NaCuZrS3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent S(1) and four equivalent S(2) atoms. Zr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Cu(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form CuS4 tetrahedra that share corners with two equivalent Cu(1)S4 tetrahedra and edges with four equivalent Zr(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), two equivalent Zr(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SNa2Zr2Cu2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Zr(1), and one Cu(1) atom.
NaCuZrS3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent S(1) and four equivalent S(2) atoms. Both Na(1)-S(1) bond lengths are 2.93 Å. All Na(1)-S(2) bond lengths are 3.05 Å. Zr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. Both Zr(1)-S(1) bond lengths are 2.66 Å. All Zr(1)-S(2) bond lengths are 2.59 Å. Cu(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form CuS4 tetrahedra that share corners with two equivalent Cu(1)S4 tetrahedra and edges with four equivalent Zr(1)S6 octahedra. Both Cu(1)-S(1) bond lengths are 2.33 Å. Both Cu(1)-S(2) bond lengths are 2.28 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), two equivalent Zr(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SNa2Zr2Cu2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Zr(1), and one Cu(1) atom.