Zr9W4S crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted T-shaped geometry to two equivalent W(2) and one S(1) atom. In the second Zr site, Zr(2) is bonded in a 5-coordinate geometry to one W(1), three equivalent W(2), and one S(1) atom. There are two inequivalent W sites. In the first W site, W(1) is bonded to six equivalent Zr(2) and six equivalent W(2) atoms to form face-sharing WZr6W6 cuboctahedra. In the second W site, W(2) is bonded in a 12-coordinate geometry to two equivalent Zr(1), six equivalent Zr(2), two equivalent W(1), and two equivalent W(2) atoms. S(1) is bonded in a 9-coordinate geometry to three equivalent Zr(1) and six equivalent Zr(2) atoms.
Zr9W4S crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted T-shaped geometry to two equivalent W(2) and one S(1) atom. Both Zr(1)-W(2) bond lengths are 2.97 Å. The Zr(1)-S(1) bond length is 3.13 Å. In the second Zr site, Zr(2) is bonded in a 5-coordinate geometry to one W(1), three equivalent W(2), and one S(1) atom. The Zr(2)-W(1) bond length is 3.02 Å. There is one shorter (2.93 Å) and two longer (3.13 Å) Zr(2)-W(2) bond lengths. The Zr(2)-S(1) bond length is 2.71 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to six equivalent Zr(2) and six equivalent W(2) atoms to form face-sharing WZr6W6 cuboctahedra. All W(1)-W(2) bond lengths are 2.73 Å. In the second W site, W(2) is bonded in a 12-coordinate geometry to two equivalent Zr(1), six equivalent Zr(2), two equivalent W(1), and two equivalent W(2) atoms. Both W(2)-W(2) bond lengths are 2.86 Å. S(1) is bonded in a 9-coordinate geometry to three equivalent Zr(1) and six equivalent Zr(2) atoms.