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Volume 70 
Part 1 
Pages m14-m15  
January 2014  

Received 27 November 2013
Accepted 29 November 2013
Online 11 December 2013

Key indicators
Single-crystal Synchrotron study
T = 100 K
Mean [sigma](C-C) = 0.005 Å
R = 0.025
wR = 0.060
Data-to-parameter ratio = 13.9
Details
Open access

Tri-[mu]-chlorido-bis­[([eta]5-penta­methyl­cyclo­penta­dien­yl)rhodium(III)] hexa­fluorido­phosphate from synchrotron radiation

aSchool of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia, and bMark Wainwright Analytical Centre, University of New South Wales, Sydney, NSW 2052, Australia
Correspondence e-mail: s.colbran@unsw.edu.au

In the title complex salt, [{([eta]5-C5Me5)Rh}2([mu]-Cl)3]PF6, the dinuclear, single-charged cation is formed by the cojoining of two classic ([eta]5-C5Me5)RhCl3 `piano-stool' units by bridging of the three choride ligand `legs'. The crystal structure shows several close H...F contacts between the hexa­fluorido­phosphate counter-ions and the C5Me5 ligands.

Related literature

Complexes of the ([eta]5-C5Me5)RhIII group, modified by innumerable co-ligands, exhibit a diverse and very useful chemistry, particularly as homogeneous catalysts, see, for example: McSkimming et al. (2013[McSkimming, A., Bhadbhade, M. M. & Colbran, S. B. (2013). Angew. Chem. Int. Ed. 52, 3411-3416.]); Brewster et al. (2013[Brewster, T. P., Miller, A. J. M., Heinekey, D. M. & Goldberg, K. I. (2013). J. Am. Chem. Soc. 135, 16022-16025.]); Yu, Wan & Li (2013[Yu, S., Wan, B. & Li, X. (2013). Org. Lett. 15, 3706-3709.]); Yu, Yu, Xiao, et al. (2013[Yu, X., Yu, S., Xiao, J., Wan, B. & Li, X. (2013). J. Org. Chem. 78, 5444-5452.]), Becerra et al. (2013[Becerra, A., Contreras, R., Carmona, D., Lahoz, F. J. & García-Orduña, P. (2013). Dalton Trans. 42, 11640-11651.]); Gupta et al. (2013[Gupta, G., Garci, A., Murray, B. S., Dyson, P. J., Fabre, G., Trouillas, P., Giannini, F., Furrer, J., Süss-Fink, G. & Therrien, B. (2013). Dalton Trans. 42, 15457-15463.]). The title complex salt, [{([eta]5-C5Me5)Rh}2([mu]-Cl)3][PF6], is a commonly encountered impurity produced in reactions of the much-used RhIII precursor [([eta]5-C5Me5)RhCl2]2 (Kang et al., 1969[Kang, J. W., Moseley, K. & Maitlis, P. M. (1969). J. Am. Chem. Soc. 91, 5970-5977.]; Booth et al., 1969[Booth, B. L., Haszeldine, R. N. & Hill, M. (1969). J. Chem. Soc. A, pp. 1299-1303.]). [{([eta]5-C5Me5)Rh}2([mu]-Cl)3][PF6] was first reported by Koelle (1990[Koelle, U. (1990). J. Electroanal. Chem. 292, 217-229.]), and often (co-)crystallizes with or instead of the desired product of a reaction employing [([eta]5-C5Me5)RhCl2]2 and anion meta­thesis with a simple [PF6]- salt. Several crystal structures of the [{([eta]5-C5Me5)Rh}2([mu]-Cl)3]+ cation with other counter-ions have been reported, including salts with [PtCl5(CH3CONH2)]- and [PtCl6]2- (Umakoshi et al., 1991[Umakoshi, K., Murata, K. & Yamashita, S. (1991). Inorg. Chim. Acta, 190, 185-191.]), [{(C6F5)2Pd([mu]-Cl)}2]2- (Ara et al., 2001[Ara, I., Berenguer, J. R., Eguizabal, E., Fornies, J., Lalinde, E. & Martin, A. (2001). Eur. J. Inorg. Chem. pp. 1631-1640.]), and BF4- (Liu et al., 2004[Liu, L., Zhang, Q.-F. & Leung, W.-H. (2004). Acta Cryst. E60, m509-m510.]) anions.

