Summary: Psilomelane has been redefined from single crystal study to be of orthorhombic symmetry with the space group P222, the dimensions a 9·45, b 13·90, c 5·72 Å, and two molecules of A3X6Mn84+O16 per unit cell, where A represents Ba²⁺, Mn²⁺, Al³⁺, Fe³⁺, Si⁴⁺ etc., and X₆ stands for (O,OH)₆ with OH about 5. This formula is very closely followed by 14 analyses of psilomelane, and the calculated density agrees fairly well with the observed density. The powder data of psilomelane cannot be indexed with Wadsley's monoclinic cell and the conditions for the space group A2/m, proposed by Wadsley for his crystal, are not satisfied by the indexing. Wadsley's crystal was not psilomelane but probably an altered phase of Vaux's neotype specimen.

The electron micrograph of shining platy crystals of psilomelane shows some almost square-faced crystals whereas that of the botryoidal material consists only of particles with irregular edges. The dehydration product of psilomelane shows gradual shrinkage of the orthorhombic cell up to 500° C, marked structural changes at 600° C, and transformation at 800° C to a monoclinic phase, similar to hollandite.