Abstract
Reactions of anhydrous chlorides VCl3 or ZnCl2 and pyridin-2-one (C5H5NO = Hhp) afforded novel homoleptic ionic [V(Hhp)6]Cl3.CH2Cl2 (1) or molecular [ZnCl2(Hhp)2] (2) complexes. Reaction of MnCl2.2H2O and Hhp in tetrahydrofuran (THF) gave cocrystals of [MnCl2(H2O)2]n.2nHhp (3). After addition of chlorotrimethylsilane to remove water in a mixture of MnCl2.2H2O and Hhp in THF, protonation of Hhp was observed and H2hpCl (4) was isolated. Single crystal X-ray analysis revealed a monodentate coordination of carbonyl oxygen in complexes 1 and 2.The results of thermal analysis of crystals 1, 2 and 4 show their thermal stability. The decomposition of complex 1 starts at 60°C, while complex 2 melts at 175°C and decomposes only at 185°C. Compound 4 can be classified as an ionic liquid due to its low melting point (86°C). The release of ligated Hhp in 1 and 2 occurs up to 450°C, while 99.4% mass loss in 4 is observed at the lower temperature of 220°C.The difference in thermal stability is explained by the ligation of Hhp, hydrogen bonds and other weak interactions. Hydrogen bonds and an off-center parallel stacking arrangement of the coordinated Hhp form a 3D structure in 2 and layers in 1. The H2hp+ and chloride ions in 4 are connected by hydrogen bonds and form only chains without other weak interactions.
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