[Scheme 1]

Experimental

Crystal data
  • [Rh2(C10H15)2Cl3]PF6

  • Mr = 727.58

  • Triclinic, [P \overline 1]

  • a = 8.0970 (16) Å

  • b = 12.604 (3) Å

  • c = 14.441 (3) Å

  • [alpha] = 64.28 (3)°

  • [beta] = 82.42 (3)°

  • [gamma] = 86.70 (3)°

  • V = 1316.1 (6) Å3

  • Z = 2

  • Synchrotron radiation

  • [lambda] = 0.71073 Å

  • [mu] = 1.67 mm-1

  • T = 100 K

  • 0.02 × 0.02 × 0.01 mm

Data collection
  • 3-BM1 Australian Synchrotron diffractometer

  • 15787 measured reflections

  • 4158 independent reflections

  • 4064 reflections with I > 2[sigma](I)

  • Rint = 0.021

Refinement
  • R[F2 > 2[sigma](F2)] = 0.025

  • wR(F2) = 0.060

  • S = 1.09

  • 4158 reflections

  • 299 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 1.03 e Å-3

  • [Delta][rho]min = -0.57 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
C8A-H8AB...F3i 0.96 2.53 3.244 (5) 131
C10A-H10A...F1ii 0.96 2.43 3.328 (4) 156
C6B-H6BB...F1 0.96 2.49 3.152 (5) 126
Symmetry codes: (i) x-1, y+1, z; (ii) -x+1, -y+1, -z.

Data collection: BLU-ICE (McPhillips et al., 2002[McPhillips, T. M., McPhillips, S. E., Chiu, H.-J., Cohen, A. E., Deacon, A. M., Ellis, P. J., Garman, E., Gonzalez, A., Sauter, N. K., Phizackerley, R. P., Soltis, S. M. & Kuhn, P. (2002). J. Synchrotron Rad. 9, 401-406.]); cell refinement: XDS (Kabsch, 1993[Kabsch, W. (1993). J. Appl. Cryst. 26, 795-800.]); data reduction: XDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: CrystalMaker (CrystalMaker, 2013[CrystalMaker (2013). CrystalMaker. CrystalMaker Software Ltd, Oxford, England.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK5276 ).


Acknowledgements

We acknowledge support from the Australian Research Council (ARC DP130103514) and are grateful for Australian Synchrotron for MX2 beamline access.

References

Ara, I., Berenguer, J. R., Eguizabal, E., Fornies, J., Lalinde, E. & Martin, A. (2001). Eur. J. Inorg. Chem. pp. 1631-1640.  [CrossRef]
Becerra, A., Contreras, R., Carmona, D., Lahoz, F. J. & García-Orduña, P. (2013). Dalton Trans. 42, 11640-11651.  [CSD] [CrossRef] [ChemPort] [PubMed]
Booth, B. L., Haszeldine, R. N. & Hill, M. (1969). J. Chem. Soc. A, pp. 1299-1303.  [CrossRef]
Brewster, T. P., Miller, A. J. M., Heinekey, D. M. & Goldberg, K. I. (2013). J. Am. Chem. Soc. 135, 16022-16025.  [Web of Science] [CrossRef] [ChemPort]
CrystalMaker (2013). CrystalMaker. CrystalMaker Software Ltd, Oxford, England.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Gupta, G., Garci, A., Murray, B. S., Dyson, P. J., Fabre, G., Trouillas, P., Giannini, F., Furrer, J., Süss-Fink, G. & Therrien, B. (2013). Dalton Trans. 42, 15457-15463.  [CSD] [CrossRef] [ChemPort] [PubMed]
Kabsch, W. (1993). J. Appl. Cryst. 26, 795-800.  [CrossRef] [ChemPort] [Web of Science] [IUCr Journals]
Kang, J. W., Moseley, K. & Maitlis, P. M. (1969). J. Am. Chem. Soc. 91, 5970-5977.  [CrossRef] [ChemPort] [Web of Science]
Koelle, U. (1990). J. Electroanal. Chem. 292, 217-229.  [CrossRef] [ChemPort] [Web of Science]
Liu, L., Zhang, Q.-F. & Leung, W.-H. (2004). Acta Cryst. E60, m509-m510.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
McPhillips, T. M., McPhillips, S. E., Chiu, H.-J., Cohen, A. E., Deacon, A. M., Ellis, P. J., Garman, E., Gonzalez, A., Sauter, N. K., Phizackerley, R. P., Soltis, S. M. & Kuhn, P. (2002). J. Synchrotron Rad. 9, 401-406.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
McSkimming, A., Bhadbhade, M. M. & Colbran, S. B. (2013). Angew. Chem. Int. Ed. 52, 3411-3416.  [Web of Science] [CSD] [CrossRef] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Umakoshi, K., Murata, K. & Yamashita, S. (1991). Inorg. Chim. Acta, 190, 185-191.  [CSD] [CrossRef] [ChemPort] [Web of Science]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Yu, S., Wan, B. & Li, X. (2013). Org. Lett. 15, 3706-3709.  [Web of Science] [CSD] [CrossRef] [ChemPort] [PubMed]
Yu, X., Yu, S., Xiao, J., Wan, B. & Li, X. (2013). J. Org. Chem. 78, 5444-5452.  [CrossRef] [ChemPort] [PubMed]


Acta Cryst (2014). E70, m14-m15   [ doi:10.1107/S1600536813032480 ]

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