Li3WP2O8 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent W(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. 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 three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. 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 Li(2)O6 octahedra and corners with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one W(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one W(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one W(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one W(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one W(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom.
Li3WP2O8 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. The Li(1)-O(5) bond length is 2.13 Å. The Li(1)-O(6) bond length is 2.14 Å. The Li(1)-O(7) bond length is 2.02 Å. The Li(1)-O(8) bond length is 1.97 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent W(1)O6 octahedra. The Li(2)-O(1) bond length is 2.10 Å. The Li(2)-O(3) bond length is 2.32 Å. The Li(2)-O(4) bond length is 2.23 Å. The Li(2)-O(5) bond length is 2.29 Å. The Li(2)-O(6) bond length is 2.27 Å. The Li(2)-O(8) bond length is 2.12 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(3)-O(1) bond length is 1.96 Å. The Li(3)-O(2) bond length is 2.02 Å. The Li(3)-O(3) bond length is 2.11 Å. The Li(3)-O(4) bond length is 2.16 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 three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. The W(1)-O(2) bond length is 2.17 Å. The W(1)-O(3) bond length is 2.19 Å. The W(1)-O(4) bond length is 2.19 Å. The W(1)-O(5) bond length is 2.19 Å. The W(1)-O(6) bond length is 2.19 Å. The W(1)-O(7) bond length is 2.17 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.52 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 Li(2)O6 octahedra and corners with three equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. The P(2)-O(1) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.58 Å. The P(2)-O(6) bond length is 1.58 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one W(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one W(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one W(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one W(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one W(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom.