Crystal structure and Hirshfeld surface analysis of two (E)- N'-(para-substituted benzyl-idene) 4-chloro-benzene-sulfono-hydrazides

Abstract

Two (E)-N'-(p-substituted benzyl-idene)-4-chloro-benzene-sulfono-hydrazides, namely, (E)-4-chloro-N'-(4-chloro-benzyl-idene)benzene-sulfono-hydrazide, C₁₃H₁₀Cl₂N₂O₂S, (I), and (E)-4-chloro-N'-(4-nitro-benzyl-idene)benzene-sulfono-hydrazide, 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 mol-ecules [(IIA) and IIB)] in the asymmetric unit. In both compounds, the configuration around the C=N bond is E. The mol-ecules 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 mol-ecules A and B of (II). The 4-chloro-phenyl-sulfonyl and 4-substituted benzyl-idene 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), mol-ecules 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 inter-actions, forming a three-dimensional structure. In the crystal of (II), mol-ecules are linked by C-H⋯π inter-actions 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 inter-actions, 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.

Keywords: Hirshfeld surface analysis; N′-(aryl­idene)aryl­sulfono­hydrazides; crystal structure; fingerprint plots; graph-set motif; hydrazones; hydrogen bonding.

Figure 1

Mol­ecular structure of (I), with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 2

Mol­ecular structure of (II), with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 3

Crystal packing of (I), viewed along the a axis, with hydrogen bonds (Table 2 ▸) shown as dashed lines and C—Cl⋯π inter­actions as blue arrows. C-bound H atoms have been omitted.

Figure 4

A partial view along the a axis of the crystal packing of (II), with hydrogen bonds (Table 3 ▸) shown as dashed lines. H atoms not involved in these inter­actions have been omitted. Colour code: black A mol­ecules; red B mol­ecules.

Figure 5

Crystal packing of (II), viewed along the b axis, with hydrogen bonds shown as dashed lines. H atoms not involved in these inter­actions have been omitted.

Figure 6

(a) View of the Hirshfeld surface mapped over d _norm for (I); (b) two views of the Hirshfeld surface mapped over d _norm for (II).

Figure 7

Two-dimensional fingerprint plots for (a) (I) and (b) (II). d _i is the closest inter­nal distance from a given point on the Hirshfeld surface and d _e is the closest external contact.

Figure 8

Qu­anti­tative results of different inter­molecular inter­actions contributing to the Hirshfield surfaces of (I) and (II).