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

The crystal structures of (E)-N′-(2-chloro­benzyl­idene)-4-nitro­benzene­sulfono­hydrazide, C(13)H(10)ClN(3)O(4)S (I), (E)-N′-(2-methyl­benzyl­idene)-4-nitro­benzene­sulfono­hydrazide, C(14)H(13)N(3)O(4)S (II), and (E)-N′-(4-methyl­benzyl­idene)-4-nitro­benzene­sulfono­hydrazide monohydrate, C(14)H(13)N(3)O(4)S·H(2)O (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 P2(1) for (I) and P2(1)/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.