Single crystals of α-Ba2P2O7, dibarium diphosphate, were obtained by solid-state reaction. The orthorhombic structure is isotypic with α-Sr2P2O7 and is the second polymorph obtained for this composition. The structure is built from two different BaO9 polyhedra (both with m symmetry), with Ba—O distances in the ranges 2.7585 (10)–3.0850 (6) and 2.5794 (13)–2.9313 (4) Å. These polyhedra are further linked by sharing corners along [010] and either edges or triangular faces perpendicularly to [010] to form the three-dimensional framework. This polyhedral linkage delimits large channels parallel to [010] where the P2O7 diphosphate anions are located. These groups (symmetry m) are characterized by a P—O—P angle of 131.52 (9)° and an eclipsed conformation. They are connected to the BaO9 polyhedra through edges and corners.
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