Crystal structure of benzyltriphenylphosphonium chloride monohydrate

The title compound, Ph3(PhCH2)P+·Cl−·H2O, was obtained unintentionally as the product of an attempted synthesis of a silver dithiocarbamate complex using benzyltriphenylphosphonium as the counter-ion. The asymmetric unit consists of a phosphonium cation and a chloride anion, and a water molecule of crystallization. In the crystal, the chloride ion is linked to the water molecule by an O—H⋯Cl hydrogen bond. The three units are further linked via C—H⋯Cl and C—H⋯O hydrogen bonds and C—H⋯ π interactions, forming a three-dimensional structure.


S1. Synthesis and crystallization
The title compound was obtained unintentionally as the product of an attempted synthesis of silver complex of dithiocarbamate using benzyltriphenylphosphonium as the counter ion. Colourless crystals were obtained upon slow evaporation of the methanolic solution at room temperature.

S2. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms of the water molecule were located in a Fourier difference map. The water molecule was then refined as a rigid group with U iso (H) = 1.5U eq (O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C-H = 0.93 Å with U iso (H) = 1.2U eq (C).

S3. Results and discussion
The asymmetric unit of the title compound, shown in Fig. 1, consists of one independent cation, one independent anion and a hydrated water molecule. The central phosphine atom coordinates with the ligands in a slightly distorted tetrahedral environment. The C-P-C bond angles vary from 108.56 (12) to 110.51 (11) °, deviating slightly from the ideal tetrahedral angle of 109.5 °. The P-C bond distances, that vary from 1.792 (2) to 1.800 (3) Å, are comparable to values found for related compounds containing the Ph 3 (PhCH 2 )P + cation (Li & He, 2011;Fischer & Wiebelhaus, 1997;Skapski & Stephens, 1974).
In the crystal, the chloride ion is linked to the water molecule by an O-H···Cl hydrogen bond (Table 1 and Fig. 1). The three units are further linked via C-H···Cl and C-H···O hydrogen bonds and C-H··· π interactions (Table 1) forming a three-dimensional structure.

S4. Experimental
The title compound was obtained unintentionally as the product of an attempted synthesis of silver complex of dithiocarbamate using benzyltriphenylphosphonium as the counter ion. The colourless crystal was obtained upon slow evaporation of the methanolic solution at room temperature.

Figure 1
The asymmetric unit of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Dotted line denotes the O-H···Cl hydrogen bond (see Table 1 for details).

Benzyltriphenylphosphonium chloride monohydrate
Crystal data Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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. Carbon-bound H-atoms were placed in calculated positions (C-H 0.93-0.97 Å) and were included in the refinement in the riding model approximation with U iso (H) = 1.2U eq (C). H atoms in water molecule (O-H 0.85 Å) were refined using a riding model with U iso (H) = 1.5U eq (O).