Dichlorido(η6-p-cymene)[tris(4-methoxyphenyl)phosphane]ruthenium(II)

The title compound, [RuCl2(C10H14)(C21H21O3P)] crystallizes with two independent complex molecules in the asymmetric unit. In the crystal, weak C—H⋯Cl/O/π interactions are observed.


Structure description
The activity of the half-sandwich Ru II -arene complexes is well known in the catalytic transfer hydrogenation of carbonyl compounds (Chen et al., 2002;Crochet et al., 2003;Aydemir et al., 2011;Wang et al., 2011). Reported here is the 6 -cymene-Ru complex containing the phosphane, P(C 6 H 4 OMe-p) 3 , as part of ongoing structural investigations into these type of complexes.
To describe the steric demand of phosphane ligands, we have implemented the two most widely used models, i.e. the solid angle (a percentage projection of the ligand onto a sphere; Immirzi & Musco, 1977) and the crystallographic cone angle (an adaptation from the Tolman cone angle model; Tolman, 1977), where the orientation of the substituents are taken from crystallographic data instead of a CPK model, and the Ru-P bond length adjusted to 2.28 Å to normalize any influence this variation may have on the cone size (Mü ller & Mingos, 1995) to calculate an effective cone angle (Otto, 2001). The effective cone angle values obtained with this An overlay diagram showing the conformational similarity between the two molecules in the asymmetric unit (r.m.s.d. = 0.0525 Å ). Table 1 Hydrogen-bond geometry (Å , ).

Figure 1
(a) and (b): Views of the title complex showing the atom-numbering scheme for the two independent molecules in the asymmetric unit and 50% probability displacement ellipsoids. Molecules were rotated independently to obtain the best view for each. method for the two independent molecules in the asymmetric unit are 149.5 and 150.2 compared to the Tolman cone angle of 145.0 obtained from the QALE website (Fernandez et al., 2003). The solid angles, utilizing SOLID-G (Guzei & Wendt, 2004) were calculated as 25.35 and 25.61 . It is interesting to note that despite these similar geometric values, the phosphane ligands of these two independent molecules show a marked variation in their orientations of substituents as the P1-phosphane has a C-HÁ Á Á interaction between two of its substituents, whereas the P2-phosphane does not show this feature. The rest of the crystal displays an array of weak C-HÁ Á ÁCl/O interactions (see Fig. 3, Table 1 for a summary of interactions).

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. The deepest residual electrondensity hole (À1.94 e Å À3 ) is located at 0.59 Å from Ru1 and the highest peak (3.95 e Å À3 ) 0.90 Å from Ru1. Initial refinement of data indicated a two-component twin with a 180 rotation about the [100] reciprocal direction. Refinement Special details Experimental. The intensity data was collected on a Bruker Apex DUO 4 K-CCD diffractometer using an exposure time of 10 s/frame. A total of 3975 frames were collected with a frame width of 0.5° covering up to θ = 28.62° with 98.4% completeness accomplished.

data-2
IUCrData (2021). 6, x211259 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 > 2sigma(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. The aromatic-, methine-and methyl-H atoms were placed in geometrically idealized positions with C-H = 0.95, 1.00, and 0.98 Å, respectively, and allowed to ride on their parent atoms, with U iso (H) = 1.5U eq (C) for methyl-H and U iso (H) = 1.2U eq (C) for aromatic-and methine-H atoms. Methyl torsion angles were refined from electron density.