Li4MoO5 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 Mo(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra, edges with three equivalent Mo(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. Mo(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted MoO6 octahedra that share corners with two equivalent Mo(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 0-10°. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one Mo(1) atom to form OLi5Mo octahedra that share  a cornercorner with one O(2)Li4Mo2 octahedra, corners with five equivalent O(1)Li5Mo octahedra, edges with three equivalent O(2)Li4Mo2 octahedra, and edges with nine equivalent O(1)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 4-16°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent Mo(1) atoms to form distorted OLi4Mo2 octahedra that share corners with two equivalent O(2)Li4Mo2 octahedra, corners with four equivalent O(1)Li5Mo octahedra, and edges with twelve equivalent O(1)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Li4MoO5 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 Mo(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra, edges with three equivalent Mo(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. The Li(1)-O(2) bond length is 2.12 Å. There are a spread of Li(1)-O(1) bond distances ranging from 1.96-2.19 Å. Mo(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted MoO6 octahedra that share corners with two equivalent Mo(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 0-10°. There is one shorter (1.81 Å) and one longer (2.39 Å) Mo(1)-O(2) bond length. All Mo(1)-O(1) bond lengths are 1.88 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one Mo(1) atom to form OLi5Mo octahedra that share  a cornercorner with one O(2)Li4Mo2 octahedra, corners with five equivalent O(1)Li5Mo octahedra, edges with three equivalent O(2)Li4Mo2 octahedra, and edges with nine equivalent O(1)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 4-16°. In the second O site, O(2) is bonded to four equivalent Li(1) and two equivalent Mo(1) atoms to form distorted OLi4Mo2 octahedra that share corners with two equivalent O(2)Li4Mo2 octahedra, corners with four equivalent O(1)Li5Mo octahedra, and edges with twelve equivalent O(1)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-9°.