NaSbS2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form NaS6 octahedra that share corners with four equivalent Na(1)S6 octahedra, corners with five equivalent Sb(1)S5 square pyramids, edges with four equivalent Na(1)S6 octahedra, and edges with five equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 5-12°. Sb(1) is bonded to two equivalent S(1) and three equivalent S(2) atoms to form SbS5 square pyramids that share corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Sb(1)S5 square pyramids, edges with five equivalent Na(1)S6 octahedra, and edges with three equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 2-88°. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and two equivalent Sb(1) atoms to form SNa3Sb2 square pyramids that share corners with five equivalent S(2)Na3Sb3 octahedra, corners with two equivalent S(1)Na3Sb2 square pyramids, edges with five equivalent S(2)Na3Sb3 octahedra, and edges with three equivalent S(1)Na3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 2-84°. In the second S site, S(2) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form SNa3Sb3 octahedra that share corners with four equivalent S(2)Na3Sb3 octahedra, corners with five equivalent S(1)Na3Sb2 square pyramids, edges with four equivalent S(2)Na3Sb3 octahedra, and edges with five equivalent S(1)Na3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 5-12°.
NaSbS2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form NaS6 octahedra that share corners with four equivalent Na(1)S6 octahedra, corners with five equivalent Sb(1)S5 square pyramids, edges with four equivalent Na(1)S6 octahedra, and edges with five equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 5-12°. There are two shorter (2.81 Å) and one longer (3.00 Å) Na(1)-S(1) bond length. There are a spread of Na(1)-S(2) bond distances ranging from 2.93-3.06 Å. Sb(1) is bonded to two equivalent S(1) and three equivalent S(2) atoms to form SbS5 square pyramids that share corners with five equivalent Na(1)S6 octahedra, corners with two equivalent Sb(1)S5 square pyramids, edges with five equivalent Na(1)S6 octahedra, and edges with three equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 2-88°. There is one shorter (2.45 Å) and one longer (2.89 Å) Sb(1)-S(1) bond length. There is one shorter (2.68 Å) and two longer (2.81 Å) Sb(1)-S(2) bond lengths. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and two equivalent Sb(1) atoms to form SNa3Sb2 square pyramids that share corners with five equivalent S(2)Na3Sb3 octahedra, corners with two equivalent S(1)Na3Sb2 square pyramids, edges with five equivalent S(2)Na3Sb3 octahedra, and edges with three equivalent S(1)Na3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 2-84°. In the second S site, S(2) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form SNa3Sb3 octahedra that share corners with four equivalent S(2)Na3Sb3 octahedra, corners with five equivalent S(1)Na3Sb2 square pyramids, edges with four equivalent S(2)Na3Sb3 octahedra, and edges with five equivalent S(1)Na3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 5-12°.