The recently defined arctite supergroup contains nine mineral members defined as hexagonal intercalated antiperovskites, most of which have been found in pyrometamorphic rocks of the Hatrurim Complex, Israel. Three members of this supergroup: nabimusaite, gazeevite and zadovite, were identified for the first time in altered carbonate–silicate xenoliths from the Caspar and Scherer quarries, Bellerberg volcano in Germany. Present work focuses on the chemical, structural and spectroscopic investigation of these minerals and their correlation with holotype counterparts. The apparent differences are mainly related to the chemical composition, types of substitution in the tetrahedral and antiperovskite layers within the crystal structure, and position of bands in the Raman spectra. In the Bellerberg volcano xenoliths, the crystallisation of nabimusaite and gazeevite is caused by high-temperature alteration of early mineral associations (clinker-like phases) and their reaction with melt or gas generated by volcanic activity. In turn, the formation of zadovite is related to the Ba-rich silicate melt that filled the intergranular space between the rock-forming minerals.