Metal Oxidation with N2O5: The Nitrosylium Nitrates (NO)Cu(NO3)3, (NO)2[Zn­(NO3)4] and (NO)6[Ni4(NO3)12](NO3)2·(HNO3)

Abstract

AbstractThe oxidation of copper, zinc and nickel by N2O5 led, respectively, to turquoise‐coloured single crystals of (NO)Cu(NO3)3 [monoclinic, P21/m, Z = 2, a = 465.90(5), b = 1111.7(1), c = 700.7(1) pm, β = 100.70(2)°, wR2 = 0.0566], light‐yellow single crystals of (NO)2[Zn(NO3)4] [orthorhombic, Fdd2, Z = 8, a = 1522.8(2), b = 2346.4(3), c = 596.18(7) pm, wR2 = 0.0452] and green single crystals of (NO)6[Ni4(NO3)12](NO3)2·(HNO3) [orthorhombic, P212121, Z = 4, a = 1167.68(4), b = 1791.97(6), c = 1834.11(6) pm, wR2 = 0.0762]. In (NO)Cu(NO3)3, the Cu2+ ion is coordinated by six oxygen atoms of monodentatenitrate groups in the form of a tetragonal distorted octahedron. The nitrate groups are connected to further copper ions leading to a two‐dimensional network. In contrast, in (NO)2[Zn(NO3)4], the nitrate anions are coordinated to only one Zn2+, ion and the coordination polyhedron is a distorted octahedron. The complex nitrate (NO)6[Ni4(NO3)12](NO3)2·(HNO3) exhibits anionic ribbon chains according to ∞1{[Ni(NO3)1/1(NO3)4/2]}22– with octahedrally coordinated Ni2+ ions as well as non‐coordinating nitrate ions and HNO3 molecules. The thermal decomposition of the copper and zinc nitrates are multistep processes and lead to a mixture of Cu and Cu2O in the case of the copper compound and to ZnO for the zinc complex.