Tetrachlorobenzenes represent one of the best known, but not yet fully understood, group of isomers of the structure–melting point relationship. The differences in melting temperatures of these structurally related compounds were rationalized in terms of the hierarchy and nature of formed noncovalent interactions, and the molecular aggregation that is influenced by molecular symmetry. The highest melting point is associated with the highly symmetric 1,2,4,5-tetrachlorobenzene isomer. The structures of less symmetrical 1,2,3,4-tetrachlorobenzene and 1,2,3,5-tetrachlorobenzene, determined at 270 and 90 K, show a distinct pattern of halogen bonds, characterized by the different numbers and types of interactions. The evolution of Cl...Cl/H distances with temperature indicates the attractive character of intermolecular interactions and their importance to the structural and thermodynamic parameters of isomeric compounds. The favoured Cl...Cl halogen bonds were found to play a decisive role in differentiating the melting temperatures of tetrachlorobenzene isomers. It was also found that, besides the molecular symmetry and ability to form specific intermolecular interactions, both the type and the distribution of interactions are the important factors responsible for the melting behaviour of the studied isomers. The observed preferences, in tetrachlorobenzenes, for the formation of specific noncovalent interactions correspond to the distribution of calculated partial atomic charges and to the magnitudes of electrostatic potential on the molecular surfaces as well as correlate with the enthalpy of melting parameters.
Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines
