In the structure of the title complex, [Fe(C5H7O2)3] or Fe(acac)3, the asymmetric unit contains one mol-ecule in a general position. The coordination sphere of the Fe(III) atom is that of a slightly distorted octahedron. The crystal under investigation was a two-component pseudo-merohedral twin in the monoclinic system with a β angle close to 90°. Twin law [100/0-10/00-1] reduced the R1 residual [I > 2σ(I)] from 0.0769 to 0.0312, and the mass ratio of twin components refined to 0.8913 (5):0.1087 (5). In the crystal, mol-ecules are arranged in sheets normal to [001] via non-classical C-H⋯O hydrogen bonding. No other significant inter-molecular inter-actions are observed. The structure is a new polymorph of Fe(acac)3 and is isotypic with one polymorph of its gallium analog.
