Cs2V5O13 crystallizes in the tetragonal I4mm space group. Cs(1) is bonded in a 12-coordinate geometry to four equivalent O(1), four 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(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  a cornercorner with one V(2)O5 trigonal bipyramid. In the second V site, V(2) is bonded to one O(4) and four equivalent O(3) atoms to form distorted corner-sharing VO5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a single-bond geometry to two equivalent Cs(1) and one V(1) atom. In the third O site, O(3) is bonded in a 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 single-bond geometry to one V(2) atom.
Cs2V5O13 crystallizes in the tetragonal I4mm space group. Cs(1) is bonded in a 12-coordinate geometry to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms. There are two shorter (3.27 Å) and two longer (3.56 Å) Cs(1)-O(1) bond lengths. All Cs(1)-O(2) bond lengths are 3.13 Å. All Cs(1)-O(3) bond lengths are 3.35 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  a cornercorner with one V(2)O5 trigonal bipyramid. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(3) bond length is 1.71 Å. Both V(1)-O(1) bond lengths are 1.79 Å. In the second V site, V(2) is bonded to one O(4) and four equivalent O(3) atoms to form distorted corner-sharing VO5 trigonal bipyramids. The V(2)-O(4) bond length is 1.61 Å. All V(2)-O(3) bond lengths are 1.93 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a single-bond geometry to two equivalent Cs(1) and one V(1) atom. In the third O site, O(3) is bonded in a 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 single-bond geometry to one V(2) atom.