Cs4U2V2O13 crystallizes in the orthorhombic Pmmn space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), and four equivalent O(4) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to two equivalent O(2), two equivalent O(3), four equivalent O(1), and four equivalent O(4) atoms. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one O(5), two equivalent O(3), and four equivalent O(4) atoms. U(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form UO6 octahedra that share corners with two equivalent U(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. V(1) is bonded to one O(3), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent U(1)O6 octahedra and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), one U(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Cs(2) and two equivalent U(1) atoms. In the third O site, O(3) is bonded in a single-bond geometry to one Cs(2), one Cs(3), two equivalent Cs(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), two equivalent Cs(1), and one U(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cs(3) and two equivalent V(1) atoms.
Cs4U2V2O13 crystallizes in the orthorhombic Pmmn space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), and four equivalent O(4) atoms. Both Cs(1)-O(1) bond lengths are 3.43 Å. Both Cs(1)-O(3) bond lengths are 3.17 Å. All Cs(1)-O(4) bond lengths are 3.23 Å. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to two equivalent O(2), two equivalent O(3), four equivalent O(1), and four equivalent O(4) atoms. Both Cs(2)-O(2) bond lengths are 3.36 Å. Both Cs(2)-O(3) bond lengths are 3.32 Å. All Cs(2)-O(1) bond lengths are 3.35 Å. All Cs(2)-O(4) bond lengths are 3.45 Å. In the third Cs site, Cs(3) is bonded in a 7-coordinate geometry to one O(5), two equivalent O(3), and four equivalent O(4) atoms. The Cs(3)-O(5) bond length is 3.11 Å. Both Cs(3)-O(3) bond lengths are 3.42 Å. All Cs(3)-O(4) bond lengths are 3.16 Å. U(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form UO6 octahedra that share corners with two equivalent U(1)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. Both U(1)-O(1) bond lengths are 2.34 Å. Both U(1)-O(2) bond lengths are 2.15 Å. Both U(1)-O(4) bond lengths are 1.88 Å. V(1) is bonded to one O(3), one O(5), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with two equivalent U(1)O6 octahedra and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. The V(1)-O(3) bond length is 1.67 Å. The V(1)-O(5) bond length is 1.82 Å. Both V(1)-O(1) bond lengths are 1.74 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), one U(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Cs(2) and two equivalent U(1) atoms. In the third O site, O(3) is bonded in a single-bond geometry to one Cs(2), one Cs(3), two equivalent Cs(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), two equivalent Cs(1), and one U(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cs(3) and two equivalent V(1) atoms.