Abstract: | Structural determinations of the magnesium(II) and barium(II) salts of pyromellitic acid (benzene‐1,2,4,5‐tetracarboxylic acid) are presented. Hexaaquamagnesium(II) benzene‐1,2,4,5‐tetracarboxylate(2−), [Mg(H2O)6](C10H4O8), (I), and pentaaqua[benzene‐1,2,4,5‐tetracarboxylato(2−)]barium(II), [Ba(C10H4O8)(H2O)5], (II), are both centrosymmetric and both possess a 1:1 metal–ligand ratio, but the two structures are found to differ in that the magnesium salt contains a hexaaqua cation and possesses only hydrogen‐bonding interactions between cations and anions, while the barium salt exhibits coordination of the carboxylate ligand to the nine‐coordinate metal centre. In (I), both ions sit on a 2/m site symmetry, and in (II), the cation and anion are located on m and i site symmetries, respectively. |