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Volume 69 
Part 1 
Pages m47-m48  
January 2013  

Received 13 November 2012
Accepted 29 November 2012
Online 12 December 2012

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Key indicators
Single-crystal Synchrotron study
T = 100 K
Mean [sigma](C-C) = 0.008 Å
Disorder in solvent or counterion
R = 0.051
wR = 0.164
Data-to-parameter ratio = 11.9
Details
Open access

A dimer of bis(N-heterocyclic carbene)rhodium(I) centres spanned by a dibenzo-18-crown-6 bridge from synchrotron radiation

Sumi Shrestha,a Mohan Bhadbhade,b Carolina Gimbert-Suriñacha and Stephen B. Colbrana*

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

The compound ([mu]-3,3',3'',3'''-{[2,5,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosa-1(22),9,11,13,23,25-hexaene-11,12,24,25-tetrayl]tetrakis(methylene)}tetrakis(1-methyl-1H-imidazol-2-yl))bis[([eta]4-cycloocta-1,4-diene)rhodium(I)] bis(hexafluoridophosphate) acetonitrile sesquisolvate dihydrate, [Rh2(C8H12)2(C40H42N8O6)](PF6)2·1.5CH3CN·2H2O, crystallized from acetonitrile under an atmosphere of diethyl ether. In the crystal structure, the complex cation exhibits two square-planar RhI centres, each bound by a cyclooctadiene (COD) ligand and by two adjacent imidazolylidene N-heterocyclic carbene (NHC) donors from the same phenoxy ring of the {[dibenzo-18-crown-6-11,12,24,25-tetrayl]tetrakis(methylene)}tetrakis(1-methyl-1H-imidazol-2-yl) (L) ligand. The dibenzo-crown ether bridge of L spans the Rh centres and forms hydrogen bonds with water molecules. One water molecule with half occupancy bridges adjacent macrocycles in the lattice. Another water with full occupancy forms weak hydrogen bonds to the crown ether O atoms and is, in turn, part hydrogen bonded by a lattice water with half occupancy. The latter water is within hydrogen-bonding distance of a fourth water also with partial occupancy. The result of these interactions is the formation of a layer in the ab plane. Two PF6- ions, one of which is twofold disordered, and one ordered and one twofold disordered (with 0.5 occupancy) lattice acetonitrile molecules complete the crystal structure.

Related literature

For the related complex [K(L){Rh(COD)}2][PF6]3, which has a potassium ion bound within the crown ether bridge of the ligand L, see: Shrestha et al. (2011[Shrestha, S., Gimbert-Suriñach, C., Bhadbhade, M. & Colbran, S. B. (2011). Eur. J. Inorg. Chem. 28, 4331-4337.]). For the well known Rh(I)(NHC)2(COD) centres, see: Mata et al. (2004[Mata, J. A., Chianese, A. R., Miecznikowski, J. R., Poyatos, M., Peris, E., Faller, J. W. & Crabtree, R. H. (2004). Organometallics, 23, 1253-1263.]); Riederer et al. (2010[Riederer, S. K. U., Gigler, P., Högerl, M. P., Herdtweck, E., Bechlars, B., Herrmann, W. A. & Kühn, F. (2010). Organometallics, 29, 5681-5692.]).

[Scheme 1]

Experimental

Crystal data

  • [Rh2(C8H12)2(C40H42N8O6)](PF6)2·1.5C2H3N·2H2O

  • Mr = 1540.55

  • Triclinic, [P \overline 1]

  • a = 10.510 (2) Å

  • b = 15.630 (3) Å

  • c = 23.280 (5) Å

  • [alpha] = 104.69 (3)°

  • [beta] = 90.20 (3)°

  • [gamma] = 109.58 (3)°

  • V = 3468.9 (12) Å3

  • Z = 2

  • Synchrotron radiation

  • [lambda] = 0.71073 Å

  • [mu] = 0.61 mm-1

  • T = 100 K

  • 0.03 × 0.02 × 0.01 mm
Data collection

  • 3-BM1 Australian Synchrotron diffractometer

  • 43942 measured reflections

  • 11473 independent reflections

  • 9939 reflections with I > 2[sigma](I)

  • Rint = 0.038
Refinement

  • R[F2 > 2[sigma](F2)] = 0.051

  • wR(F2) = 0.164

  • S = 1.33

  • 11473 reflections

  • 964 parameters

  • 270 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 1.15 e Å-3

  • [Delta][rho]min = -1.40 e Å-3

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O1M-H1MB...O2i 0.86 (1) 2.51 (3) 3.226 (5) 141 (3)
O1M-H1MB...O3i 0.86 (1) 2.50 (4) 3.076 (4) 125 (4)
O1M-H1MA...O1i 0.86 (1) 2.38 (3) 3.149 (5) 149 (4)
O1M-H1MA...O6i 0.86 (1) 2.39 (2) 3.138 (5) 145 (4)
O3W-H3WB...O5i 0.87 (1) 2.21 (9) 3.03 (2) 158 (23)
O3W-H3WA...O2ii 0.87 (1) 2.16 (10) 2.99 (2) 160 (27)
O1W-H1WA...O1M 0.87 (1) 2.00 (1) 2.796 (9) 151 (3)
O1W-H1WB...N1CN 0.87 (1) 2.06 (6) 2.805 (18) 143 (9)
Symmetry codes: (i) x, 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: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); 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: TK5170 ).

Acknowledgements

The authors thank the Australian Research Council (DP0988410) for financial support. They also thank the Australian Synchrotron Facility, Melbourne, for the X-ray data.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.  [ISI] [CrossRef] [ChemPort] [details]
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [ISI] [CrossRef] [ChemPort] [details]
Kabsch, W. (1993). J. Appl. Cryst. 26, 795-800.  [CrossRef] [ChemPort] [ISI] [details]
Mata, J. A., Chianese, A. R., Miecznikowski, J. R., Poyatos, M., Peris, E., Faller, J. W. & Crabtree, R. H. (2004). Organometallics, 23, 1253-1263.  [CSD] [CrossRef] [ChemPort]
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.  [ISI] [CrossRef] [ChemPort] [details]
Riederer, S. K. U., Gigler, P., Högerl, M. P., Herdtweck, E., Bechlars, B., Herrmann, W. A. & Kühn, F. (2010). Organometallics, 29, 5681-5692.  [CSD] [CrossRef] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Shrestha, S., Gimbert-Suriñach, C., Bhadbhade, M. & Colbran, S. B. (2011). Eur. J. Inorg. Chem. 28, 4331-4337.  [ISI] [CSD] [CrossRef]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]

Acta Cryst (2013). E69, m47-m48   [ doi:10.1107/S160053681204901X ]

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