Hf9V4S crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Hf sites. In the first Hf site, Hf(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 Hf site, Hf(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 Hf(1) and six equivalent V(2) atoms to form VHf6V6 cuboctahedra that share faces with two equivalent V(1)Hf6V6 cuboctahedra and faces with six equivalent V(2)Hf8V4 cuboctahedra. In the second V site, V(2) is bonded to two equivalent Hf(2), six equivalent Hf(1), two equivalent V(1), and two equivalent V(2) atoms to form distorted VHf8V4 cuboctahedra that share corners with four equivalent V(2)Hf8V4 cuboctahedra, faces with two equivalent V(1)Hf6V6 cuboctahedra, and faces with six equivalent V(2)Hf8V4 cuboctahedra. S(1) is bonded in a 9-coordinate geometry to three equivalent Hf(2) and six equivalent Hf(1) atoms.
Hf9V4S crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a distorted single-bond geometry to one V(1), three equivalent V(2), and one S(1) atom. The Hf(1)-V(1) bond length is 2.94 Å. There is one shorter (2.86 Å) and two longer (3.03 Å) Hf(1)-V(2) bond lengths. The Hf(1)-S(1) bond length is 2.64 Å. In the second Hf site, Hf(2) is bonded in a distorted T-shaped geometry to two equivalent V(2) and one S(1) atom. Both Hf(2)-V(2) bond lengths are 2.92 Å. The Hf(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 Hf(1) and six equivalent V(2) atoms to form VHf6V6 cuboctahedra that share faces with two equivalent V(1)Hf6V6 cuboctahedra and faces with six equivalent V(2)Hf8V4 cuboctahedra. All V(1)-V(2) bond lengths are 2.64 Å. In the second V site, V(2) is bonded to two equivalent Hf(2), six equivalent Hf(1), two equivalent V(1), and two equivalent V(2) atoms to form distorted VHf8V4 cuboctahedra that share corners with four equivalent V(2)Hf8V4 cuboctahedra, faces with two equivalent V(1)Hf6V6 cuboctahedra, and faces with six equivalent V(2)Hf8V4 cuboctahedra. Both V(2)-V(2) bond lengths are 2.75 Å. S(1) is bonded in a 9-coordinate geometry to three equivalent Hf(2) and six equivalent Hf(1) atoms.