Li4WO6 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent W(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. W(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form WO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one W(1) atom to form a mixture of corner and edge-sharing OLi4W square pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one W(1) atom to form a mixture of corner and edge-sharing OLi4W square pyramids.
Li4WO6 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. Both Li(1)-O(2) bond lengths are 2.16 Å. There are two shorter (2.06 Å) and two longer (2.25 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent W(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. Both Li(2)-O(2) bond lengths are 2.01 Å. There are two shorter (2.08 Å) and two longer (2.32 Å) Li(2)-O(1) bond lengths. W(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form WO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both W(1)-O(2) bond lengths are 1.95 Å. All W(1)-O(1) bond lengths are 1.94 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one W(1) atom to form a mixture of corner and edge-sharing OLi4W square pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one W(1) atom to form a mixture of corner and edge-sharing OLi4W square pyramids.