Crystal structure and Hirshfeld surface analysis of (E)-N′-benzylidene-4-chlorobenzenesulfonohydrazide and of its (E)-4-chloro-N′-(ortho- and para-methylbenzylidene)benzenesulfonohydrazide derivatives

Abstract

(E)-N′-Benzylidene-4-chlorobenzenesulfonohydrazide, C13H11ClN2O2S, (I), and its ortho- and para-methylsubstituted derivatives, C14H13ClN2O2S, namely (E)-4-chloro-N′-(2-methylbenzylidene)benzenesulfonohydrazide, (II), and (E)-4-chloro-N′-(4-methylbenzylidene)benzenesulfonohydrazide, (III), have been synthesized, characterized spectroscopically and their crystal structures determined to investigate the effect of the substitution site of the benzylidene group on the structural and supramolecular features in these compounds. Compounds (I) and (II) are isotypic while compound (III) is different. All three molecules are bent at the S atom with C—S—N—N torsion angles of −66.0 (3), −66.0 (3) and −58.4 (2)° for (I), (II) and (III), respectively. The hydrazone portions of the molecules, S—N—N=C, are slightly twisted from planarity, with a torsion angle of 166.5 (3)° in (I), 165.4 (3)° in (II) and 157.9 (2)° in (III). The two aromatic rings present in the compounds are inclined to each other by 78.4 (2), 74.8 (2) and 76.9 (1)° in (I), (II) and (III), respectively. In the crystal structure of the parent compound (I), and of the ortho-methyl derivative (II), an N—H...O hydrogen bond links the molecules into chains along [001], which are interconnected by weak intermolecular C—H...O interactions, generating layers lying parallel to the bc plane. In the crystal of the para derivative (III), however, the packing is significantly different. Here molecules are linked by pairs of N—H...O hydrogen bonds, forming inversion dimers with an R 2 2(8) ring motif. The dimers are then linked by C—Cl...π interactions, forming ribbons propagating along [1\overline{1}0]. Hirshfeld surface analyses show that the van der Waals interactions constitute the major contribution to the intermolecular interactions in the crystal structures of all three compounds. The fingerprint plots indicate that the H...H contacts make the largest contributions to the Hirshfeld surfaces.