Journal of the Chemical Society, Dalton Transactions p. 1967 - 1971 (1996)
Update date:2022-09-26
Topics:
Deguchi, Shuhei
Fujioka, Mamoru
Okamoto, Yoshihiko
Yasuda, Tsutomu
Nakamura, Nobuhumi
Yamaguchi, Kazuya
Suzuki, Shinnichiro
(Z)-2-(2-Aminothiazol-4-yl)-N-(2-hydroxyethyl)-2-(hydroxyimino)acetamide (HL) has been employed as a model compound for a cephalosporin antibiotic, Cefdinir. A trinuclear iron(III) complex [Fe3L6]Cl[OH]2 1 has been obtained from a methanol solution containing HL and FeCl3 and its structure determined by X-ray crystallography: monoclinic, space group P21/n, a = 15.559(1), b = 19.295(2), c = 10.963(1) A, β = 101.29(1)°, Z = 2. The molecular structure contains a linear Fe(1)-Fe(2)-Fe(1′) arrangement, the central atom Fe(2) being an inversion centre. Atom Fe(1) is co-ordinated to three molecules of L through the thiazole and oximate nitrogen atoms to form Fe(1)L3, and Fe(2) to six oximate oxygen atoms of the two Fe(1)L3 units. The two Fe(1)L3 units are bridged by the central iron atom Fe(2). The Moessbauer spectrum of 1 gave an apparent doublet signal consisting of two doublets, A and B, assigned to Fe(1) and Fe(2), respectively. The isomer shifts δ of these doublets are the same (0.26 mm s-1), and are typical for high-spin iron(III). In addition, the reflectance spectrum did not show any intervalence bands. These spectral data indicate that the three iron atoms are high-spin iron(III). The compound co-ordinates to iron(III) via the thiazole ring nitrogen atom and the oximate nitrogen atom (2N mode) in methanol which is different from that in water, where L prefers to co-ordinate to an iron(III) through the oximate oxygen atom and the amide oxygen atom (2O mode).
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(1997)
