Positional Isomerism and Steric Effects in the Self-Assemblies of Phenylene Bis-Monothiooxalamides

The potential interplay of steric and substitution pattern effects of the monothiooxalamide side arms on the structure, conformational features, and self-assembly of a series of phenylene bis-monothiooxalamides was investigated. Herein we have demonstrated that phenylene bis-monothiooxalamides self-associate in the solid state, through intermolecular hydrogen bonding as meso-helices when the thioamide NR group is sBu and through dispersive CO···CX (X = O, S, π), S···S, and C–H···S interactions when R is tBu, independently from the substitution pattern in the phenyl ring. The helical structures are exclusively developed through NCSH···O hydrogen bonding. The steric strain imposed by the ortho-substitution pattern has the effect of moving both monothiooxalyl units out of the phenyl plane enabling dimerization through strong NCOH···O intermolecular hydrogen bonds and promotes the formation of meso-helices. The steric demand of the thioamide NR group rules the conformation adopted by meta-substituted derivati...