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

Two (E)-N′-(p-substituted benzyl­idene)-4-chloro­benzene­sulfono­hydrazides, namely, (E)-4-chloro-N′-(4-chloro­benzyl­idene)benzene­sulfono­hydrazide, C(13)H(10)Cl(2)N(2)O(2)S, (I), and (E)-4-chloro-N′-(4-nitro­benzyl­idene)benzene­sulfono­hydrazide, C(13)H(10)ClN(3)O(4)S, (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.