Hydrogen-Bonded Chain of Rings Motif in <i>N</i>-(4-Methoxyphenyl)piperazin-1-ium Salts with Benzoate Anions: Supramolecular Assemblies and Their Energy Frameworks

Abstract

The crystal structures of three salts, namely N-(4-methoxyphenyl)piperazin-1-ium ethoxybenzoate monohydrate (I), N-(4-methoxyphenyl)piperazin-1-ium methoxybenzoate monohydrate (II) and N-(4-methoxyphenyl)piperazin-1-ium hydroxybenzoate monohydrate (III), have been determined and compared. In each of them, the ionic components and the water molecules are linked by a combination of N—H···O and O—H···O hydrogen bonds to form infinite chains of edge-fused centrosymmetric rings running parallel to the [100] direction. The C—H···O, C—H···π(arene) interactions and O—H···O in (III) are responsible for the further propagation of the aforementioned chains into di-periodic layers or tri-periodic networks. From an energetic point of view, all structures are primarily di-periodic; the very strong ionic interactions determine the periodicity. For comparison purposes, quantum chemical calculations were performed to show the difference between the ionic and neutral components. The energy of the hydrogen-bonded ring motifs was also estimated.

Keywords

• crystal structure
• piperazines
• hydrogen bonding
• chain of rings
• binding energy
• energy frameworks