NaBiS2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to six equivalent S(1) atoms to form NaS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with eight equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with eight equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. S(1) is bonded to three equivalent Na(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SNa3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 3-9°.
NaBiS2 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to six equivalent S(1) atoms to form NaS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with eight equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 7°. There are a spread of Na(1)-S(1) bond distances ranging from 2.88-3.06 Å. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with eight equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. There are a spread of Bi(1)-S(1) bond distances ranging from 2.67-3.10 Å. S(1) is bonded to three equivalent Na(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SNa3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 3-9°.