Metal Oxidation with N 2 O 5 : The Nitrosylium Nitrates (NO)Cu(NO 3 ) 3 , (NO)2[Zn(NO3)4] and (NO)6Ni4(NO3)122•(HNO3). -N2O5 is prepared by reaction of fuming HNO3 with P4O10 and directly condensed on the metal powders. The crystal structures of the resulting title compounds are determined by single crystal XRD. (II) crystallizes in the monoclinic space group P21/m with Z = 2. Cu 2+ is coordinated by six oxygen atoms of monodentate nitrate groups in the form of a tetragonal distorted octahedron. The nitrate groups are connected to further copper ions to form a two-dimensional network. (IV) crystallizes in the orthorhombic space group Fdd2 with Z = 8. The nitrate anions are coordinated to only one Zn 2+ ion in a distorted octahedral fashion. (VI) crystallizes in the orthorhombic space group P212121 with Z = 4. The structure contains ∞ 1 {[Ni(NO 3 )(NO 3 ) 4/2 chains with octahedrally coordinated Ni 2+ ions, non-coordinated nitrate ions, and HNO3 molecules. The thermal decomposition of (II) and (IV) is discussed. -(GAGELMANN, S.; RIESS, K.; WICKLEDER*, M.