LiTi2S4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form LiS6 octahedra that share corners with twelve equivalent Ti(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form TiS6 octahedra that share corners with six equivalent Li(1)S6 octahedra, edges with six equivalent Ti(1)S6 octahedra, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Ti(1) atoms. In the second S site, S(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing SLi2Ti3 trigonal bipyramids.
LiTi2S4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form LiS6 octahedra that share corners with twelve equivalent Ti(1)S6 octahedra, edges with two equivalent Li(1)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. Both Li(1)-S(1) bond lengths are 2.58 Å. All Li(1)-S(2) bond lengths are 2.58 Å. Ti(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form TiS6 octahedra that share corners with six equivalent Li(1)S6 octahedra, edges with six equivalent Ti(1)S6 octahedra, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. There are two shorter (2.42 Å) and one longer (2.44 Å) Ti(1)-S(1) bond length. There is one shorter (2.44 Å) and two longer (2.47 Å) Ti(1)-S(2) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Ti(1) atoms. In the second S site, S(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing SLi2Ti3 trigonal bipyramids.