LiNbSe2 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mmc space group. Li(1) is bonded to six equivalent Se(1) atoms to form LiSe6 octahedra that share corners with twelve equivalent Nb(1)Se6 pentagonal pyramids, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent Nb(1)Se6 pentagonal pyramids. Nb(1) is bonded to six equivalent Se(1) atoms to form distorted NbSe6 pentagonal pyramids that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent Nb(1)Se6 pentagonal pyramids, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 45°. Se(1) is bonded to three equivalent Li(1) and three equivalent Nb(1) atoms to form a mixture of distorted face, corner, and edge-sharing SeLi3Nb3 pentagonal pyramids.
LiNbSe2 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mmc space group. Li(1) is bonded to six equivalent Se(1) atoms to form LiSe6 octahedra that share corners with twelve equivalent Nb(1)Se6 pentagonal pyramids, edges with six equivalent Li(1)Se6 octahedra, and faces with two equivalent Nb(1)Se6 pentagonal pyramids. All Li(1)-Se(1) bond lengths are 2.67 Å. Nb(1) is bonded to six equivalent Se(1) atoms to form distorted NbSe6 pentagonal pyramids that share corners with twelve equivalent Li(1)Se6 octahedra, edges with six equivalent Nb(1)Se6 pentagonal pyramids, and faces with two equivalent Li(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 45°. All Nb(1)-Se(1) bond lengths are 2.63 Å. Se(1) is bonded to three equivalent Li(1) and three equivalent Nb(1) atoms to form a mixture of distorted face, corner, and edge-sharing SeLi3Nb3 pentagonal pyramids.