LiHfS2 is Caswellsilverite-like structured and crystallizes in the trigonal R3m space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted LiS6 pentagonal pyramids that share corners with nine equivalent Hf(1)S6 octahedra, edges with three equivalent Hf(1)S6 octahedra, edges with six equivalent Li(1)S6 pentagonal pyramids, and  a faceface with one Hf(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-46°. Hf(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form HfS6 octahedra that share corners with nine equivalent Li(1)S6 pentagonal pyramids, edges with six equivalent Hf(1)S6 octahedra, edges with three equivalent Li(1)S6 pentagonal pyramids, and  a faceface with one Li(1)S6 pentagonal pyramid. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and three equivalent Hf(1) atoms to form a mixture of distorted face, corner, and edge-sharing SLi3Hf3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-45°. In the second S site, S(2) is bonded to three equivalent Li(1) and three equivalent Hf(1) atoms to form a mixture of face, corner, and edge-sharing SLi3Hf3 octahedra.
LiHfS2 is Caswellsilverite-like structured and crystallizes in the trigonal R3m space group. Li(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted LiS6 pentagonal pyramids that share corners with nine equivalent Hf(1)S6 octahedra, edges with three equivalent Hf(1)S6 octahedra, edges with six equivalent Li(1)S6 pentagonal pyramids, and  a faceface with one Hf(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-46°. All Li(1)-S(1) bond lengths are 2.70 Å. All Li(1)-S(2) bond lengths are 2.63 Å. Hf(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form HfS6 octahedra that share corners with nine equivalent Li(1)S6 pentagonal pyramids, edges with six equivalent Hf(1)S6 octahedra, edges with three equivalent Li(1)S6 pentagonal pyramids, and  a faceface with one Li(1)S6 pentagonal pyramid. All Hf(1)-S(1) bond lengths are 2.56 Å. All Hf(1)-S(2) bond lengths are 2.57 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and three equivalent Hf(1) atoms to form a mixture of distorted face, corner, and edge-sharing SLi3Hf3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 0-45°. In the second S site, S(2) is bonded to three equivalent Li(1) and three equivalent Hf(1) atoms to form a mixture of face, corner, and edge-sharing SLi3Hf3 octahedra.