LAUSR

We report the synthesis and X-ray solid state structures of five squaric acid derivatives, i.e. a zwitterionic compound, namely 3-hydroxy-4-(2-pyridin-2-yl-ethylamino)cyclobut-3-ene-1,2-dione (1), a squaramide monoester, 3-ethoxy-4-(2-pyridin-2-yl-ethylamino)cyclobut-3-ene-1,2-dione (2), two differently solvated (EtOH and DMSO/water) disquaramides 3,4-bis((4-hydroxyphenethyl)amino)cyclobut-3-ene-1,2-dione (3 and 4, respectively), and a mixed hydrogen squarate and disquarate 2-(2-aminoethyl)pyridinium salt (5). All compounds form interesting supramolecular assemblies in the solid state that have been analyzed using high level DFT calculations and Bader's theory of “atoms-in-molecules”. An intricate combination of ion-pair and H-bonding interactions along with π–π stacking and anion–π contacts of the cyclobutenedione rings is crucial for the formation of the supramolecular assemblies in the solid state.