BaVSe2S crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent Se(1), two equivalent Se(3), four equivalent Se(2), and four equivalent S(1) atoms to form BaSe8S4 cuboctahedra that share corners with six equivalent Ba(1)Se8S4 cuboctahedra, corners with six equivalent V(1)Se4S2 octahedra, faces with two equivalent Ba(1)Se8S4 cuboctahedra, faces with six equivalent Ba(2)Se8S4 cuboctahedra, and faces with six equivalent V(1)Se4S2 octahedra. The corner-sharing octahedral tilt angles range from 16-22°. In the second Ba site, Ba(2) is bonded to two equivalent Se(1), two equivalent Se(3), four equivalent Se(2), and four equivalent S(1) atoms to form BaSe8S4 cuboctahedra that share corners with six equivalent Ba(2)Se8S4 cuboctahedra, corners with six equivalent V(1)Se4S2 octahedra, faces with two equivalent Ba(2)Se8S4 cuboctahedra, faces with six equivalent Ba(1)Se8S4 cuboctahedra, and faces with six equivalent V(1)Se4S2 octahedra. The corner-sharing octahedral tilt angles range from 18-20°. V(1) is bonded to one Se(1), one Se(3), two equivalent Se(2), and two equivalent S(1) atoms to form VSe4S2 octahedra that share corners with three equivalent Ba(1)Se8S4 cuboctahedra, corners with three equivalent Ba(2)Se8S4 cuboctahedra, faces with three equivalent Ba(1)Se8S4 cuboctahedra, faces with three equivalent Ba(2)Se8S4 cuboctahedra, and faces with two equivalent V(1)Se4S2 octahedra. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-68°. In the second Se site, Se(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the third Se site, Se(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-68°. S(1) is bonded in a 2-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms.
BaVSe2S crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent Se(1), two equivalent Se(3), four equivalent Se(2), and four equivalent S(1) atoms to form BaSe8S4 cuboctahedra that share corners with six equivalent Ba(1)Se8S4 cuboctahedra, corners with six equivalent V(1)Se4S2 octahedra, faces with two equivalent Ba(1)Se8S4 cuboctahedra, faces with six equivalent Ba(2)Se8S4 cuboctahedra, and faces with six equivalent V(1)Se4S2 octahedra. The corner-sharing octahedral tilt angles range from 16-22°. Both Ba(1)-Se(1) bond lengths are 3.59 Å. Both Ba(1)-Se(3) bond lengths are 3.46 Å. There are two shorter (3.45 Å) and two longer (3.53 Å) Ba(1)-Se(2) bond lengths. All Ba(1)-S(1) bond lengths are 3.65 Å. In the second Ba site, Ba(2) is bonded to two equivalent Se(1), two equivalent Se(3), four equivalent Se(2), and four equivalent S(1) atoms to form BaSe8S4 cuboctahedra that share corners with six equivalent Ba(2)Se8S4 cuboctahedra, corners with six equivalent V(1)Se4S2 octahedra, faces with two equivalent Ba(2)Se8S4 cuboctahedra, faces with six equivalent Ba(1)Se8S4 cuboctahedra, and faces with six equivalent V(1)Se4S2 octahedra. The corner-sharing octahedral tilt angles range from 18-20°. Both Ba(2)-Se(1) bond lengths are 3.46 Å. Both Ba(2)-Se(3) bond lengths are 3.59 Å. All Ba(2)-Se(2) bond lengths are 3.58 Å. There are two shorter (3.44 Å) and two longer (3.53 Å) Ba(2)-S(1) bond lengths. V(1) is bonded to one Se(1), one Se(3), two equivalent Se(2), and two equivalent S(1) atoms to form VSe4S2 octahedra that share corners with three equivalent Ba(1)Se8S4 cuboctahedra, corners with three equivalent Ba(2)Se8S4 cuboctahedra, faces with three equivalent Ba(1)Se8S4 cuboctahedra, faces with three equivalent Ba(2)Se8S4 cuboctahedra, and faces with two equivalent V(1)Se4S2 octahedra. The V(1)-Se(1) bond length is 2.60 Å. The V(1)-Se(3) bond length is 2.48 Å. Both V(1)-Se(2) bond lengths are 2.55 Å. Both V(1)-S(1) bond lengths are 2.35 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-68°. In the second Se site, Se(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-67°. In the third Se site, Se(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms to form a mixture of distorted corner, edge, and face-sharing SeBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 2-68°. S(1) is bonded in a 2-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms.