Received 17 June 2013
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 HX contacts, especially some involving the Cl- ligand.
For a related crystal structure, see: Zakeeruddin et al. (1997). For the structures of terpyridyl/bipyridyl RuII-chlorido compounds relevant to the comparative discussion, see: Chen et al. (2011, 2013); Jude et al. (2008, 2009, 2013). For literature used in the synthetic preparations, see: Evans et al. (1973); Jakubikova et al. (2009); Zakeeruddin et al. (1997). For the catalytic properties of related complexes, see: Chen et al. (2009); Concepcion et al. (2008); Masaoka & Sakai (2009); Tseng et al. (2008); Wasylenko et al. (2010); Yagi et al. (2011).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) and SHELXLE (Hübschle et al., 2011); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2555 ).
This work was supported by the US Department of Energy through the Laboratory Directed Research and Development (LDRD) program at LANL.
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