(η6-Benzene)(carbonato-κ2 O,O′)[dicyclohexyl(naphthalen-1-ylmethyl)phosphane-κP]ruthenium(II) chloroform trisolvate

The title compound, [Ru(CO3)(η6-C6H6){(C6H11)2P(CH2C10H7)}]·3CHCl3, was synthesized by carbonation of [RuCl2(η6-C6H6){(C6H11)2P(CH2C10H7)}] with NaHCO3 in methanol at room temperature. The RuII atom is surrounded by a benzene ligand, a chelating carbonate group and a phosphane ligand in a piano-stool configuration. The crystal packing is consolidated by C—H⋯O and C—H⋯Cl hydrogen-bonding interactions between adjacent metal complexes and between the complexes and the solvent molecules. The asymmetric unit contains one metal complex and three chloroform solvent molecules of which only one was modelled. The estimated diffraction contributions of the other two strongly disordered chloroform solvent molecules were substracted from the observed diffraction data using the SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155].

Supporting information for this paper is available from the IUCr electronic archives (Reference: WM5028).
The asymmetric unit contains one complex and one chloroform solvent molecule (Fig. 1). Contributions of two further strongly disordered solvent molecules (chloroform) were removed from the diffraction data with the SQUEEZE option in PLATON (Spek, 2009). The Ru II atom is surrounded by a benzene ligand, a chelating carbonate group and a phosphane ligand (C 6 H 11 ) 2 P(CH 2 C 10 H 7 ) in a piano-stool geometry. The phosphane ligand is linked through its P atom with a Ru-P bond length of 2.3705 (8) Å; both cyclohexyl rings at the P atom adopt a chair conformation. The molecular structure shows a planar arrangement of the Ru(CO 3 ) fragment (mean deviation of the best plane defined by Ru1, O1, C1, O2, O3 is 0.036 Å). As expected, the exocyclic C-O bond in the Ru(CO 3 ) unit is with 1.242 (4) Å significantly shorter than the two endocyclic C-O bonds (C1-O1 = 1.326 (4) and C1-O2 = 1.309 (4) Å). The complex molecules as well as complex and solvent molecules are linked by C-H···Cl and C-H···O hydrogen bonds (Fig. 2).

Experimental
At room temperature, a mixture consisting of [RuCl 2 (η 6 -C 6 H 6 ){(C 6 H 11 ) 2 P(1-methylnaphthyl)}] (20 mg, 0.034 mmol), NaHCO 3 (63 mg, 0.34 mmol) and methanol (5 ml) was stirred under argon in a Schlenk tube. The orange suspension changed to a yellow solution. The reaction was completed within 10 min and the solution was filtered over celite. The solvent was removed in vacuo and 18 mg (94%) of a yellow solid was obtained. Crystals suitable for X-ray analysis were grown from a CHCl 3 /heptane mixture at 245 K. 1

Refinement
H atoms were placed in idealized positions with d(C-H) = 0.95 -1.00 Å (CH), 0.99 Å (CH 2 ) and refined using a riding model with U iso (H) fixed at 1.2U eq (C). Contributions of further disordered solvent molecules were removed from the diffraction data with PLATON / SQUEEZE (Spek, 2009). SQUEEZE estimated the electron count in the void volume of 1149 Å 3 to be 501; two voids are given. The highest peak in the final difference Fourier map is located 0.86 Å from Ru1 and the deepest hole 0.75 Å from Cl3.

Figure 1
The molecular structure of the title compound with atoms at the 30% probability level for the displacement ellipsoids.
Hydrogen atoms are omitted for clarity.