Gaps in cubic closest packing: from MgO via spinel to the pharmacosiderite crystal structure type

Numerous ordered defect structures are known that are related to the sodium chloride (or MgO) structure type, thus they are basically cubic closest packed (ccp) arrangements with vacancies. For example the NbO type is an MgO type in which one quarter each of the anions and the cations are missing compared to the ccp in such a way that both anions and cations are in square-planar coordination. In spinel, Al 2 MgO 4 , one half of the octahedrally coordinated cations are missing compared with the MgO type and only one eighth of the tetrahedrally coordinated sites within the ccp are occupied. What these cases have in common is that all these derivatives are rather dense. This is different in pharmacosiderite, K[Fe 4 (OH) 4 As 3 O 12 ]. 6 to 7H 2 O, where one half of the anion positions, three quarters of the octahedral sites and five eighth of the tetrahedral sites remain vacant, compared to the spinel type. Pharmacosiderite is a wide open porous structure with zeolitic properties. We are illustrating these relationships using a Bärnighausen symmetry tree and by tables relating the various structure types to each other.