BaVSe3 crystallizes in the orthorhombic Cmc2_1 space group. Ba(1) is bonded to four equivalent Se(2) and eight equivalent Se(1) atoms to form BaSe12 cuboctahedra that share corners with six equivalent Ba(1)Se12 cuboctahedra, corners with six equivalent V(1)Se6 octahedra, faces with eight equivalent Ba(1)Se12 cuboctahedra, and faces with six equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 13-26°. V(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form distorted VSe6 octahedra that share corners with six equivalent Ba(1)Se12 cuboctahedra, faces with six equivalent Ba(1)Se12 cuboctahedra, and faces with two equivalent V(1)Se6 octahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent V(1) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent V(1) atoms.
BaVSe3 crystallizes in the orthorhombic Cmc2_1 space group. Ba(1) is bonded to four equivalent Se(2) and eight equivalent Se(1) atoms to form BaSe12 cuboctahedra that share corners with six equivalent Ba(1)Se12 cuboctahedra, corners with six equivalent V(1)Se6 octahedra, faces with eight equivalent Ba(1)Se12 cuboctahedra, and faces with six equivalent V(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 13-26°. There are a spread of Ba(1)-Se(2) bond distances ranging from 3.47-3.67 Å. There are a spread of Ba(1)-Se(1) bond distances ranging from 3.50-3.65 Å. V(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form distorted VSe6 octahedra that share corners with six equivalent Ba(1)Se12 cuboctahedra, faces with six equivalent Ba(1)Se12 cuboctahedra, and faces with two equivalent V(1)Se6 octahedra. There is one shorter (2.34 Å) and one longer (2.77 Å) V(1)-Se(2) bond length. There are two shorter (2.47 Å) and two longer (2.58 Å) V(1)-Se(1) bond lengths. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent V(1) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent V(1) atoms.