The coordination chemistry of some six–coordinated manganese(III) complexes with oxygen donor ligands in the solid state has been studied by EXAFS. The structures of tris(acetylacetonato)manganese(III), as purchased and recrystallized from methanol and acetone, show that they have non–centrosymmetric tetragonally elongated octahedral coordination with significantly different axial Mn–O bond distances due to pseudo-Jahn-Teller distortion. When recrystallization was performed in 2–propanol and acetonitrile, a partial reduction to tris(bis(μ₂–acetylacetonato)manganese(II)) was observed. Solid manganese(III) phosphate hydrate is shown to have the same kind of non–centrosymmetric tetragonally elongated octahedral coordination, while the crystallographic study reports centrosymmetric coordination with an axial Mn–O bond distance equal to the mean of the distances observed by EXAFS. A literature survey has been performed to study the symmetry of six-coordinated metal ions with possibility to form Jahn-Teller distorted complexes, those with d⁹, high–spin d⁴ and low–spin d⁷ electron configuration. It shows that when a compound crystallizes in a non–centrosymmetric space group or when the metal ion is out of the center of symmetry in a centrosymmetric space group, the axial M–O bond distances are significantly different. In crystallographic studies a random orientation of the axial bonds in tetragonally elongated octahedral complexes results in seemingly centrosymmetric complexes even though the axial bond distances are different in the individual complexes. The literature survey was used to estimate the ionic radii of the chromium(II), manganese(III), nickel(III) and silver(II) ions in their low– and high–spin states.