Bent and Linear Forms of the (μ-Oxo)bis[trichloroferrate(III)] Dianion: An Intermolecular Effect - Structural, Electronic and Magnetic Properties

Agustí Lledós, Marcial Moreno-Mañas, Mariona Sodupe, Adelina Vallribera, Ignasi Mata, Benjamín Martínez, Elies Molins

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9 Citations (Scopus)

Abstract

We have analyzed the great diversity of Fe-O-Fe angles, 140-180°, found in the X-ray structures of the (p-oxo)bis-[trichloroferrate(III)] dianion [Cl3FeOFeCl3]2- from both experimental and theoretical points of view. Theoretical calculations show that only the linear isomer is found as a minimum on the potential energy surface. Detailed analysis of the crystal packing indicates that the angular form is due to attractive intermolecular interactions. Analysis of a selected reduced set of the 45 crystal structures retrieved from the Cambridge Structural Database allowed us to classify the bending of the [Cl3FeOFeCl3]2- dianion in three categories, depending on the balance and strength of the intermolecular O⋯H-X contacts. A crystal diffraction study on the bis(benzyltrimethylammonium) salt has shown both bent (144.6°) and linear (180°) forms of the (μ-oxo)bis[trichloroferrate(III)] dianion. The magnetic susceptibility of this compound has been fitted by assuming two equally weighted contributions (Jang and Jlin) of the two forms, considering Jang - Jlin estimated by theoretical calculations. The obtained Jang and Jlin of -117 and -133 cm-1 respectively, agree well with B3LYP results. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Original languageEnglish
Pages (from-to)4187-4194
JournalEur. J. Inorg. Chem.
Issue number23
DOIs
Publication statusPublished - 5 Dec 2003

Keywords

  • (μ-Oxo)trichloroferrate dianion
  • DFT calculations
  • Iron
  • Magnetic properties
  • Oxygen
  • Packing effects

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