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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 31, Number 12
BKCSDE 31(12)
December 20, 2010 

Synthesis, Crystal structure, and Magnetic Properties of Dinuclear Iron(III) Complexes with Methoxo Bridges
Jong Won Shin, Jeong Hyeong Han, Sankara Rao Rowthu, Bong Gon Kim, Kil Sik Min*
Iron(III) complex, Ligand, Crystal structure, Stacking interactions, Magnetic properties
The reaction of stoichiometric amount of FeCl2·4H2O, (2-pyridylmethyl, 3-pyridylmethyl)amine (2,3-pyma) and sodium azide/sodium thiocyanate in methanol under aerobic conditions affords the dinuclear Fe(III) complexes, [(2,3-pyma) (N3)2Fe(μ-OCH3)2Fe(N3)2(2,3-pyma)]·CH3OH (1) and [(2,3-pyma)(NCS)2Fe(μ-OCH3)2Fe(NCS)2(2,3-pyma)] (2) in good yield. Two bis-methoxy-bridged diiron(III) complexes are isolated and characterized. The coordination geometries around iron(III) ions in 1 and 2 are the same tetragonally distorted octahedron. The iron(III) ions are coordinated by two nitrogens of a 2,3-pyma, two nitrogens of two azide/thiocyanate ions, and two oxygens of two methoxy groups. Both compounds are isomorphous. The structures of 1 and 2 display the C-H···π and/or π-π stacking interactions as well as hydrogen bonding interactions, respectively. Compounds 1 and 2 show significant antiferromagnetic couplings through the bridged methoxy groups between the iron(III) ions in the temperature range from 5 to 300 K (H = ‒2JS1·S2, J = ‒19.1 and ‒13.9 cm‒1 for 1 and 2).
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