Li(TiTe2)2 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form LiTe6 octahedra that share corners with twelve equivalent Ti(1)Te6 octahedra, edges with two equivalent Li(1)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Ti(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form TiTe6 octahedra that share corners with six equivalent Li(1)Te6 octahedra, edges with six equivalent Ti(1)Te6 octahedra, and  a faceface with one Li(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Ti(1) atoms. In the second Te site, Te(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing TeLi2Ti3 trigonal bipyramids.
Li(TiTe2)2 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form LiTe6 octahedra that share corners with twelve equivalent Ti(1)Te6 octahedra, edges with two equivalent Li(1)Te6 octahedra, and faces with two equivalent Ti(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Both Li(1)-Te(1) bond lengths are 2.90 Å. All Li(1)-Te(2) bond lengths are 2.92 Å. Ti(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form TiTe6 octahedra that share corners with six equivalent Li(1)Te6 octahedra, edges with six equivalent Ti(1)Te6 octahedra, and  a faceface with one Li(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. All Ti(1)-Te(1) bond lengths are 2.78 Å. There are two shorter (2.82 Å) and one longer (2.83 Å) Ti(1)-Te(2) bond length. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Ti(1) atoms. In the second Te site, Te(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing TeLi2Ti3 trigonal bipyramids.