Novel modification of anhydrous transition metal oxalates from powder diffraction.

The known metal-C2O4 structures may be divided into two modifications, α and ß. The α-modification has an order-disorder struxture, revealing one-dimensional disordering of the metal-oxalate chains, and the ß-modification is ordered. The crystal structures of orthorhombic γ-MnC2O4 {poly[µ-oxalato-manganese(II)]; space group Pmna, a = 7.1333 (1), b = 5.8787 (1), c = 9.0186 (2) Å, V = 378.19 (1) Å3, Z = 4 and Dx = 2.511 Mg m-3} and γ-CdC2O4 {poly[µ-oxalato-cadmium(II)]; space group Pmna, a = 7.3218 (1), b = 6.0231 (1), c = 9.2546 (2) Å, V = 408.13 (1) Å3, Z = 4 and Dx = 3.262 Mg m-3} have been obtained from powder diffraction patterns. The structures are isostructural. Each metal atom in each structure is coordinated by seven O atoms which belong to five oxalate ions. The crystal packing, which contains noticeable cavities in the [101] and [001] directions, is not close packed and essentially differs from the known disordered α- and ordered ß-modifications of transition metal oxalates. This modification seems to be metastable. It was found that a spontaneous Î³â†’ß phase transition takes place for γ-CdC2O4.