LiTiSe2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to six equivalent Se(1) atoms to form LiSe6 octahedra that share corners with twelve equivalent Ti(1)Se6 octahedra, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent Ti(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 47°. Ti(1) is bonded to six equivalent Se(1) atoms to form TiSe6 octahedra that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent Ti(1)Se6 octahedra, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 47°. Se(1) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted edge and corner-sharing SeLi3Ti3 pentagonal pyramids.
LiTiSe2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Li(1) is bonded to six equivalent Se(1) atoms to form LiSe6 octahedra that share corners with twelve equivalent Ti(1)Se6 octahedra, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent Ti(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 47°. All Li(1)-Se(1) bond lengths are 2.71 Å. Ti(1) is bonded to six equivalent Se(1) atoms to form TiSe6 octahedra that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent Ti(1)Se6 octahedra, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 47°. All Ti(1)-Se(1) bond lengths are 2.61 Å. Se(1) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form a mixture of distorted edge and corner-sharing SeLi3Ti3 pentagonal pyramids.