Crystal structures and the Hirshfeld surface analysis of (E)-4-nitro-N′-(o-chloro, o- and p-methylbenzylidene)benzenesulfonohydrazides

Abstract

The crystal structures of (E)-N′-(2-chlorobenzylidene)-4-nitrobenzenesulfonohydrazide, C13H10ClN3O4S (I), (E)-N′-(2-methylbenzylidene)-4-nitrobenzenesulfonohydrazide, C14H13N3O4S (II), and (E)-N′-(4-methylbenzylidene)-4-nitrobenzenesulfonohydrazide monohydrate, C14H13N3O4S·H2O (III), have been synthesized, characterized and their crystal structures determined to study the effects of the nature and sites of substitutions on the structural parameters and the hydrogen-bonding interactions. All three compounds crystallize in the monoclinic crystal system, with space group P21 for (I) and P21/c for (II) and (III). Compound (III) crystallizes as a monohydrate. All three compounds adopt an E configuration around the C=N bond. The molecules are bent at the S atom with C—S—N—N torsion angles of −59.0 (3), 58.0 (2) and −70.2 (1)° in (I), (II) and (III), respectively. The sulfonohydrazide parts are also non-linear, as is evident from the S—N—N—C torsional angles of 159.3 (3), −164.2 (1) and 152.3 (1)° in (I), (II) and (III), respectively, while the hydrazide parts are almost planar with the N—N=C—C torsion angles being −179.1 (3)° in (I), 176.7 (2)° in (II) and 175.0 (2)° in (III). The 4-nitro-substituted phenylsulfonyl and 2/4-substituted benzylidene rings are inclined to each other by 81.1 (1)° in (I), 81.4 (1)° in (II) and 74.4 (1)° in (III). The compounds show differences in hydrogen-bonding interactions. In the crystal of (I), molecules are linked via N—H...O hydrogen bonds, forming C(4) chains along the a-axis direction that are interconnected by weak C—H...O hydrogen bonds, generating layers parallel to the ac plane. In the crystal of (II), the amino H atom shows bifurcated N—H...O(O) hydrogen bonding with both O atoms of the nitro group generating C(9) chains along the b-axis direction. The chains are linked by weak C—H...O hydrogen bonds, forming a three-dimensional framework. In the crystal of (III), molecules are linked by Ow—H...O, N—H...Ow and C—H...O hydrogen bonds, forming layers lying parallel to the bc plane. The fingerprint plots generated for the three compounds show that for (I) and (II) the O...H/H...O contacts make the largest contributions, while for the para-substituted compound (III), H...H contacts are the major contributors to the Hirshfeld surfaces.