Cs2V3O8 crystallizes in the tetragonal P4bm space group. Cs(1) is bonded in a 10-coordinate geometry to one O(4), two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form corner-sharing VO4 tetrahedra. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(3) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to four equivalent Cs(1) and one V(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Cs(1) and two equivalent V(1) atoms.
Cs2V3O8 crystallizes in the tetragonal P4bm space group. Cs(1) is bonded in a 10-coordinate geometry to one O(4), two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. The Cs(1)-O(4) bond length is 3.12 Å. Both Cs(1)-O(1) bond lengths are 3.67 Å. There is one shorter (2.95 Å) and two longer (3.10 Å) Cs(1)-O(2) bond lengths. There are two shorter (3.18 Å) and two longer (3.45 Å) Cs(1)-O(3) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form corner-sharing VO4 tetrahedra. The V(1)-O(2) bond length is 1.64 Å. The V(1)-O(4) bond length is 1.81 Å. Both V(1)-O(3) bond lengths are 1.73 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(3) atoms. The V(2)-O(1) bond length is 1.62 Å. All V(2)-O(3) bond lengths are 1.96 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to four equivalent Cs(1) and one V(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Cs(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Cs(1) and two equivalent V(1) atoms.