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)

✍ Scribed by Steffen Gagelmann; Katja Rieß; Mathias S. Wickleder

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 972 KB
• Volume: 2011
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.201100565

✦ Synopsis

Abstract

The oxidation of copper, zinc and nickel by N~2~O~5~ led, respectively, to turquoise‐coloured single crystals of (NO)Cu(NO~3~)~3~ [monoclinic, __P__2~1~/m, Z = 2, a = 465.90(5), b = 1111.7(1), c = 700.7(1) pm, β = 100.70(2)°, wR~2~ = 0.0566], light‐yellow single crystals of (NO)~2~[Zn(NO~3~)~4~] [orthorhombic, __Fdd__2, Z = 8, a = 1522.8(2), b = 2346.4(3), c = 596.18(7) pm, wR~2~ = 0.0452] and green single crystals of (NO)~6~Ni~4~(NO~3~)~12~~2~·(HNO~3~) [orthorhombic, __P__2~1~2~1~2~1~, Z = 4, a = 1167.68(4), b = 1791.97(6), c = 1834.11(6) pm, wR~2~ = 0.0762]. In (NO)Cu(NO~3~)~3~, the Cu^2+^ 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(NO~3~)~4~], the nitrate anions are coordinated to only one Zn^2+^, ion and the coordination polyhedron is a distorted octahedron. The complex nitrate (NO)~6~Ni~4~(NO~3~)~12~~2~·(HNO~3~) exhibits anionic ribbon chains according to ~∞~^1^{[Ni(NO~3~)~1/1~(NO~3~)~4/2~]}~2~^2–^ with octahedrally coordinated Ni^2+^ ions as well as non‐coordinating nitrate ions and HNO~3~ molecules. The thermal decomposition of the copper and zinc nitrates are multistep processes and lead to a mixture of Cu and Cu~2~O in the case of the copper compound and to ZnO for the zinc complex.