Decacarbonyl-1κ3 C,2κ3 C,3κ4 C-bis[tris(3-chlorophenyl)phosphine]-1κP,2κP-triangulo-triruthenium(0) monohydrate

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C18H12Cl3P)2(CO)10]·H2O, consists of one triangulo-triruthenium complex and one disordered water solvent molecule. Two of the 3-chlorophenyl rings are disordered over two positions with refined site occupancies of 0.671 (3)/0.329 (3) and 0.628 (3)/0.372 (3). The water molecule is disordered over two positions with refined site occupancies of 0.523 (7) and 0.477 (7). Two equatorial carbonyl groups have been substituted by the two monodentate phosphine ligands, leaving one equatorial and two axial carbonyl substituents on the two Ru atoms. The remaining Ru atom carries two equatorial and two axial terminal carbonyl ligands. In the crystal structure, molecules are linked into columns along the a axis by intermolecular C—H⋯Cl and C—H⋯O hydrogen bonds. The molecular structure is stabilized by weak intramolecular C—H⋯O hydrogen bonds.

The asymmetric unit of the title triangulo-triruthenium compound, [Ru 3 (C 18 H 12 Cl 3 P) 2 (CO) 10 ]ÁH 2 O, consists of one triangulo-triruthenium complex and one disordered water solvent molecule. Two of the 3-chlorophenyl rings are disordered over two positions with refined site occupancies of 0.671 (3)/0.329 (3) and 0.628 (3)/0.372 (3). The water molecule is disordered over two positions with refined site occupancies of 0.523 (7) and 0.477 (7). Two equatorial carbonyl groups have been substituted by the two monodentate phosphine ligands, leaving one equatorial and two axial carbonyl substituents on the two Ru atoms. The remaining Ru atom carries two equatorial and two axial terminal carbonyl ligands. In the crystal structure, molecules are linked into columns along the a axis by intermolecular C-HÁ Á ÁCl and C-HÁ Á ÁO hydrogen bonds. The molecular structure is stabilized by weak intramolecular C-HÁ Á ÁO hydrogen bonds.

Related literature
For related structures, see: Bruce et al. (1988a,b); Chin-Choy et al. (1988). For the synthesis, see: Bruce et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Comment
Syntheses and structures of substituted triangulo-triruthenium clusters have been of interest to researchers due to observed structural variations and their potential catalytic activity. As part of our ongoing studies of phosphine substituted triangulotriruthenium clusters, we report herein the structure of title compound (I).
The asymmetric unit of title compound (I) consists of one triangulo-triruthenium complex and one disordered water solvent ( Fig. 1). The geometric parameters of title compound are comparable to those found in a related structure (Chin-Choy et al., 1988 (Bruce et al., 1988b), there is no pronounced difference in the Ru-Ru separations that can be correlated to the presence of the ligand.
The Ru-Ru separations are in the range 2.8517 (3) to 2.8645 (3) Å. The differences in the two Ru-P separations are almost identical with those in the analogous complexes synthesized by Bruce et al. (1988a). In this complex, the equatorial CO groups are more inclined to preserve linearity, equatorial Ru-C-O angles averaging 176.3° while the average value of the axial Ru-C-O groups is 173.8°.

Experimental
All the manipulations were performed under a dry oxygen-free nitrogen atmosphere using standard Schlenk techniques.
THF was dried over sodium wire and freshly distilled from sodium benzophenone ketyl solution. The title compound (I) was prepared by mixing Ru 3 (CO) 12 (Aldrich) and P(3-Cl-C 6 H 4 ) 3 (Maybridge) in a 1:2 molar ratio in THF at 40 °C. About 0.2 ml of diphenylketyl radical anion initiator (synthesized as per the method of Bruce et al., 1987)  These disordered benzene rings were subjected to rigid bond and similarity restraints. The same U ij parameters were used for the atom pairs C15A/C15B. The water molecule is also disordered over two positions with refined site-occupancies of 0.523 (7) and 0.477 (7). The O atom of the disordered water molecule was refined isotropically. The maximum and minimum residual electron density peaks were located 1.79 Å and 0.39 Å from the H1WA and Cl6 atoms, respectively. Fig. 1. The molecular structure of the title compound with 50% probability ellipsoids for non-H atoms. Decacarbonyl-1κ 3 C,2κ 3 C,3κ 4 C-bis[tris(3-chlorophenyl)phosphine]-1κP,2κP-triangulo-triruthenium (0)

Special details
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > σ(F 2 ) is used only for calculating Rfactors(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.