Crystal structure and Hirshfeld surface analysis of two (E)-N′-(para-substituted benzylidene) 4-chlorobenzenesulfonohydrazides

Abstract

Two (E)-N′-(p-substituted benzylidene)-4-chlorobenzenesulfonohydrazides, namely, (E)-4-chloro-N′-(4-chlorobenzylidene)benzenesulfonohydrazide, C13H10Cl2N2O2S, (I), and (E)-4-chloro-N′-(4-nitrobenzylidene)benzenesulfonohydrazide, C13H10ClN3O4S, (II), have been synthesized, characterized and their crystal structures studied to explore the effect of the nature of substituents on the structural parameters. Compound (II) crystallized with two independent molecules [(IIA) and IIB)] in the asymmetric unit. In both compounds, the configuration around the C=N bond is E. The molecules are twisted at the S atom with C—S—N—N torsion angles of −62.4 (2)° in (I), and −46.8 (2)° and 56.8 (2)° in the molecules A and B of (II). The 4-chlorophenylsulfonyl and 4-substituted benzylidene rings form dihedral angles of 81.0 (1)° in (I), 75.9 (1)° in (IIA) and 73.4 (1)° in (IIB). In the crystal of (I), molecules are linked via pairs of N—H...O hydrogen bonds, forming inversion dimers with an R 2 2(8) ring motif. The dimers are linked by C—Cl...π interactions, forming a three-dimensional structure. In the crystal of (II), molecules are linked by C—H...π interactions and N—H...O hydrogen bonds, forming –A–B–A–B– chains along the c-axis direction. The chains are linked via C—H...O and C—H...π interactions, forming layers parallel to the bc plane. Two-dimensional fingerprint plots show that the most significant contacts contributing to the Hirshfeld surface for (I) are H...H contacts (26.6%), followed by Cl...H/H...Cl (21.3%), O...H/H...O (15.5%) and Cl...C/C...Cl (10.7%), while for (II) the O...H/H...O contacts are dominant, with a contribution of 34.8%, followed by H...H (15.2%), C...H/H...C (14.0%) and Cl...H/H...Cl (10.0%) contacts.