Extreme Molecular Orientations in a Dimorphic System: Polar/Centric and Polar/Polar Cogrowth Crystal Architectures

(4-Pyrrolidinopyridyl)bis(acetylacetonato)zinc(II) forms perfectly polar as well as centrosymmetric crystal
structures depending sensitively on the solvent and the rate of crystallization. Semiempirical computational modeling of
molecular clusters, incorporating solvation effects, highlights the delicate balance of energetics involved in the solvent
polarity preference of the extreme structures. A suitable choice of solvents provides crystals exhibiting an unusual cogrowth
of polar/centric as well as polar/polar domains. This material provides a vivid illustration of the subtle nature of
supramolecular assembly leading to extreme organizational motifs and opens up possibilities of realizing novel multidomain
architectures in crystals.