. & Noltemeyer, M. (2007). Dalton Trans. pp. 4149-4159.]). Dalton Trans. pp. 4149-4159; Kakaliou et al. (1999[Kakaliou, L., Scanlon, W. J., Qian, B. S., Baek, S. W., Smith, M. R. & Motry, D. H. (1999). Inorg. Chem. 38, 5964-5977.]). Inorg. Chem. 38, 5964-5977]. There is a crystallographic mirror plane containing the Hf atom, one chloride ligand and the central diketiminate C atom. The HfIV ion has slightly distorted square-pyramidal geometry surrounded by two N atoms from the [beta]-diketiminate ligand and by three Cl- anions. Coordination bond lengths are Hf-N = 2.181 (3) Å, and Hf-Cl = 2.3148 (15) and 2.3727 (12) Å.

Related literature

For complexes bearing [beta]-diketiminate ligands, see: Bourget-Merle et al. (2002[Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev. 102, 3031-3065.]); Hamaki et al. (2006[Hamaki, H., Takeda, N. & Tokitoh, N. (2006). Organometallics, 25, 2457-2464.]). For the synthesis of the precursor of the [beta]-diketiminate in the title compound, see: Stender et al. (2001[Stender, M., Wright, R. J., Eichler, B. E., Prust, J., Olmstead, M. M., Roesky, H. W. & Power, P. P. (2001). J. Chem. Soc. Dalton Trans. pp. 3465-3469.]). For isotypic TiIV and ZrIV complexes, see: Nikiforov et al. (2007[Nikiforov, G. B., Roesky, H. W., Jones, P. G., Oswald, R. B. & Noltemeyer, M. (2007). Dalton Trans. pp. 4149-4159.]) and Kakaliou et al. (1999[Kakaliou, L., Scanlon, W. J., Qian, B. S., Baek, S. W., Smith, M. R. & Motry, D. H. (1999). Inorg. Chem. 38, 5964-5977.]), respectively.

[Scheme 1]

Experimental

Crystal data
  • [Hf(C29H41N2)Cl3]

  • Mr = 702.51

  • Orthorhombic, P n m a

  • a = 13.980 (3) Å

  • b = 21.808 (4) Å

  • c = 9.8492 (16) Å

  • V = 3002.8 (9) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 3.75 mm-1

  • T = 173 K

  • 0.20 × 0.10 × 0.10 mm

Data collection
  • Rigaku Mercury70 diffractometer

  • 22083 measured reflections

  • 3527 independent reflections

  • 3132 reflections with F2 > 2[sigma](F2)

  • Rint = 0.049

Refinement
  • R[F2 > 2[sigma](F2)] = 0.029

  • wR(F2) = 0.068

  • S = 1.10

  • 3527 reflections

  • 163 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 2.65 e Å-3

  • [Delta][rho]min = -1.02 e Å-3

Data collection: CrystalClear (Rigaku/MSC, 2006[Rigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2006[Rigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.]); software used to prepare material for publication: CrystalStructure.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2479 ).


Acknowledgements

We gratefully acknowledge support of this work by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, and in part by a grant from the Knowledge Cluster Program.

References

Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev. 102, 3031-3065.  [ISI] [CrossRef] [PubMed] [ChemPort]
Hamaki, H., Takeda, N. & Tokitoh, N. (2006). Organometallics, 25, 2457-2464.  [CSD] [CrossRef] [ChemPort]
Kakaliou, L., Scanlon, W. J., Qian, B. S., Baek, S. W., Smith, M. R. & Motry, D. H. (1999). Inorg. Chem. 38, 5964-5977.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Nikiforov, G. B., Roesky, H. W., Jones, P. G., Oswald, R. B. & Noltemeyer, M. (2007). Dalton Trans. pp. 4149-4159.  [CSD] [CrossRef]
Rigaku/MSC (2006). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [details]
Stender, M., Wright, R. J., Eichler, B. E., Prust, J., Olmstead, M. M., Roesky, H. W. & Power, P. P. (2001). J. Chem. Soc. Dalton Trans. pp. 3465-3469.  [CSD] [CrossRef]


Acta Cryst (2013). E69, m505  [ doi:10.1107/S1600536813022745 ]

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