The use of 2-pyridyl ketone oximes, pyC(R)NOH (R=H, Me), in iron(III) carboxylate chemistry yielded the tetranuclear complexes [Fe 4 O 2 Cl 2 (O 2 CPh) 2 {pyC(R)NO} 4 ] (R=H, 1; R=Me, 2). The crystal structure of 2 revealed the presence of a central [Fe 4 (μ 3 -O) 2 ] 8+ core comprising four Fe III ions in a ‘butterfly’ disposition and two μ 3 -O 2− ions, each bridging three Fe III ions forming the ‘wings’ of the ‘butterfly’. The Mössbauer spectra from polycrystalline samples of 2 consist of composite quadrupole-split doublets, with parameters typical for high-spin iron(III) in octahedral environments. Magnetic susceptibility measurements on 2 revealed antiferromagnetic interactions between the S=5/2 ferric ions; fits to the data required the use of two different parameters for the wingtip–body interactions. The best-fit values for these interactions were J 1 =−85cm −1 and J 2 =−27cm −1 (-2J ij S i S j Hamiltonian formalism) resulting to a diamagnetic ground state.