Zr3S4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of edge and corner-sharing ZrS6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the second Zr site, Zr(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form edge-sharing ZrS6 octahedra. There are two inequivalent S sites. In the first S site, S(2) is bonded to one Zr(2) and four equivalent Zr(1) atoms to form a mixture of edge and corner-sharing SZr5 square pyramids. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1) and two equivalent Zr(2) atoms.
Zr3S4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of edge and corner-sharing ZrS6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. Both Zr(1)-S(1) bond lengths are 2.55 Å. All Zr(1)-S(2) bond lengths are 2.60 Å. In the second Zr site, Zr(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form edge-sharing ZrS6 octahedra. Both Zr(2)-S(2) bond lengths are 2.65 Å. All Zr(2)-S(1) bond lengths are 2.61 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded to one Zr(2) and four equivalent Zr(1) atoms to form a mixture of edge and corner-sharing SZr5 square pyramids. In the second S site, S(1) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1) and two equivalent Zr(2) atoms.