BaVS3 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded to four equivalent S(2) and eight equivalent S(1) atoms to form BaS12 cuboctahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, corners with three equivalent V(1)S6 octahedra, corners with three equivalent V(2)S6 octahedra, faces with eight equivalent Ba(1)S12 cuboctahedra, faces with three equivalent V(1)S6 octahedra, and faces with three equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, faces with six equivalent Ba(1)S12 cuboctahedra, and faces with two equivalent V(2)S6 octahedra. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, faces with six equivalent Ba(1)S12 cuboctahedra, and faces with two equivalent V(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing SBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°. In the second S site, S(2) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing SBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°.
BaVS3 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded to four equivalent S(2) and eight equivalent S(1) atoms to form BaS12 cuboctahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, corners with three equivalent V(1)S6 octahedra, corners with three equivalent V(2)S6 octahedra, faces with eight equivalent Ba(1)S12 cuboctahedra, faces with three equivalent V(1)S6 octahedra, and faces with three equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are a spread of Ba(1)-S(2) bond distances ranging from 3.36-3.52 Å. There are a spread of Ba(1)-S(1) bond distances ranging from 3.36-3.51 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, faces with six equivalent Ba(1)S12 cuboctahedra, and faces with two equivalent V(2)S6 octahedra. Both V(1)-S(2) bond lengths are 2.37 Å. All V(1)-S(1) bond lengths are 2.39 Å. In the second V site, V(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form VS6 octahedra that share corners with six equivalent Ba(1)S12 cuboctahedra, faces with six equivalent Ba(1)S12 cuboctahedra, and faces with two equivalent V(1)S6 octahedra. Both V(2)-S(2) bond lengths are 2.39 Å. All V(2)-S(1) bond lengths are 2.37 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing SBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°. In the second S site, S(2) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing SBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-69°.