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Molecular structure and magnetic properties of copper(II), manganese(II) and iron(II) croconate tri-hydrate

✍ Scribed by Andrea Cornia; Antonio C. Fabretti; Aleardo Giusti; Fabrizio Ferraro; Dante Gatteschi

Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
762 KB
Volume
212
Category
Article
ISSN
0020-1693

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✦ Synopsis

The compounds

MnC505 .3H,O with M =Cu (I), Mn (II), Fe (III), were prepared and characterized by means of structural and magnetic measurements.

The crystals are orthorhombic, space group Pbca, with a = 11.770( 2), b = 8.085(2), c = 15.571(2) 8, for I, a = 12.063(3), b = 8.213(2), c = 15.652(3) 8, for II, a = 11.999(2), b =8.158(l), c = 15.536(4) A for III; Z = 8. The previously reported structures of I and II, refined in this work, and the novel structure of III were solved by direct methods and least-squares refinement of structural parameters led to conventional R factors of 0.029, 0.025 and 0.025 for I, II and III, respectively. The overall structure is similar for the three compounds and consists of infinite one-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 zerofield splitting contributions.

Weak antiferromagnetic intrachain interactions via the croconate dianion (J= 0.99(3), 0.22(l) and ~0.54 cm-' for I, II and III, respectively) appear to be responsible of most of the observed magnetic behavior.

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## Abstract Treatment of anhydrous MCl~2~ (M = Mn, Fe) with (Ph~2~PMe~2~Si)~3~CH in toluene at elevated temperature resulted in the isolation of colorless (MnCl~2~{(Ph~2~PMe~2~Si)~3~CH}) (1) and light yellow (FeCl~2~{(Ph~2~PMe~2~Si)~3~CH}) (2) in high yield. These paramagnetic complexes have been c