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Single crystals of dibarium vanadate(V) bromide, Ba2VO4Br, were grown from a melt of Ba3(VO4)2 and BaBr2. Ba2VO4Br crystallizes in the space group Pbcm and is isotypic with the structure of chlorspodiosite, Ca2PO4Cl. Although the ionic radii in chlorspodiosite are different from those in dibarium vanadate bromide, the structures are very similar to one another. The V atom is coordinated by four O atoms, forming a slightly distorted tetrahedron. The Ba atoms occupy two different sites and are coordinated by six O atoms and three or four Br atoms, depending on the site occupied