A few suitably long dialdehyde and primary diamine building blocks of a predetermined chirality have been designed and synthesized to enable controlled and efficient synthesis of all 6 possible diastereomers...

This study focuses on selected members of the general salen-analogues family possessing two O-H⋯N hydrogen bonds, namely three isomers of N,N’-bis(salicylidene)-X-phenylenediamine, denoted as ortho, meta and para. Two of the isomers are not planar in the published crystal structures. The current study tackles the problem of symmetry and interactions within the molecules, as well as in the crystal lattice. The aromaticity of the phenyl rings is evaluated using the Harmonic Oscillator Model of Aromaticity (HOMA) index. Intra- and inter-molecular non-covalent interactions are studied via Hirshfeld surface analysis, Independent Gradient Model (IGM), Quantum Theory of Atoms in Molecules (QTAIM), Non-Covalent Interaction (NCI) index, Electron Localisation Function (ELF), Core-Valence Bifurcation (CVB) index and Symmetry-Adapted Perturbation Theory (SAPT). Density Functional Theory (DFT) simulations were carried out in vacuo and with solvent reaction field based on Polarisable Continuum Model (IEF-PCM formulation) at the ωB97XD/6-311+G(2d,2p) level. Crystal structure analyses were performed for the data reported previously in the literature. The obtained results demonstrate that the three isomers differ greatly in their structural properties (molecular symmetry is broken for the ortho and meta isomers in the solid state) and ability to form intermolecular interactions, while retaining overall similar physico-chemical characteristics, e.g., aromaticity of the phenyl rings. It was found that the presence of the polar solvent does not significantly affect the structure of the studied compounds. An application of the Hirshfeld surface analysis revealed the nature of the non-covalent interactions present in the investigated crystals. The SAPT results showed that the stability of the dimers extracted from the crystals of the Schiff base derivatives arises from electrostatics and dispersion.