Li2WP2O8 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with four equivalent W(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. W(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form WO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. 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 W(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) 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 tetrahedral geometry to one Li(1), one Li(2), one W(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like 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 trigonal planar geometry to one Li(1), one Li(2), 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 Li(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one W(1), and one P(2) atom.
Li2WP2O8 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Li(1)-O(2) bond length is 2.53 Å. The Li(1)-O(3) bond length is 2.55 Å. The Li(1)-O(4) bond length is 2.09 Å. The Li(1)-O(5) bond length is 2.39 Å. The Li(1)-O(6) bond length is 1.95 Å. The Li(1)-O(7) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with four equivalent W(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Li(2)-O(1) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.22 Å. The Li(2)-O(5) bond length is 2.34 Å. The Li(2)-O(6) bond length is 2.10 Å. The Li(2)-O(7) bond length is 2.09 Å. The Li(2)-O(8) bond length is 2.32 Å. W(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form WO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. The W(1)-O(1) bond length is 2.14 Å. The W(1)-O(2) bond length is 2.11 Å. The W(1)-O(3) bond length is 2.14 Å. The W(1)-O(4) bond length is 2.17 Å. The W(1)-O(5) bond length is 2.04 Å. The W(1)-O(8) bond length is 2.00 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-61°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The P(2)-O(5) bond length is 1.62 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.60 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 W(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) 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 tetrahedral geometry to one Li(1), one Li(2), one W(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like 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 trigonal planar geometry to one Li(1), one Li(2), 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 Li(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one W(1), and one P(2) atom.