2,4-Dichloro-N-[ethyl(2-hydroxyethyl)carbamothioyl]benzamide

In the title compound, C12H14Cl2N2O2S, the molecule adopts a cis conformation with respect to the dichlorobenzoyl group against the thiono group about the C—N bond. However, the dichlorobenzene group and the thiourea moiety are twisted by 75.41 (8)°. An intramolecular N—H⋯O hydrogen bond occurs between the amido H atom and hydroxyl O atom. In the crystal, O—H⋯S and O—H⋯O hydrogen bonds link the molecules, forming chains along the b-axis direction.

In the title compound, C 12 H 14 Cl 2 N 2 O 2 S, the molecule adopts a cis conformation with respect to the dichlorobenzoyl group against the thiono group about the C-N bond. However, the dichlorobenzene group and the thiourea moiety are twisted by 75.41 (8) . An intramolecular N-HÁ Á ÁO hydrogen bond occurs between the amido H atom and hydroxyl O atom. In the crystal, O-HÁ Á ÁS and O-HÁ Á ÁO hydrogen bonds link the molecules, forming chains along the b-axis direction.   Table 1 Hydrogen-bond geometry (Å , ). Data collection: SMART (Bruker,2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Comment
Most of the aroyl or carbonoyl thiourea compounds reported so far are based on primary amines. The two amino hydrogen atoms play an important role on the geometry of the thiourea moiety such as that in 3-chloro-N-[N-(furan-2carbonyl)hydrazinocarbothioyl]benzamide (Yamin et al., 2013) where it adopts trans geometry. However, in the secondary amine based thiourea, only the amido hydrogen atom is present (Nasir et al., 2011;Al-abbasi et al., 2012).
Therefore, it can be expected that in the secondary amine carbonoyl thiourea, cis configuration is more likely to occur due to the absence of intrahydrogen bond involving the carbonyl oxygen atom and thioamide hydrogen atom. The title compound consists of dichloro substituted benzoyl and ethylethanol groups attached to the terminal nitrogen atoms respectively (Fig.1). The dichlorobenzoyl group is cis against thiono group across the C7-N1 bond. They are not coplanar but twisted by the dihedral angle between thiourea fragment S1/N1/N2/C8 and the dichlorobenzene ring, Cl1/Cl2/C1-C6, of 75.41 (8)°. Each fragment is planar with the maximum deviation of 0.025 (1)Å for atom Cl1 from the least-squares plane. The bond lengths and angles are in normal ranges (Allen et al.,1987). There is an intramolecular hydrogen bond N1-H1A···O2 between the amido hydrogen and hydroxyl oxygen atom. In the crystal structure, the molecules are linked by O2-H2A···S1 and O2-H2A···O1 intermolecular hydrogen bonds (see Table 1 for symmetry codes) to form one-dimensional chains along the b-axis (Fig.2).

Experimental
An acetone (30 ml) solution of (ethylamino)ethanol (0.18 g, 2 mmol) was added to a round-bottomed flask containing 2,4-dichlorobenzoyl isothiocyanate (0.58 g,2 mmol). The mixture was refluxed for 3h. After cooling the solution was filtered off and the filtrate was left to evaporate at room temperature. The solid formed was washed with water and cold ethanol. Crystals suitable for X-ray study were obtained by recrystallization from DMSO.

Refinement
All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C-H= 0.93-0.97Å and N-H = 0.86Å with U iso (H)= 1.2U eq [C (methylene and aromatic),N] and 1.5 U eq [C (methyl)]. The hydroxyl hydrogen atom was located from Fourier map and refined isotropically with O-H restraint to 0.82Å with an esd of 0.01.  The molecular structure of (I), with displacement ellipsods drawn at the 50% probability level. The dashed line indicates the intramolecular hydrogen bond.

Figure 2
Molecular packing of (I) viewed down the a-axis. The dashed lines indicate intermolecular hydrogen bonds.

Special details
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.