Crystallographic and Theoretical Evidence of Acetonitrile−π Interactions with the Electron-Deficient 1,3,5-Triazine Ring

Reaction of zinc(II) chloride with the ligand N,N‘-{2,4-(di-2-pyridylamino)-1,3,5-triazin-6-yl}-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (oxodendtriz) in acetonitrile/methanol results in the formation the tetranuclear complex [Zn4(oxodendtriz)Cl8](CH3CN)2(H2O)1.5. Notably, its crystal structure reveals unique π-interactions with the first experimental evidence of electron-rich/electron-poor molecule pairing, which is corroborated by computational studies. In addition, infinite helical water chains with both right- and left-handed configurations are present in the crystal lattice.