New electron-microprobe analyses of mayenite from the Ettringer Bellerberg volcano near Mayen in the Eifel district, Germany have high Cl contents and Raman spectroscopy indicates the presence of OH groups. Neither of these components is included in the generally accepted chemical formula, Ca12Al14O33. A refinement of the crystal structure by single-crystal X-ray methods reveals a previously unrecognized partial substitution. The O2 site which forms one of the apices of an AlO4 tetrahedron (with 3×O1 sites) is replaced by 3×O2a sites, which change the coordination of the central Al atom from tetrahedral to octahedral. This substitution is related to partial hydration of Ca12Al14O32Cl2 according to the isomorphic scheme (O2− + Cl)↔3(OH). The revised composition of Eifel mayenite is best described by the formula Ca12Al14O32–xCl2–x(OH)3x (x ~0.75); the original formula, Ca12Al14O33, is inadequate. The analysed mineral can be considered to consist of endmember Ca12Al14O32Cl2 (62.5 mol.%) and endmember Ca12Al14O30(OH)6 (37.5 mol.%).

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