Li2(TaS2)3 crystallizes in the hexagonal P6_322 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent S(1) atoms to form LiS6 octahedra that share corners with twelve equivalent Ta(2)S6 pentagonal pyramids, edges with three equivalent Li(2)S6 octahedra, and faces with two equivalent Ta(1)S6 pentagonal pyramids. In the second Li site, Li(2) is bonded to six equivalent S(1) atoms to form LiS6 octahedra that share corners with six equivalent Ta(1)S6 pentagonal pyramids, corners with six equivalent Ta(2)S6 pentagonal pyramids, edges with three equivalent Li(1)S6 octahedra, and faces with two equivalent Ta(2)S6 pentagonal pyramids. There are two inequivalent Ta sites. In the first Ta site, Ta(1) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with six equivalent Li(2)S6 octahedra, edges with six equivalent Ta(2)S6 pentagonal pyramids, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 45°. In the second Ta site, Ta(2) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with three equivalent Li(2)S6 octahedra, corners with six equivalent Li(1)S6 octahedra, edges with three equivalent Ta(1)S6 pentagonal pyramids, edges with three equivalent Ta(2)S6 pentagonal pyramids, and  a faceface with one Li(2)S6 octahedra. The corner-sharing octahedral tilt angles are 45°. S(1) is bonded to one Li(1), one Li(2), one Ta(1), and two equivalent Ta(2) atoms to form a mixture of distorted corner, edge, and face-sharing SLi2Ta3 trigonal bipyramids.
Li2(TaS2)3 crystallizes in the hexagonal P6_322 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent S(1) atoms to form LiS6 octahedra that share corners with twelve equivalent Ta(2)S6 pentagonal pyramids, edges with three equivalent Li(2)S6 octahedra, and faces with two equivalent Ta(1)S6 pentagonal pyramids. All Li(1)-S(1) bond lengths are 2.56 Å. In the second Li site, Li(2) is bonded to six equivalent S(1) atoms to form LiS6 octahedra that share corners with six equivalent Ta(1)S6 pentagonal pyramids, corners with six equivalent Ta(2)S6 pentagonal pyramids, edges with three equivalent Li(1)S6 octahedra, and faces with two equivalent Ta(2)S6 pentagonal pyramids. All Li(2)-S(1) bond lengths are 2.55 Å. There are two inequivalent Ta sites. In the first Ta site, Ta(1) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with six equivalent Li(2)S6 octahedra, edges with six equivalent Ta(2)S6 pentagonal pyramids, and faces with two equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles are 45°. All Ta(1)-S(1) bond lengths are 2.48 Å. In the second Ta site, Ta(2) is bonded to six equivalent S(1) atoms to form distorted TaS6 pentagonal pyramids that share corners with three equivalent Li(2)S6 octahedra, corners with six equivalent Li(1)S6 octahedra, edges with three equivalent Ta(1)S6 pentagonal pyramids, edges with three equivalent Ta(2)S6 pentagonal pyramids, and  a faceface with one Li(2)S6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are three shorter (2.47 Å) and three longer (2.49 Å) Ta(2)-S(1) bond lengths. S(1) is bonded to one Li(1), one Li(2), one Ta(1), and two equivalent Ta(2) atoms to form a mixture of distorted corner, edge, and face-sharing SLi2Ta3 trigonal bipyramids.