TY - JOUR
T1 - Bent and Linear Forms of the (μ-Oxo)bis[trichloroferrate(III)] Dianion: An Intermolecular Effect - Structural, Electronic and Magnetic Properties
AU - Lledós, Agustí
AU - Moreno-Mañas, Marcial
AU - Sodupe, Mariona
AU - Vallribera, Adelina
AU - Mata, Ignasi
AU - Martínez, Benjamín
AU - Molins, Elies
PY - 2003/12/5
Y1 - 2003/12/5
N2 - 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.
AB - 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.
KW - (μ-Oxo)trichloroferrate dianion
KW - DFT calculations
KW - Iron
KW - Magnetic properties
KW - Oxygen
KW - Packing effects
U2 - 10.1002/ejic.200300336
DO - 10.1002/ejic.200300336
M3 - Article
SN - 1434-1948
SP - 4187
EP - 4194
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 23
ER -