Li3TiS3 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form distorted LiS4 trigonal pyramids that share corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Li(2)S4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 41-65°. Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(2)S4 trigonal pyramids, and faces with two equivalent Ti(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded to four equivalent Li(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Ti2 pentagonal pyramids.
Li3TiS3 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(2) atoms. There is one shorter (2.37 Å) and one longer (2.55 Å) Li(1)-S(1) bond length. There is one shorter (2.44 Å) and one longer (2.55 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form distorted LiS4 trigonal pyramids that share corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Li(2)S4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 41-65°. There are two shorter (2.40 Å) and two longer (2.56 Å) Li(2)-S(1) bond lengths. Ti(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form TiS6 octahedra that share corners with four equivalent Li(2)S4 trigonal pyramids, edges with two equivalent Li(2)S4 trigonal pyramids, and faces with two equivalent Ti(1)S6 octahedra. Both Ti(1)-S(2) bond lengths are 2.53 Å. All Ti(1)-S(1) bond lengths are 2.54 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent Ti(1) atoms. In the second S site, S(2) is bonded to four equivalent Li(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Ti2 pentagonal pyramids.