TlV5Se8 crystallizes in the monoclinic C2/m space group. The structure consists of two 7440-28-0 atoms inside a V5Se8 framework. In the V5Se8 framework, there are three inequivalent V sites. In the first V site, V(1) is bonded to one Se(3), two equivalent Se(4), and three equivalent Se(2) atoms to form a mixture of distorted face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the second V site, V(2) is bonded to one Se(3), two equivalent Se(2), and three equivalent Se(1) atoms to form a mixture of face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the third V site, V(3) is bonded to two equivalent Se(4) and four equivalent Se(3) atoms to form a mixture of corner and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to two equivalent V(2) and three equivalent V(1) atoms. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent V(3) atoms. In the fourth Se site, Se(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms.
TlV5Se8 crystallizes in the monoclinic C2/m space group. The structure consists of two 7440-28-0 atoms inside a V5Se8 framework. In the V5Se8 framework, there are three inequivalent V sites. In the first V site, V(1) is bonded to one Se(3), two equivalent Se(4), and three equivalent Se(2) atoms to form a mixture of distorted face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The V(1)-Se(3) bond length is 2.42 Å. Both V(1)-Se(4) bond lengths are 2.46 Å. There are two shorter (2.63 Å) and one longer (2.74 Å) V(1)-Se(2) bond length. In the second V site, V(2) is bonded to one Se(3), two equivalent Se(2), and three equivalent Se(1) atoms to form a mixture of face, corner, and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The V(2)-Se(3) bond length is 2.59 Å. Both V(2)-Se(2) bond lengths are 2.60 Å. There is one shorter (2.51 Å) and two longer (2.54 Å) V(2)-Se(1) bond lengths. In the third V site, V(3) is bonded to two equivalent Se(4) and four equivalent Se(3) atoms to form a mixture of corner and edge-sharing VSe6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both V(3)-Se(4) bond lengths are 2.55 Å. All V(3)-Se(3) bond lengths are 2.54 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to two equivalent V(2) and three equivalent V(1) atoms. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(2), and two equivalent V(3) atoms. In the fourth Se site, Se(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms.