Solvent-induced polymorphism in dipodal N-donor ligands containing a biphenyl core

Polymorph screenings for two related dipodal N-donor ligands containing a biphenyl core, namely 4,4′-bis(pyridin-4-ylmethyl)-1,1′-biphenyl (1) and 4,4′-bis(1H-imidazol-1-ylmethyl)-1,1′-biphenyl (2) were performed, and the new phases were isolated and their crystal structures analysed. Profiling included methods such as PXRD and thermal analysis. Hirshfeld surface analyses, as well as crystal lattice energy calculations provided deeper insight in the interplay of the intermolecular forces and the stability of the isolated phases. Furthermore, our studies revealed the presence of solvent-induced polymorphism, whereby the metastable phase is dominant upon crystallisation from THF (1a) and EtOH (2c). Upon heating, these phases transform into a more stable form, whereby the transformations were followed by PXRD studies (1, 2).