The magnetization of [Fe(OD2)6]2+ in ammonium ferrous Tutton salt studied by polarized neutron diffraction - a canted paramagnet

A polarized neutron diffraction experiment has been done on deuterated ammonium ferrous Tutton salt at 1.5 K, 4.6 T with orientations of the magnetic field along the crystal b and c* axes. The flipping ratios of 303 and 280 reflections respectively were used, after correction for extinction, to give 121 and 118 unique values of the magnetic structure factor FM, Z(hkl) (eff). Those values were used in refinements of models for a description of the magnetization density in the crystal. All models resulted in substantial (37° and 45°) canting of the magnetization direction in the paramagnet away from the magnetic field, to an almost constant direction with respect to the O6 ligand framework, indicating large magnetic anisotropy at the iron atom sites. There is delocalization of magnetization density away from the iron atom into the Fe-O overlap region ( — 4.5%) and onto the OD 2 ligands (6.5%), values comparable with the delocalization of spin from the metal atom in other Tutton salts studied. An earlier ligand field model for the electronic structure of the ion based upon spectroscopic and magnetic data is shown to be inadequate, because it is incompatible with the observed anisotropy in the magnetization around the iron atoms.