Ferromagnetic Coupling in the Three-Dimensional Malonato-Bridged Gadolinium(III) Complex [Gd2(mal)3(H2O)6] (H2mal = Malonic Acid)

The novel gadolinium(III) complex of formula [Gd2(mal)3(H2O)6] (1) (H2mal = 1,3-propanedioic acid) has been prepared and characterized by X-ray diffraction analysis. Crystal data for 1:  monoclinic, space group I2/a, a = 11.1064(10) Å, b = 12.2524(10) Å, c = 13.6098(2) Å, β = 92.925(10)°, U = 1849.5...

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Bibliographic Details
Published in:Inorganic chemistry 2003-09, Vol.42 (18), p.5456-5458
Main Authors: Hernández-Molina, María, Ruiz-Pérez, Catalina, López, Trinidad, Lloret, Francesc, Julve, Miguel
Format: Article
Language:English
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Summary:The novel gadolinium(III) complex of formula [Gd2(mal)3(H2O)6] (1) (H2mal = 1,3-propanedioic acid) has been prepared and characterized by X-ray diffraction analysis. Crystal data for 1:  monoclinic, space group I2/a, a = 11.1064(10) Å, b = 12.2524(10) Å, c = 13.6098(2) Å, β = 92.925(10)°, U = 1849.5(3) Å3, Z = 4. Compound 1 is a three-dimensional network made up of malonate-bridged gadolinium(III) ions where the malonate exhibits two bridging modes, η5-bidentate + unidentate and η3:η3 + bis(unidentate). The gadolinium atom is nine-coordinate with three water molecules and six malonate oxygen atoms from three malonate ligands forming a distorted monocapped square antiprism. The shortest metal−metal separations are 4.2763(3) Å [through the oxo-carboxylate bridge] and 6.541(3) Å [through the carboxylate in the anti − syn coordination mode]. The value of the angle at the oxo-carboxylate atom is 116.8(2)°. Variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction through the oxo-carboxylate pathway (J = +0.048(1) cm-1, H = −JS Gd(1)·S Gd(1a)).
ISSN:0020-1669
1520-510X
DOI:10.1021/ic034175w