cis,cis,cis-(Acetato-κ2 O,O′)bis[1,2-bis(diphenylphosphanyl)ethane-κ2 P,P′]ruthenium(II) 0.75-trifluoromethanesulfonate 0.25-chloride

In the title RuII carboxylate compound, [Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25, the distorted tris-bidentate octahedral stereochemistry about the RuII atom in the complex cation comprises four P-atom donors from two 1,2-bis(diphenylphosphanyl)ethane ligands [Ru—P = 2.2881 (13)–2.3791 (13) Å] and two O-atom donors from the acetate ligand [Ru—O = 2.191 (3) and 2.202 (3) Å]. The disordered counter-anions are located on the same site in the structure in a 3:1 ratio, the expanded formula comprising four complex cations, three trifluoromethanesulfonate anions and one chloride anion, with two such formula units in the unit cell.


Related literature
respectively] result in a distorted octahedral geometry consistent with similar complexes having the cis-configuration (Holle et al., 1997, Lucas et al., 2000, Wyman et al., 2004. The Ru-P bond distances in the title complex are shorter than those in complexes in which the acetate group is trans-related but are well within reported ranges (Holle et al., 1997, Lucas et al., 2000, Wyman et al., 2004. The disordered counter anions are located on the same site in the structure in a 3:1 ratio, the complete complex unit having the formula 4[Ru(C 2 H 3 O 2 )(C 26 H 24 P 2 ) 2 ] (CF 3 O 3 S) 3 Cl, with two such formula units in the unit cell.

Experimental
The title compound was obtained as a by-product in the attempted crystallization of the products of the reaction of [RuCl(dppe) 2 ][PF 6 ] and 1,4-diheptoxy-2,5-diethynylbenzene, using a dichloromethane-diethyl ether solvent mixture at -20 °C.

Refinement
All H atoms were visible in electron density maps, but they were included at calculated positions and allowed to ride on the C atoms with C-H = 0.95 Å (aromatic), 0.98 Å (methyl) and 0.99 Å (methylene), with U iso (H) = 1.2 (or 1.5 for methyl) times U eq (C). Two positions for each of the methyl protons on C54 were found and this disorder was handled by refining these positions constrained over 60° rotational sites with 0.5 site occupancy. The trifluoromethanesulfonate and chloride anions were found to occupy a common site, with occupancies of 0.75 and 0.25, respectively. Small geometrical disorder in the trifluoromethanesulfonate anion was handled by restraining the C-F (1.320 Å), S-C (1.820 Å) and F···F (2.150 Å) distances (s = 0.001). The anisotropic displacement parameters were made equal for S1 and C55. program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figure 1
Plot of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.

cis,cis,cis-(Acetato-κ 2 O,O′)bis[1,2-bis(diphenylphosphanyl)ethane-κ
Special details Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.