NaVS2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Na(1) is bonded to six equivalent S(1) atoms to form distorted NaS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with six equivalent Na(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with twelve equivalent Na(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and faces with two equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. S(1) is bonded in a 6-coordinate geometry to three equivalent Na(1) and three equivalent V(1) atoms.
NaVS2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. Na(1) is bonded to six equivalent S(1) atoms to form distorted NaS6 octahedra that share corners with twelve equivalent V(1)S6 octahedra, edges with six equivalent Na(1)S6 octahedra, and faces with two equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. All Na(1)-S(1) bond lengths are 2.86 Å. V(1) is bonded to six equivalent S(1) atoms to form VS6 octahedra that share corners with twelve equivalent Na(1)S6 octahedra, edges with six equivalent V(1)S6 octahedra, and faces with two equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. All V(1)-S(1) bond lengths are 2.45 Å. S(1) is bonded in a 6-coordinate geometry to three equivalent Na(1) and three equivalent V(1) atoms.