BaVS3 crystallizes in the monoclinic Cm space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one S(2), one S(4), two equivalent S(3), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(1)S12 cuboctahedra, corners with four equivalent Ba(3)S12 cuboctahedra,  a cornercorner with one V(2)S6 octahedra,  a cornercorner with one V(3)S6 octahedra, corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(4)S6 octahedra, faces with two equivalent Ba(3)S12 cuboctahedra, faces with three equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra,  a faceface with one V(4)S6 octahedra, faces with two equivalent V(2)S6 octahedra, and faces with two equivalent V(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 13-24°. In the second Ba site, Ba(2) is bonded to one S(1), one S(3), two equivalent S(4), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(2)S12 cuboctahedra, corners with four equivalent Ba(4)S12 cuboctahedra,  a cornercorner with one V(3)S6 octahedra,  a cornercorner with one V(4)S6 octahedra, corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, faces with two equivalent Ba(4)S12 cuboctahedra, faces with three equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra,  a faceface with one V(2)S6 octahedra, faces with two equivalent V(3)S6 octahedra, and faces with two equivalent V(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-26°. In the third Ba site, Ba(3) is bonded to one S(2), one S(4), two equivalent S(1), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(3)S12 cuboctahedra, corners with four equivalent Ba(1)S12 cuboctahedra,  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(4)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(3)S6 octahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra,  a faceface with one V(3)S6 octahedra, faces with two equivalent V(1)S6 octahedra, and faces with two equivalent V(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 15-23°. In the fourth Ba site, Ba(4) is bonded to one S(1), one S(3), two equivalent S(2), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(4)S12 cuboctahedra, corners with four equivalent Ba(2)S12 cuboctahedra,  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(2)S6 octahedra, corners with two equivalent V(3)S6 octahedra, corners with two equivalent V(4)S6 octahedra, faces with two equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(3)S6 octahedra,  a faceface with one V(4)S6 octahedra, faces with two equivalent V(1)S6 octahedra, and faces with two equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-22°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(3)S12 cuboctahedra,  a cornercorner with one Ba(4)S12 cuboctahedra, corners with two equivalent Ba(1)S12 cuboctahedra, corners with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one Ba(1)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra, faces with two equivalent Ba(3)S12 cuboctahedra, faces with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra, and  a faceface with one V(4)S6 octahedra. In the second V site, V(2) is bonded to one S(2), one S(3), two equivalent S(6), and two equivalent S(7) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(1)S12 cuboctahedra,  a cornercorner with one Ba(4)S12 cuboctahedra, corners with two equivalent Ba(2)S12 cuboctahedra, corners with two equivalent Ba(3)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(3)S12 cuboctahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(3)S6 octahedra. In the third V site, V(3) is bonded to one S(3), one S(4), two equivalent S(7), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(1)S12 cuboctahedra,  a cornercorner with one Ba(2)S12 cuboctahedra, corners with two equivalent Ba(3)S12 cuboctahedra, corners with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one Ba(3)S12 cuboctahedra,  a faceface with one Ba(4)S12 cuboctahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra, and  a faceface with one V(4)S6 octahedra. In the fourth V site, V(4) is bonded to one S(1), one S(4), two equivalent S(5), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(3)S12 cuboctahedra, corners with two equivalent Ba(1)S12 cuboctahedra, corners with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one Ba(1)S12 cuboctahedra,  a faceface with one Ba(4)S12 cuboctahedra, faces with two equivalent Ba(2)S12 cuboctahedra, faces with two equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(3)S6 octahedra. