NaSbS2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six S(1,1,1) atoms to form NaS6 octahedra that share corners with two equivalent Sb(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with eight equivalent Sb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Sb(1) is bonded to six S(1,1) atoms to form SbS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Sb(1)S6 octahedra, edges with four equivalent Sb(1)S6 octahedra, and edges with eight equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the fourth S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
NaSbS2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six S(1,1,1) atoms to form NaS6 octahedra that share corners with two equivalent Sb(1)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with eight equivalent Sb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are four shorter (2.79 Å) and two longer (3.01 Å) Na(1)-S(1,1,1) bond lengths. Sb(1) is bonded to six S(1,1) atoms to form SbS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Sb(1)S6 octahedra, edges with four equivalent Sb(1)S6 octahedra, and edges with eight equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are two shorter (2.76 Å) and four longer (2.79 Å) Sb(1)-S(1,1) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There is one shorter (2.76 Å) and two longer (2.79 Å) S(1)-Sb(1) bond lengths. In the second S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are two shorter (2.79 Å) and one longer (3.01 Å) S(1)-Na(1) bond length. There is one shorter (2.76 Å) and two longer (2.79 Å) S(1)-Sb(1) bond lengths. In the fourth S site, S(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.