Metal ion interactions with nucleobases in the tripodal tris(2-aminoethyl)amine (tren) ligand-system. Crystal structures of [Zn(tren)(adeninato)] · ClO 4, [Cd(tren)(adeninato)] · ClO 4, [Ni(tren)(adeninato)(ClO 4)], [Zn(tren)(hypoxanthinato)] · ClO 4 · H 2O, [{Cd(tren)} 2(hypoxanthinato)] · (ClO 4) 3 · 0.5H 2O, [Ni(tren)(uracilato)(H 2O)] · ClO 4 · (0.5H 2O) 2, and [Cu(tren)(uracilato)] · ClO 4 · 0.5H 2O

Abstract

Reaction between nucleobases (adenine, hypoxanthine, cytosine, and uracil), tris(2-aminoethyl)amine (tren) and M(ClO 4) 2 (M 2+ = Zn 2+, Cd 2+, Ni 2+ or Cu 2+) under pH 8–9 gave eight ternary tren-metal ion-nucleobase complexes, among which seven crystal structures, [Zn(tren)(adeninato)] · ClO 4 ( 1), [Cd(tren)(adeninato)] · ClO 4 ( 2), [Ni(tren)(adeninato)(ClO 4)] ( 3), [Zn(tren)(hypoxanthinato)] · ClO 4 · H 2O ( 4), [{Cd(tren)} 2(hypoxanthinato)] · (ClO 4) 3 · 0.5 H 2O ( 5), [Ni(tren)(uracilato)(H 2O)] · ClO 4 · (0.5H 2O) 2 ( 7), and [Cu(tren)(uracilato)] · ClO 4 · 0.5H 2O ( 8) were determined by X-ray diffraction. In each of the adenine complexes with Zn 2+ ( 1), Cd 2+ ( 2), and Ni 2+ ( 3), among which 1 and 2 are isostructural to each other, a tren-capped metal ion binds to an adeninato ligand through N(9) with the formation of an intramolecular interligand hydrogen bond between the amino nitrogen of tren and N(3) of the base. In the hypoxanthine complexes 4 and 5, a tren-capped Zn 2+ ion in 4 binds to a hypoxanthinato ligand through N(9) with the formation of an intramolecular N(tren)–H⋯N(3) hydrogen bond, while in 5 two tren-capped Cd 2+ ions bind to a hypoxanthinato ligand, one through N(7) with the formation of an intramolecular N(tren)–H⋯O(6) hydrogen bond and the other through N(9) to form an intramolecular N(tren)–H⋯N(3) hydrogen bond. In each of the uracil complexes with Ni 2+ ( 7) and Cu 2+ ( 8), a tren-capped metal ion binds to an uracilato ligand through N(1) with the formation of an intracomplex O(aqua)–H⋯O(2) hydrogen bond in 7 or an intramolecular N(tren)–H⋯O(2) hydrogen bond in 8. Tren-capped metal ion-bonded nucleobases act as building blocks for the assembly of supramolecular structures, by versatile hydrogen bonding and/or stacking abilities of nucleobases. The significance of intramolecular interligand interaction as a factor that affects metal-binding site(s) on nucleobases is emphasized.