V5Se8 is beta indium sulfide-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form a mixture of face and corner-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the second V site, V(2) is bonded to one Se(2), one Se(3), and four equivalent Se(1) atoms to form a mixture of face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the third V site, V(3) is bonded to two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms to form a mixture of corner and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the second Se site, Se(2) is bonded to one V(1), one V(2), and two equivalent V(3) atoms to form a mixture of corner and edge-sharing SeV4 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(3) atoms.
V5Se8 is beta indium sulfide-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form a mixture of face and corner-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both V(1)-Se(2) bond lengths are 2.58 Å. All V(1)-Se(1) bond lengths are 2.54 Å. In the second V site, V(2) is bonded to one Se(2), one Se(3), and four equivalent Se(1) atoms to form a mixture of face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles are 51°. The V(2)-Se(2) bond length is 2.57 Å. The V(2)-Se(3) bond length is 2.55 Å. All V(2)-Se(1) bond lengths are 2.54 Å. In the third V site, V(3) is bonded to two equivalent Se(1), two equivalent Se(2), and two equivalent Se(3) atoms to form a mixture of corner and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both V(3)-Se(1) bond lengths are 2.57 Å. Both V(3)-Se(2) bond lengths are 2.60 Å. Both V(3)-Se(3) bond lengths are 2.44 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms. In the second Se site, Se(2) is bonded to one V(1), one V(2), and two equivalent V(3) atoms to form a mixture of corner and edge-sharing SeV4 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(3) atoms.