NaYZrS4 crystallizes in the monoclinic P2/m space group. Na(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NaS6 octahedra that share corners with six equivalent Zr(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Y(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Y(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form YS6 octahedra that share edges with two equivalent Y(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. Zr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form ZrS6 octahedra that share corners with six equivalent Na(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Y(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), one Y(1), and two equivalent Zr(1) atoms to form a mixture of corner and edge-sharing SNa2YZr2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Y(1), and one Zr(1) atom.
NaYZrS4 crystallizes in the monoclinic P2/m space group. Na(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form NaS6 octahedra that share corners with six equivalent Zr(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Y(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Na(1)-S(2) bond lengths are 2.96 Å. All Na(1)-S(1) bond lengths are 2.96 Å. Y(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form YS6 octahedra that share edges with two equivalent Y(1)S6 octahedra, edges with four equivalent Na(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. Both Y(1)-S(1) bond lengths are 2.73 Å. All Y(1)-S(2) bond lengths are 2.72 Å. Zr(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form ZrS6 octahedra that share corners with six equivalent Na(1)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with four equivalent Y(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Zr(1)-S(2) bond lengths are 2.55 Å. All Zr(1)-S(1) bond lengths are 2.63 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(1), one Y(1), and two equivalent Zr(1) atoms to form a mixture of corner and edge-sharing SNa2YZr2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Y(1), and one Zr(1) atom.