Li4WO5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4 space group. Li(1) is bonded to one O(2) and five equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra, edges with three equivalent W(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-16°. W(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with twelve equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one W(1) atom to form OLi5W octahedra that share  a cornercorner with one O(2)Li4W2 octahedra, corners with five equivalent O(1)Li5W octahedra, edges with three equivalent O(2)Li4W2 octahedra, and edges with nine equivalent O(1)Li5W octahedra. The corner-sharing octahedral tilt angles range from 2-16°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent W(1) atoms to form OLi4W2 octahedra that share corners with two equivalent O(2)Li4W2 octahedra, corners with four equivalent O(1)Li5W octahedra, and edges with twelve equivalent O(1)Li5W octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Li4WO5 is Caswellsilverite-like structured and crystallizes in the tetragonal I4 space group. Li(1) is bonded to one O(2) and five equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra, edges with three equivalent W(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-16°. The Li(1)-O(2) bond length is 2.17 Å. There are a spread of Li(1)-O(1) bond distances ranging from 1.96-2.22 Å. W(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with twelve equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There is one shorter (1.85 Å) and one longer (2.25 Å) W(1)-O(2) bond length. All W(1)-O(1) bond lengths are 1.90 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one W(1) atom to form OLi5W octahedra that share  a cornercorner with one O(2)Li4W2 octahedra, corners with five equivalent O(1)Li5W octahedra, edges with three equivalent O(2)Li4W2 octahedra, and edges with nine equivalent O(1)Li5W octahedra. The corner-sharing octahedral tilt angles range from 2-16°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent W(1) atoms to form OLi4W2 octahedra that share corners with two equivalent O(2)Li4W2 octahedra, corners with four equivalent O(1)Li5W octahedra, and edges with twelve equivalent O(1)Li5W octahedra. The corner-sharing octahedral tilt angles range from 0-7°.