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Volume 69 
Part 9 
Pages m510-m511  
September 2013  

Received 17 June 2013
Accepted 14 August 2013
Online 21 August 2013

Key indicators
Single-crystal X-ray study
T = 120 K
Mean [sigma](C-C) = 0.009 Å
Disorder in main residue
R = 0.062
wR = 0.141
Data-to-parameter ratio = 10.9
Details
Open access

(2,2'-Bipyridine)chlorido[diethyl (2,2':6',2''-terpyridin-4-yl)phosphonate]ruthenium(II) hexafluoridophosphate acetonitrile/water solvate

The cationic complex in the title compound, [RuCl(C10H8N2)(C19H20N3O3P)]PF6·0.83CH3CN·0.17H2O, is a water-oxidation precatalyst functionalized for TiO2 attachment via terpyridine phosphonate. The The RuII atom in the complex has a distorted octahedral geometry due to the restricted bite angle [159.50 (18)°] of the terpyridyl ligand. The dihedral angle between the least-squares planes of the terpyridyl and bipyridyl moieties is 86.04 (14)°. The mean Ru-N bond length for bipyridine is 2.064 (5) Å, with the bond opposite to Ru-Cl being 0.068 Å shorter. For the substituted terpyridine, the mean Ru-N distance involving the outer N atoms trans to each other is 2.057 (6) Å, whereas the bond length involving the central N atom is 1.944 (5) Å. The Ru-Cl distance is 2.4073 (15) Å. The P atom of the phosphonate group lies in the same plane as its adjacent pyridyl ring, with the ordinary character of the bond between P and Ctpy [1.801 (6) Å] allowing for free rotation of the terpyridine substituent around the P-Ctpy axis. The acetonitrile solvent molecule was refined to be disordered with two water molecules; occupancies for the acetontrile and water molecules were 0.831 (9) and 0.169 (9), respectively. Also disordered was the PF6- counter-ion (over three positions) and one of the ethoxy substituents (with two positions). The crystal structure shows significant intra- and intermolecular H...X contacts, especially some involving the Cl- ligand.

Related literature

For a related crystal structure, see: Zakeeruddin et al. (1997[Zakeeruddin, S. M., Nazeeruddin, M. K., Pechy, P., Rotzinger, F. P., Humphry-Baker, R., Kalyanasundaram, K. & Grätzel, M. (1997). Inorg. Chem. 36, 5937-5946.]). For the structures of terpyridyl/bipyridyl RuII-chlorido compounds relevant to the comparative discussion, see: Chen et al. (2011[Chen, W., Rein, F. N., Scott, B. L. & Rocha, R. C. (2011). Chem. Eur. J. 17, 5595-5604.], 2013[Chen, W., Rein, F. N., Scott, B. L. & Rocha, R. C. (2013). Acta Cryst. E69, m79-m80.]); Jude et al. (2008[Jude, H., Rein, F. N., White, P. S., Dattelbaum, D. M. & Rocha, R. C. (2008). Inorg. Chem. 47, 7695-7702.], 2009[Jude, H., Rein, F. N., Chen, W., Scott, B. L., Dattelbaum, D. M. & Rocha, R. C. (2009). Eur. J. Inorg. Chem. pp. 683-690.], 2013[Jude, H., Scott, B. L. & Rocha, R. C. (2013). Acta Cryst. E69, m81-m82.]). For literature used in the synthetic preparations, see: Evans et al. (1973[Evans, I. P., Spencer, A. & Wilkinson, G. (1973). J. Chem. Soc. Dalton Trans. pp. 204-209.]); Jakubikova et al. (2009[Jakubikova, E., Chen, W., Dattelbaum, D. M., Rein, F. N., Rocha, R. C., Martin, R. L. & Batista, E. R. (2009). Inorg. Chem. 48, 10720-10725.]); Zakeeruddin et al. (1997[Zakeeruddin, S. M., Nazeeruddin, M. K., Pechy, P., Rotzinger, F. P., Humphry-Baker, R., Kalyanasundaram, K. & Grätzel, M. (1997). Inorg. Chem. 36, 5937-5946.]). For the catalytic properties of related complexes, see: Chen et al. (2009[Chen, W., Rein, F. N. & Rocha, R. C. (2009). Angew. Chem. Int. Ed. 48, 9672-9675.]); Concepcion et al. (2008[Concepcion, J. J., Jurss, J. W., Templeton, J. L. & Meyer, T. J. (2008). J. Am. Chem. Soc. 130, 16462-16463.]); Masaoka & Sakai (2009[Masaoka, S. & Sakai, K. (2009). Chem. Lett. 38, 182-183.]); Tseng et al. (2008[Tseng, H.-W., Zong, R., Muckerman, J. T. & Thummel, R. (2008). Inorg. Chem. 47, 11763-11773.]); Wasylenko et al. (2010[Wasylenko, D. J., Ganesamoorthy, C., Koivisto, B. D., Henderson, M. A. & Berlinguette, C. P. (2010). Inorg. Chem. 49, 2202-2209.]); Yagi et al. (2011[Yagi, M., Tajima, S., Komia, M. & Yamazakia, H. (2011). Dalton Trans. 40, 3802-3804.]).

