Li2ReO3 is Caswellsilverite-like structured and crystallizes in the trigonal R-3c space group. Li(1) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Re(1)O6 octahedra, corners with nine equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Re(1)O6 octahedra,  a faceface with one Li(1)O6 octahedra, and  a faceface with one Re(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-51°. Re(1) is bonded to six equivalent O(1) atoms to form ReO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Re(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. O(1) is bonded to four equivalent Li(1) and two equivalent Re(1) atoms to form a mixture of distorted corner and edge-sharing OLi4Re2 pentagonal pyramids.
Li2ReO3 is Caswellsilverite-like structured and crystallizes in the trigonal R-3c space group. Li(1) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Re(1)O6 octahedra, corners with nine equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Re(1)O6 octahedra,  a faceface with one Li(1)O6 octahedra, and  a faceface with one Re(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-51°. All Li(1)-O(1) bond lengths are 2.11 Å. Re(1) is bonded to six equivalent O(1) atoms to form ReO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Re(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. All Re(1)-O(1) bond lengths are 2.04 Å. O(1) is bonded to four equivalent Li(1) and two equivalent Re(1) atoms to form a mixture of distorted corner and edge-sharing OLi4Re2 pentagonal pyramids.