LiW2P3O13 crystallizes in the monoclinic P2/c space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(7) atoms. W(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form WO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-34°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent W(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-45°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one W(1) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a water-like geometry to one Li(1) and one W(1) atom.
LiW2P3O13 crystallizes in the monoclinic P2/c space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(7) atoms. Both Li(1)-O(3) bond lengths are 2.44 Å. Both Li(1)-O(7) bond lengths are 1.97 Å. W(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form WO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The W(1)-O(2) bond length is 2.12 Å. The W(1)-O(3) bond length is 2.06 Å. The W(1)-O(4) bond length is 2.03 Å. The W(1)-O(5) bond length is 2.10 Å. The W(1)-O(6) bond length is 2.06 Å. The W(1)-O(7) bond length is 1.77 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-34°. Both P(1)-O(3) bond lengths are 1.55 Å. Both P(1)-O(4) bond lengths are 1.54 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent W(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-45°. The P(2)-O(1) bond length is 1.62 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.53 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the second O site, O(2) is bonded in a 2-coordinate geometry to one W(1) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a water-like geometry to one Li(1) and one W(1) atom.