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The structures of ZrNCl on one hand and TiOCl and AlOCl on the other hand are analysed in comparison with the Zintl phases Ca[Al 2 Si 2 ] and Na[AlSi], respectively. In the former, the [ZrN] +  sublattice is isostructural to the [Al 2 Si 2 ] 2-  skeleton whereas the latter are orthorhombic distortions of the Na[AlSi] structure. The three structures can be rationalised by means of an inverse Zintl-Klemm concept, in similarity with the Zintl-Klemm concept which accounts for the structures of the Zintl phases. In addition, Ca[Al 2 Si 2 ] presents the same structure than the hexacelsian oxide Ca[Al 2 Si 2 O 8 ] providing a new example of how the cation arrays, in oxides, maintain the structure of their respective alloy.

The structures of ZrNCl, TiOCl and AlOCl in the light of the Zintl-Klemm concept