Li6(TeO6) crystallizes in the trigonal R-3 space group. Li(1) is bonded to five equivalent O(1) atoms to form distorted LiO5 square pyramids that share  a cornercorner with one Te(1)O6 octahedra, corners with eight equivalent Li(1)O5 square pyramids, edges with two equivalent Te(1)O6 octahedra, and edges with six equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 12°. Te(1) is bonded to six equivalent O(1) atoms to form TeO6 octahedra that share corners with six equivalent Li(1)O5 square pyramids and edges with twelve equivalent Li(1)O5 square pyramids. O(1) is bonded to five equivalent Li(1) and one Te(1) atom to form a mixture of distorted corner and edge-sharing OLi5Te octahedra. The corner-sharing octahedral tilt angles range from 0-18°.
Li6(TeO6) crystallizes in the trigonal R-3 space group. Li(1) is bonded to five equivalent O(1) atoms to form distorted LiO5 square pyramids that share  a cornercorner with one Te(1)O6 octahedra, corners with eight equivalent Li(1)O5 square pyramids, edges with two equivalent Te(1)O6 octahedra, and edges with six equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 12°. There are a spread of Li(1)-O(1) bond distances ranging from 1.94-2.38 Å. Te(1) is bonded to six equivalent O(1) atoms to form TeO6 octahedra that share corners with six equivalent Li(1)O5 square pyramids and edges with twelve equivalent Li(1)O5 square pyramids. All Te(1)-O(1) bond lengths are 1.93 Å. O(1) is bonded to five equivalent Li(1) and one Te(1) atom to form a mixture of distorted corner and edge-sharing OLi5Te octahedra. The corner-sharing octahedral tilt angles range from 0-18°.