Zr9V4S 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 single-bond geometry to one V(1), three equivalent V(2), and one S(1) atom. In the second Zr site, Zr(2) is bonded in a distorted T-shaped geometry to two equivalent V(2) and one S(1) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Zr(1) and six equivalent V(2) atoms to form VZr6V6 cuboctahedra that share faces with two equivalent V(1)Zr6V6 cuboctahedra and faces with six equivalent V(2)Zr8V4 cuboctahedra. In the second V site, V(2) is bonded to two equivalent Zr(2), six equivalent Zr(1), two equivalent V(1), and two equivalent V(2) atoms to form VZr8V4 cuboctahedra that share corners with four equivalent V(2)Zr8V4 cuboctahedra, faces with two equivalent V(1)Zr6V6 cuboctahedra, and faces with six equivalent V(2)Zr8V4 cuboctahedra. S(1) is bonded in a 9-coordinate geometry to three equivalent Zr(2) and six equivalent Zr(1) atoms.
Zr9V4S 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 single-bond geometry to one V(1), three equivalent V(2), and one S(1) atom. The Zr(1)-V(1) bond length is 2.96 Å. There is one shorter (2.92 Å) and two longer (3.06 Å) Zr(1)-V(2) bond lengths. The Zr(1)-S(1) bond length is 2.67 Å. In the second Zr site, Zr(2) is bonded in a distorted T-shaped geometry to two equivalent V(2) and one S(1) atom. Both Zr(2)-V(2) bond lengths are 2.98 Å. The Zr(2)-S(1) bond length is 3.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Zr(1) and six equivalent V(2) atoms to form VZr6V6 cuboctahedra that share faces with two equivalent V(1)Zr6V6 cuboctahedra and faces with six equivalent V(2)Zr8V4 cuboctahedra. All V(1)-V(2) bond lengths are 2.64 Å. In the second V site, V(2) is bonded to two equivalent Zr(2), six equivalent Zr(1), two equivalent V(1), and two equivalent V(2) atoms to form VZr8V4 cuboctahedra that share corners with four equivalent V(2)Zr8V4 cuboctahedra, faces with two equivalent V(1)Zr6V6 cuboctahedra, and faces with six equivalent V(2)Zr8V4 cuboctahedra. Both V(2)-V(2) bond lengths are 2.70 Å. S(1) is bonded in a 9-coordinate geometry to three equivalent Zr(2) and six equivalent Zr(1) atoms.