Crystal structure and Hirshfeld surface analysis of (Z)-4-chloro-N′-(4-oxothiazolidin-2-ylidene)benzenesulfonohydrazide monohydrate

The asymmetric unit contains two independent molecules and two water molecules. The central parts of both the molecules are twisted as both molecules are bent at both the S and N atoms. The crystal structure features N—H⋯N, N—H⋯O, C—H⋯O and O—H⋯O intermolecular interactions. Two-dimensional fingerprint plots show that the largest contributions to the crystal stability come from O⋯H/H⋯O and H⋯H interactions.


Chemical context
Sulfonamides are of interest as this class of compounds exhibits a wide array of biological activities such as antitumor, antibacterial, diuretic and hypoglycaemic activities (Kamal et al., 2007). It has been reported that incorporation of hydrazine moieties increases the carbonic anhydrase inhibition activity (Winum et al., 2005). Along with the sulfonamide group, the presence of the 2-hydrazino-thiazole moiety enhances the pharmacological activities. The thiozoyl group is of interest because of its medicinal use in antitumor (Holla et al., 2003;Kappe et al., 2004), hyposensitive (Dash et al., 1980), anti-HIV (Patt et al., 1992), antimicrobial and anticancer agents (Frè re et al., 2003). Sulfonylhydrazines and their derivatives can easily be prepared and are stable. We report herein the synthesis and structure of the title compound, which is a new thiazole compound containing a sulfonylhydrazinic moiety.

Supramolecular features
In the crystal, the two independent molecules are linked into dimers by pairs of N-HÁ Á ÁN hydrogen bonds, forming rings with an R 2 2 (8) graph-set motif. These dimers are connected by C-HÁ Á ÁO hydrogen bonds involving the thiazole C-H and a sulfonyl O atom into chains running parallel to the a axis (Table 1, Fig. 2). The water molecules are involved both in the enforcement of the dimers through N-HÁ Á ÁO and O-HÁ Á ÁO hydrogen bonds, forming R 3 3 (9) rings, and in inter-chain O-HÁ Á ÁO hydrogen-bonding interactions, forming layers parallel to the ab plane.

Figure 2
The molecular packing of the title compound, with hydrogen bonds (Table 1) shown as dashed lines.

Figure 1
The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level.

Hirshfeld Surface Analysis
In order to explore the role of weak intermolecular interactions in the crystal packing, Hirshfeld surfaces (d norm ) and related fingerprint plots were generated using Crystal-Explorer17.5 (McKinnon et al., 2007;Spackman et al., 2008;Spackman & Jayatilaka, 2009;Wolff et al., 2012). The threedimensional molecular Hirshfeld surfaces were generated using a high standard surface resolution over a colour scale of À0.6355 to 1.5137 a.u. for d norm . To identify the normalized contacts, the d norm function is used, which is expressed as; (Shit et al., 2016), where d i and d e are the distances from internal and external atoms to the Hirshfeld surface and r i vdw and r e vdw are the van der Waals radii of the atoms inside and outside the surface. On the Hirshfeld surfaces mapped over d norm (Fig. 3), strong N-HÁ Á ÁN and S-OÁ Á ÁH interactions are observed as red spots close to atoms N5, N6 and O6. Furthermore, the two-dimensional fingerprint plots indicate that the largest contributions are from OÁ Á ÁH/HÁ Á ÁO contacts, which contribute 32.9% to the Hirshfeld surface ( Fig. 4a) with d i + d e $ 1.9 Å . The presence of water molecules in the unit cell provides the largest contribution to the stability of the crystal packing. The next largest contributor is from HÁ Á ÁH interactions, which contribute 22.6%. A single sharp spike can be seen in the middle region of the plot, at d i = d e = 0.9 Å (Fig. 4b). The NÁ Á ÁH contacts, which refer to N-HÁ Á ÁN interactions, contribute 5.3% to the surface. Two sharp spikes having d i + d e = 1.8 Å (Fig. 4c) are observed. The CÁ Á ÁH contacts contribute 5.9% to the Hirshfeld surface, featuring a wide region with d i + d e = 3.1 Å (Fig. 4d). The different interatomic contacts and percentage contributions to the Hirshfeld surface are ClÁ Á ÁH/ HÁ Á ÁCl (8.3%), SÁ Á ÁH/HÁ Á ÁS (6.1%), ClÁ Á ÁO/OÁ Á ÁCl (3.0%), ClÁ Á ÁC/CÁ Á ÁCl (2.4%), SÁ Á ÁO/OÁ Á ÁS (1.7%), and CÁ Á ÁO/OÁ Á ÁC (1.6%) as depicted in the fingerprint plots ( Fig. 5a-f).

Synthesis and crystallization
4-Chloro-N 0 -(4-oxo-4,5-dihydro-1,3-thiazol-2-yl)benzene-1sulfonohydrazide was prepared by adding 4-chloro benzenesulfonyl chloride (0.02 mol) under stirring to a solution of thiosemicarbazide (0.02 mol) in 5% aqueous NaOH solution (20 ml). The reaction mixture was stirred at room temperature for 1 h, then diluted twofold with water and neutralized with glacial acetic acid. The solid 2-(4-chlorobenzene-1-sulfonyl)hydrazine-1-carbothioamide (A) obtained was crystallized from acetic acid. Monochloroacetic acid (0.01 mol) and anhydrous sodium acetate (0.04 mol) were added to A (0.01 mol) in glacial acetic acid. The reaction mixture was refluxed for 8-10 h and the completion of the reaction was checked by TLC. The reaction mixture was then poured into cold water. The resulted precipitate of the title compound was separated by vacuum filtration. Prismatic colourless single crystals of the title compound were grown from a mixture of acetonitrile-DMF (5:1 v/v) by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by IR spectroscopy. The characteristic IR absorptions observed at 3095.9, 1639.5, 1458.7, 1343.2, 1139.4, and 1215.7 cm À1

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to C were positioned with idealized geometry using a riding model with C-H = 0.93 Å (aromatic) or 0.97 Å (methylene). The H atoms of the NH groups and the H atoms of the water molecules were located in a difference-Fourier map and later refined with the N-H and O-H bond lengths constrained to be 0.86 (2) and 0.82 (2) Å , respectively. All H atoms were refined with isotropic displacement parameters set at 1.2U eq of the parent atom.   software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

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.