NaCdSbS3 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to one S(3), two equivalent S(1), and three equivalent S(2) atoms to form NaS6 octahedra that share  a cornercorner with one Cd(2)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Cd(1)S6 octahedra, and edges with two equivalent Cd(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 16-22°. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form distorted CdS6 octahedra that share corners with four equivalent Cd(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Cd(2)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the second Cd site, Cd(2) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form distorted CdS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Cd(2)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Cd(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 12-22°. Sb(1) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(3) is bonded to one Na(1), two equivalent Cd(1), two equivalent Cd(2), and one Sb(1) atom to form distorted SNaCd4Sb octahedra that share corners with four equivalent S(3)NaCd4Sb octahedra, corners with two equivalent S(2)Na3CdSb square pyramids, edges with four equivalent S(3)NaCd4Sb octahedra, and edges with three equivalent S(2)Na3CdSb square pyramids. The corner-sharing octahedral tilt angles range from 10-12°. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Cd(1), and one Sb(1) atom. In the third S site, S(2) is bonded to three equivalent Na(1), one Cd(2), and one Sb(1) atom to form SNa3CdSb square pyramids that share corners with two equivalent S(3)NaCd4Sb octahedra, corners with three equivalent S(2)Na3CdSb square pyramids, edges with three equivalent S(3)NaCd4Sb octahedra, and edges with two equivalent S(2)Na3CdSb square pyramids. The corner-sharing octahedral tilt angles range from 10-85°.
NaCdSbS3 crystallizes in the monoclinic C2/c space group. Na(1) is bonded to one S(3), two equivalent S(1), and three equivalent S(2) atoms to form NaS6 octahedra that share  a cornercorner with one Cd(2)S6 octahedra, corners with four equivalent Na(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Cd(1)S6 octahedra, and edges with two equivalent Cd(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 16-22°. The Na(1)-S(3) bond length is 3.05 Å. There is one shorter (2.94 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 2.91-3.03 Å. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form distorted CdS6 octahedra that share corners with four equivalent Cd(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Cd(2)S6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both Cd(1)-S(1) bond lengths are 2.59 Å. There are two shorter (2.72 Å) and two longer (3.15 Å) Cd(1)-S(3) bond lengths. In the second Cd site, Cd(2) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form distorted CdS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with four equivalent Cd(2)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Cd(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 12-22°. Both Cd(2)-S(2) bond lengths are 2.61 Å. There are two shorter (2.72 Å) and two longer (3.16 Å) Cd(2)-S(3) bond lengths. Sb(1) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(3) atom. The Sb(1)-S(1) bond length is 2.48 Å. The Sb(1)-S(2) bond length is 2.48 Å. The Sb(1)-S(3) bond length is 2.50 Å. There are three inequivalent S sites. In the first S site, S(3) is bonded to one Na(1), two equivalent Cd(1), two equivalent Cd(2), and one Sb(1) atom to form distorted SNaCd4Sb octahedra that share corners with four equivalent S(3)NaCd4Sb octahedra, corners with two equivalent S(2)Na3CdSb square pyramids, edges with four equivalent S(3)NaCd4Sb octahedra, and edges with three equivalent S(2)Na3CdSb square pyramids. The corner-sharing octahedral tilt angles range from 10-12°. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Cd(1), and one Sb(1) atom. In the third S site, S(2) is bonded to three equivalent Na(1), one Cd(2), and one Sb(1) atom to form SNa3CdSb square pyramids that share corners with two equivalent S(3)NaCd4Sb octahedra, corners with three equivalent S(2)Na3CdSb square pyramids, edges with three equivalent S(3)NaCd4Sb octahedra, and edges with two equivalent S(2)Na3CdSb square pyramids. The corner-sharing octahedral tilt angles range from 10-85°.