An investigation of the interaction between copper(II) ion, oxalyldihydrazide, and molecular oxygen: crystal and molecular structures of products resulting from the addition of an excess of acetaldehyde

Abstract

The end products of the reaction between copper(II) ion, an oxalyldihydrazide, ammonia, and excess of acetaldehyde, in air, have been isolated for oxalyldihydrazide itself and N-phenyloxalyldihydrazide. The two products are purple (I) and green (II) respectively and show very high absorption (ε 20 000–30 000 dm³ mol^–1 cm^–1) in the visible region of the spectrum. X-Ray analysis reveals that (I) crystallises in the monoclinic system [a= 9.373(2), b= 14.34(2), c= 26.129(4)Åβ= 102.25(1)° with space group P2₁/c] whereas the latter is orthorhombic [a= 16.331(2), b= 15.319(2), c= 15.336(4)Å with space group Cmc2,]. Both crystal structures contain anionic complex ions which have cage-like structures resulting from ring-closing reactions with acetaldehyde. The structures were solved from diffractometer data by the heavy-atom-method and refined by least-squares techniques to R 0.088 (1 836 reflections) and 0.077 (1 184 reflections).