MC5O5.3H2O (I - III; M = Cu, Mn, Fe, resp., H2C5O5 = croconic acid) were prepd. and characterized by structural and magnetic measurements. The crystals are orthorhombic, space group Pbca, Z = 8. The previously reported structures of I and II, refined here, and the novel structure of III were solved by direct methods (R = 0.029, 0.025 and 0.025, resp.). The overall structure is similar for the 3 compds. and consists of infinite 1-dimensional chains of metal ions bridged by croconate ligands acting in a monodentate and bidentate fashion. The magnetic properties of I, II and III are reported and discussed on the basis of intrachain and interchain exchange couplings and, for III, of single-ion axial zero-field splitting contributions. Weak antiferromagnetic intrachain interactions via the croconate dianion (J = 0.99(3), 0.22(1) and ≤0.54 cm-1 for I, II and III, resp.) appear to be responsible of most of the obsd. magnetic behavior.
Molecular Structure and Magnetic Properties of Copper(II), Manganese(II) and Iron(II) Croconate Tri-hydrate / Cornia, Andrea; FABRETTI COSTANTINO, Antonio; Giusti, Aleardo; F., Ferraro; D., Gatteschi. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - STAMPA. - 212:(1993), pp. 87-94.
Molecular Structure and Magnetic Properties of Copper(II), Manganese(II) and Iron(II) Croconate Tri-hydrate
CORNIA, Andrea;FABRETTI COSTANTINO, Antonio;GIUSTI, Aleardo;
1993
Abstract
MC5O5.3H2O (I - III; M = Cu, Mn, Fe, resp., H2C5O5 = croconic acid) were prepd. and characterized by structural and magnetic measurements. The crystals are orthorhombic, space group Pbca, Z = 8. The previously reported structures of I and II, refined here, and the novel structure of III were solved by direct methods (R = 0.029, 0.025 and 0.025, resp.). The overall structure is similar for the 3 compds. and consists of infinite 1-dimensional chains of metal ions bridged by croconate ligands acting in a monodentate and bidentate fashion. The magnetic properties of I, II and III are reported and discussed on the basis of intrachain and interchain exchange couplings and, for III, of single-ion axial zero-field splitting contributions. Weak antiferromagnetic intrachain interactions via the croconate dianion (J = 0.99(3), 0.22(1) and ≤0.54 cm-1 for I, II and III, resp.) appear to be responsible of most of the obsd. magnetic behavior.
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