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Combining laboratory X-ray powder diffraction with in-situ high-temperature synchrotron experiments and differential scanning calorimetry, it has been shown that Ba 21 Al 40 , Ba 3 Al 5 , Ba 7 Al 10  and Ba 4 Al 5  decompose peritectically at 914, 826, 756, and 732°C, respectively. In addition, a new binary compound with the composition Ba 4 Al 7+ x   ( x  = 0.17) and the formation temperature of 841°C was found. The initial structural model (space group  P 6 3 / mmc ,  a  = 6.0807(1),  c  = 39.2828(8) Å) with four Ba and five Al crystallographic positions was developed. It is based on the intergrowth concept involving the neighboring Ba 21 Al 40  and Ba 3 Al 5  phases and the derived atomic arrangement is subsequently refined using X-ray diffraction data. The crystal structures of all phases in the Ba–Al system, except BaAl 4 , exhibit Kagomé nets of aluminum atoms resembling those observed for the  B  atoms in the Laves phases  AB  2 . In the crystal structure of Ba 4 Al 7+ x  , single Kagomé layers alternate with double slabs (MgZn 2  motif) along [001] and are separated by Ba cations. Intergrowth features of Ba 4 Al 7+ x   are discussed together with the neighboring Ba–Al compounds and Sr 5 Al 9 .

The new barium compound Ba 4 Al 7+ x : formation and crystal structure