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AgCaCdMg₂(PO₄)₃ and AgCd₂Mg₂(PO₄)₃, two new compounds with the alluaudite-type structure, were synthesized by a solid state reaction in air at 750°C. The X-ray powder diffraction pattern of AgCaCdMg₂(PO₄)₃ indicates the presence of small amounts of (Ca, Mg)₃(PO₄)₂ with the whitlockite structure, as impurity, whereas AgCd₂Mg₂(PO₄)₃ is constituted by pure alluaudite. The Rietveld refinements of the X-ray powder diffraction patterns indicate an ordered cationic distribution for AgCd₂Mg₂(PO₄)₃, with Ag on A(2)′, Cd on A(1) and M(1), and Mg on M(2), whereas a disordered distribution of Cd and Ca between the A(1) and M(1) sites is observed for AgCaCdMg₂(PO₄)₃. The catalytic properties of these compounds has been measured in reaction of butan-2-ol dehydrogenation. In the absence of oxygen, both samples exhibit poor dehydrogenation activity. All samples displayed no dehydration activity …