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2H20 (Leblanc & Ferey, 1989) contain tetrahedrally coordinated V atoms. We describe here the structure of piperazine metavanadate trihydrate, (I). IH N~-~N H13-The solution of the structure of piperazine metavanadate trihydrate shows that the asymmetric unit of the crystal structure consists of a V30~-unit, which is part of a polymeric anion, two piperazine cations unequally protonated (one cation is doubly protonated and the other is singly protonated) and three molecules of water. The metavanadate anions are infinite chains of VO4 corner-sharing tetrahedra with each V atom in the centre of a tetrahedron formed by four O atoms. The V--O distances, 1.600 (4)-1.796 (4),~,, are within the range observed in other metavanadate anions. The O---V-----O angles are in the range 107.5 (2)-111.5 (2) °, and give no indication of any strong distortion of the tetrahedral environment. The CmN distances in the piperazine cations are within the range observed in the cations in ethylenediammonium vanadate (Bensch, Hug, Relier & Oswald, 1987), n-hexylammonium metavanadate (Roman, Aranzabe, Luque & Guti6rrez-Zorrilla, 1991) and 3-aza-1,5-pentamethylenediammonium metavanadate (Roman, AbstractThe structure of piperazine-l,4-diium piperazin-l-ium metavanadate trihydrate,