LiVSe2 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 V(1)Se6 octahedra, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 46°. V(1) is bonded to six equivalent Se(1) atoms to form VSe6 octahedra that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 46°. Se(1) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing SeLi3V3 pentagonal pyramids.
LiVSe2 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 V(1)Se6 octahedra, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 46°. All Li(1)-Se(1) bond lengths are 2.67 Å. V(1) is bonded to six equivalent Se(1) atoms to form VSe6 octahedra that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 46°. All V(1)-Se(1) bond lengths are 2.54 Å. Se(1) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing SeLi3V3 pentagonal pyramids.