Supramolecular Energetic and Topological Study of Halogenated Aryl Carboxylic Acids

Abstract

A supramolecular energetic and topological study of 12 monohalogenated aryl carboxylic acids (F, Cl, Br, I) in the ortho, meta, and para positions was performed. The energy of intermolecular interactions was determined from long-range corrected hybrid density functional theoretical computational calculations, using the ωB97X-D3 method. The surface of contact between the molecules and the molecular coordination numbers were determined. From these data, all intermolecular interactions were classified, and the robustness of the interactions was evaluated. Thus, the molecule (Mn) allocations around a central molecule (M1) are proposed. In addition, the energy from the intermolecular interactions present in the first coordination sphere, which involves the central molecule, the energy resulting from the interactions between the peripheral molecules and the total energy of the cluster provided by all interactions, was determined. The role of hydrogen bonding (O–H···O, C–H···O, and C–H···X), π···π interactions, and halogen bonding (X···X) were evaluated, in the formation of the first coordination sphere and in the nucleation process.