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), two equivalent Ba(3), one V(1), and one V(4) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(4), one V(1), and one V(2) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), two equivalent Ba(1), one V(2), and one V(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one V(3), and one V(4) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(1), and one V(4) atom. In the sixth S site, S(6) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(1), and one V(2) atom to form distorted face-sharing SBa4V2 octahedra. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(2), and one V(3) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(3), and one V(4) atom.
BaVS3 crystallizes in the monoclinic Cm space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one S(2), one S(4), two equivalent S(3), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(1)S12 cuboctahedra, corners with four equivalent Ba(3)S12 cuboctahedra,  a cornercorner with one V(2)S6 octahedra,  a cornercorner with one V(3)S6 octahedra, corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(4)S6 octahedra, faces with two equivalent Ba(3)S12 cuboctahedra, faces with three equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra,  a faceface with one V(4)S6 octahedra, faces with two equivalent V(2)S6 octahedra, and faces with two equivalent V(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 13-24°. The Ba(1)-S(2) bond length is 3.42 Å. The Ba(1)-S(4) bond length is 3.46 Å. Both Ba(1)-S(3) bond lengths are 3.42 Å. Both Ba(1)-S(5) bond lengths are 3.43 Å. Both Ba(1)-S(6) bond lengths are 3.42 Å. Both Ba(1)-S(7) bond lengths are 3.34 Å. Both Ba(1)-S(8) bond lengths are 3.51 Å. In the second Ba site, Ba(2) is bonded to one S(1), one S(3), two equivalent S(4), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(2)S12 cuboctahedra, corners with four equivalent Ba(4)S12 cuboctahedra,  a cornercorner with one V(3)S6 octahedra,  a cornercorner with one V(4)S6 octahedra, corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, faces with two equivalent Ba(4)S12 cuboctahedra, faces with three equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra,  a faceface with one V(2)S6 octahedra, faces with two equivalent V(3)S6 octahedra, and faces with two equivalent V(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-26°. The Ba(2)-S(1) bond length is 3.53 Å. The Ba(2)-S(3) bond length is 3.40 Å. Both Ba(2)-S(4) bond lengths are 3.42 Å. Both Ba(2)-S(5) bond lengths are 3.50 Å. Both Ba(2)-S(6) bond lengths are 3.36 Å. Both Ba(2)-S(7) bond lengths are 3.46 Å. Both Ba(2)-S(8) bond lengths are 3.35 Å. In the third Ba site, Ba(3) is bonded to one S(2), one S(4), two equivalent S(1), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(3)S12 cuboctahedra, corners with four equivalent Ba(1)S12 cuboctahedra,  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(4)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent V(3)S6 octahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra,  a faceface with one V(3)S6 octahedra, faces with two equivalent V(1)S6 octahedra, and faces with two equivalent V(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 15-23°. The Ba(3)-S(2) bond length is 3.49 Å. The Ba(3)-S(4) bond length is 3.37 Å. Both Ba(3)-S(1) bond lengths are 3.42 Å. Both Ba(3)-S(5) bond lengths are 3.37 Å. Both Ba(3)-S(6) bond lengths are 3.48 Å. Both Ba(3)-S(7) bond lengths are 3.39 Å. Both Ba(3)-S(8) bond lengths are 3.45 Å. In the fourth Ba site, Ba(4) is bonded to one S(1), one S(3), two equivalent S(2), two equivalent S(5), two equivalent S(6), two equivalent S(7), and two equivalent S(8) atoms to form BaS12 cuboctahedra that share corners with two equivalent Ba(4)S12 cuboctahedra, corners with four equivalent Ba(2)S12 cuboctahedra,  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(2)S6 octahedra, corners with two equivalent V(3)S6 octahedra, corners with two equivalent V(4)S6 octahedra, faces