W2O3(PO4)2 crystallizes in the orthorhombic Pnnm space group. W(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedra are not tilted. P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-41°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one W(1) and one P(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one W(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(1) atoms.
W2O3(PO4)2 crystallizes in the orthorhombic Pnnm space group. W(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedra are not tilted. The W(1)-O(2) bond length is 2.12 Å. The W(1)-O(3) bond length is 1.70 Å. The W(1)-O(4) bond length is 1.98 Å. The W(1)-O(5) bond length is 1.88 Å. Both W(1)-O(1) bond lengths are 1.96 Å. P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-41°. The P(1)-O(2) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.54 Å. Both P(1)-O(1) bond lengths are 1.54 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one W(1) and one P(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one W(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(1) atoms.