Abstract: | The crystal structures of Mn5O8 and Cd2Mn3O8 are determined from single crystal and high resolution X-ray powder data. Both structures have very similar monoclinic unit cells, space group C–C2/m, and are isotypic: Hence, the true formula of Mn5O8 is MnMnO8. The crystal structure consists of pseudohexagonal MnIV sheets (bc) with similar oxygen sheets on either side, giving a distorted octahedral coordination to the MnIV. As every fourth MnIV is missing in these “main layers”, their composition becomes Mn3O8, and chains of coordination octahedra linked by common edges become distinct. Above and below the empty MnIV sites are either MnII or CdII completing the composition MnMnO8 or Cd2Mn3O8 respectively. Examples of similar “double layer” structures are given. |