with two equivalent Ba(2)S12 cuboctahedra, faces with three equivalent Ba(1)S12 cuboctahedra, faces with three equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(3)S6 octahedra,  a faceface with one V(4)S6 octahedra, faces with two equivalent V(1)S6 octahedra, and faces with two equivalent V(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 14-22°. The Ba(4)-S(1) bond length is 3.37 Å. The Ba(4)-S(3) bond length is 3.42 Å. Both Ba(4)-S(2) bond lengths are 3.42 Å. Both Ba(4)-S(5) bond lengths are 3.41 Å. Both Ba(4)-S(6) bond lengths are 3.34 Å. Both Ba(4)-S(7) bond lengths are 3.51 Å. Both Ba(4)-S(8) bond lengths are 3.47 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(3)S12 cuboctahedra,  a cornercorner with one Ba(4)S12 cuboctahedra, corners with two equivalent Ba(1)S12 cuboctahedra, corners with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one Ba(1)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra, faces with two equivalent Ba(3)S12 cuboctahedra, faces with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra, and  a faceface with one V(4)S6 octahedra. The V(1)-S(1) bond length is 2.21 Å. The V(1)-S(2) bond length is 2.69 Å. Both V(1)-S(5) bond lengths are 2.40 Å. Both V(1)-S(6) bond lengths are 2.35 Å. In the second V site, V(2) is bonded to one S(2), one S(3), two equivalent S(6), and two equivalent S(7) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(1)S12 cuboctahedra,  a cornercorner with one Ba(4)S12 cuboctahedra, corners with two equivalent Ba(2)S12 cuboctahedra, corners with two equivalent Ba(3)S12 cuboctahedra,  a faceface with one Ba(2)S12 cuboctahedra,  a faceface with one Ba(3)S12 cuboctahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(3)S6 octahedra. The V(2)-S(2) bond length is 2.19 Å. The V(2)-S(3) bond length is 2.74 Å. Both V(2)-S(6) bond lengths are 2.43 Å. Both V(2)-S(7) bond lengths are 2.33 Å. In the third V site, V(3) is bonded to one S(3), one S(4), two equivalent S(7), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(1)S12 cuboctahedra,  a cornercorner with one Ba(2)S12 cuboctahedra, corners with two equivalent Ba(3)S12 cuboctahedra, corners with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one Ba(3)S12 cuboctahedra,  a faceface with one Ba(4)S12 cuboctahedra, faces with two equivalent Ba(1)S12 cuboctahedra, faces with two equivalent Ba(2)S12 cuboctahedra,  a faceface with one V(2)S6 octahedra, and  a faceface with one V(4)S6 octahedra. The V(3)-S(3) bond length is 2.21 Å. The V(3)-S(4) bond length is 2.63 Å. Both V(3)-S(7) bond lengths are 2.46 Å. Both V(3)-S(8) bond lengths are 2.31 Å. In the fourth V site, V(4) is bonded to one S(1), one S(4), two equivalent S(5), and two equivalent S(8) atoms to form distorted VS6 octahedra that share  a cornercorner with one Ba(2)S12 cuboctahedra,  a cornercorner with one Ba(3)S12 cuboctahedra, corners with two equivalent Ba(1)S12 cuboctahedra, corners with two equivalent Ba(4)S12 cuboctahedra,  a faceface with one Ba(1)S12 cuboctahedra,  a faceface with one Ba(4)S12 cuboctahedra, faces with two equivalent Ba(2)S12 cuboctahedra, faces with two equivalent Ba(3)S12 cuboctahedra,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(3)S6 octahedra. The V(4)-S(1) bond length is 2.60 Å. The V(4)-S(4) bond length is 2.22 Å. Both V(4)-S(5) bond lengths are 2.33 Å. Both V(4)-S(8) bond lengths are 2.43 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), two equivalent Ba(3), one V(1), and one V(4) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(4), one V(1), and one V(2) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), two equivalent Ba(1), one V(2), and one V(3) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one V(3), and one V(4) atom. In the fifth S site, S(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(1), and one V(4) atom. In the sixth S site, S(6) is bonded to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(1), and one V(2) atom to form distorted face-sharing SBa4V2 octahedra. In the seventh S site, S(7) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(2), and one V(3) atom. In the eighth S site, S(8) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(4), one V(3), and one V(4) atom.