Structural Study of N-(1,3-Benzothiazol-2-yl)-4-Halobenzenesulfonylhydrazides: Hirshfeld Surface Analysis and PIXEL Calculations

Abstract

Hydrazonylsulfones such as Bt-NHNHSO2R and their iminotautomers have been studied as optical materials and for their biological potential. In this work, a structural study has been carried out on N-(1,3-benzothiazol-2-yl)-4-(halogenobenzenesulfonyl)-hydrazides (1: X = F, Cl, Br). For (1: X = F), single-crystal X-ray diffraction, Hirshfeld surface analysis, and PIXEL calculations were conducted, while in (1: X = Cl) and (1: X = Br), only single-crystal X-ray diffraction studies were successfully conducted due to the disordering of the solvent. Each compound crystallises with two independent but similar amino tautomers in the asymmetric units: compound (1: X = F) crystallises in the monoclinic P21/c, and the isostructural pair (X: 1 = Cl and Br) crystallises in the tetragonal P-421c space group. In the most stable motif of the supramolecular arrangement, the molecules of the asymmetric unit are connected by classical N–H(hydrazinyl)···N(thiazoyl) hydrogen bonds and several face-to-face, offset π···π interactions. This motif has a very powerful influence on the crystal structure due to its direct links with the other weaker motifs. Other significant intermolecular interactions found in the structure include N–H(hydrazonyl)···O(sulfonate) bonds. Analogous intermolecular interactions were found in similar compounds, leading to the conclusion that those interactions are the most important instabilizing the solid state of hydrazonylsulfones.