Crystal structure of 3-({[(morpholin-4-yl)carbonothioyl]sulfanyl}acetyl)phenyl benzoate

In the crystal structure of the title compound, the morpholine ring adopts the expected chair conformation. The central phenyl ring makes dihedral angles of 67.97 (4) and 7.74 (3)°, respectively, with the benzoate phenyl ring and the lattice mean plane. In the crystal, molecules are linked by C—H⋯O hydrogen bonds.


Chemical context
The title compound is a dithiocarbamate ester derivative of 3-(2-bromacetyl) phenyl benzoate, a key starting material used in the synthesis of phenylephrine, (R)-3-[À1-hydroxy-2-(methylamino)ethyl] phenol, which is a selective 1-adrenergic receptor agonist used primarily as a decongestant and as an agent to dilate the pupil and to increase blood pressure. Our current research work is aimed at the synthesis of a series of 3-(2-bromacetyl) phenyl benzoate dithiocarbamate ester derivatives. Dithiocarbamate acid esters exhibit a range of biological effects, including anti-bacterial, anti-fungal and anti-oxidant activity (Hirschelman et al., 2002) and inhibition of cardiac hypertrophy (Naoto et al. 2008). Recently, it was found that 5-oxohexyl dithiocarbamic acid methyl esters are potent phase II enzyme inducers, which could be used as cancer chemo-preventive agents (Scozzafava et al., 2000).

Supramolecular features
In the crystal, molecules are linked by weak C-HÁ Á ÁO hydrogen bonds, forming zigzag chains along the b axis. C-HÁ Á Á interactions link centrosymmetrically related molecules, reinforcing the three-dimensional structure (Fig. 2)

Synthesis and Crystallization
To a solution of NaOH (1 mmol) in 3 ml water was added to a mixture of morpholine (1 mmol) in ethanol (25 ml). After stirring at room temperature for about 20 min, carbon disulfide (1.2 mmol) was added dropwise and the resulting mixture was further stirred at room temperature for 90 min. Then 3-(2-bromacetyl) phenyl benzoate (1 mmol) was added and stirring was continued. After completion of the reaction (monitored by TLC), the solvent was removed under vacuum and the residue was extracted with dichloromethane (2 Â 25 ml) and dried over anhydrous MgSO 4 . The solvent was evaporated and the compound recrystallized from an ethanolchloroform mixture (3:1) to give the title compound as colourless crystals in 81% yield.

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C-H = 0.93-0.97Å and U iso (H) = 1.2U eq (C).

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.