[Scheme 1]

Experimental

Crystal data
  • [RuCl(C10H8N2)(C19H20N3O3P)]PF6·0.83C2H3N·0.17H2O

  • Mr = 847.23

  • Monoclinic, P 21 /n

  • a = 8.6367 (14) Å

  • b = 31.515 (5) Å

  • c = 12.696 (2) Å

  • [beta] = 100.155 (2)°

  • V = 3401.5 (9) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.71 mm-1

  • T = 120 K

  • 0.28 × 0.20 × 0.08 mm

Data collection
  • Bruker D8 with APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.826, Tmax = 0.945

  • 24414 measured reflections

  • 6233 independent reflections

  • 5056 reflections with I > 2[sigma](I)

  • Rint = 0.055

Refinement
  • R[F2 > 2[sigma](F2)] = 0.062

  • wR(F2) = 0.141

  • S = 1.14

  • 6233 reflections

  • 574 parameters

  • 394 restraints

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

  • [Delta][rho]max = 0.94 e Å-3

  • [Delta][rho]min = -1.20 e Å-3

Table 1
Selected bond lengths (Å)

Ru1-N2 1.944 (5)
Ru1-N4 2.030 (5)
Ru1-N1 2.053 (5)
Ru1-N3 2.061 (5)
Ru1-N5 2.098 (5)
Ru1-Cl1 2.4073 (15)
P1-O1 1.483 (5)
P1-O2 1.540 (5)
P1-O3B 1.541 (6)
P1-O3 1.554 (17)
P1-C8 1.801 (6)

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); 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: ZL2555 ).


Acknowledgements

This work was supported by the US Department of Energy through the Laboratory Directed Research and Development (LDRD) program at LANL.

References

Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Chen, W., Rein, F. N. & Rocha, R. C. (2009). Angew. Chem. Int. Ed. 48, 9672-9675.  [ISI] [CrossRef] [ChemPort]
Chen, W., Rein, F. N., Scott, B. L. & Rocha, R. C. (2011). Chem. Eur. J. 17, 5595-5604.  [CSD] [CrossRef] [ChemPort] [PubMed]
Chen, W., Rein, F. N., Scott, B. L. & Rocha, R. C. (2013). Acta Cryst. E69, m79-m80.  [CSD] [CrossRef] [ChemPort] [details]
Concepcion, J. J., Jurss, J. W., Templeton, J. L. & Meyer, T. J. (2008). J. Am. Chem. Soc. 130, 16462-16463.  [ISI] [CrossRef] [PubMed] [ChemPort]
Evans, I. P., Spencer, A. & Wilkinson, G. (1973). J. Chem. Soc. Dalton Trans. pp. 204-209.  [CrossRef]
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.  [ISI] [CrossRef] [details]
Jakubikova, E., Chen, W., Dattelbaum, D. M., Rein, F. N., Rocha, R. C., Martin, R. L. & Batista, E. R. (2009). Inorg. Chem. 48, 10720-10725.  [ISI] [CrossRef] [PubMed] [ChemPort]
Jude, H., Rein, F. N., Chen, W., Scott, B. L., Dattelbaum, D. M. & Rocha, R. C. (2009). Eur. J. Inorg. Chem. pp. 683-690.  [CSD] [CrossRef]
Jude, H., Rein, F. N., White, P. S., Dattelbaum, D. M. & Rocha, R. C. (2008). Inorg. Chem. 47, 7695-7702.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Jude, H., Scott, B. L. & Rocha, R. C. (2013). Acta Cryst. E69, m81-m82.  [CSD] [CrossRef] [ChemPort] [details]
Masaoka, S. & Sakai, K. (2009). Chem. Lett. 38, 182-183.  [ISI] [CrossRef] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [details]
Tseng, H.-W., Zong, R., Muckerman, J. T. & Thummel, R. (2008). Inorg. Chem. 47, 11763-11773.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Wasylenko, D. J., Ganesamoorthy, C., Koivisto, B. D., Henderson, M. A. & Berlinguette, C. P. (2010). Inorg. Chem. 49, 2202-2209.  [ISI] [CrossRef] [ChemPort] [PubMed]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [ISI] [CrossRef] [ChemPort] [details]
Yagi, M., Tajima, S., Komia, M. & Yamazakia, H. (2011). Dalton Trans. 40, 3802-3804.  [CSD] [CrossRef] [ChemPort] [PubMed]
Zakeeruddin, S. M., Nazeeruddin, M. K., Pechy, P., Rotzinger, F. P., Humphry-Baker, R., Kalyanasundaram, K. & Grätzel, M. (1997). Inorg. Chem. 36, 5937-5946.  [CSD] [CrossRef] [PubMed] [ChemPort] [ISI]


Acta Cryst (2013). E69, m510-m511   [ doi:10.1107/S1600536813022940 ]

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