Supramolecular architectures in N-(4-bromobenzoyl)-arylsulfonamides: crystal structures and Hirshfeld surface analysis

Abstract

Abstract A detailed analysis of the molecular packing of five N-(4-bromobenzoyl)-substituted benzenesulfonamides, i-X~4-Br (1–5) [i-X=H, 2-CH3, 4-CH3, 2-Cl, 4-Cl] is presented. The intermolecular interactions and the packing patterns are evaluated along with an analysis of their Hirshfeld surfaces and fingerprint plots (FP). The crystals feature molecular self-assembly through N–H···O hydrogen-bonds forming three types of supramolecular synthon:  C 1 1 ( 4 ) ${\rm{C}}_1^1(4)$ chain, R 4 4 ( 16 ) ${\rm{R}}_4^4(16)$ tetramer and R 2 2 ( 8 ) ${\rm{R}}_2^2(8)$ ring. These molecular assemblies extend to form one-dimensional (1D), 2D or 3D supramolecular architectures via diverse intermolecular interactions. A study of 33 i-X~4-Y (Y=H, CH3, OCH3, NO2, F, Cl, Br) structures shows the substituent on the sulfonamide ring modulates the intermolecular interactions and the subsequent supramolecular architectures drastically, with the fluoro- and bromo-substituted analogues providing distinctive self-assemblies. The R 4 4 ( 16 ) ${\rm{R}}_4^4(16)$ synthon produced by N–H···O hydrogen-bonds in the 4-CH3~4-Br derivative is a rare phenomenon amongst a set of 74 i-X~j-Y structures.