CsV2O13I3 crystallizes in the orthorhombic Ima2 space group. Cs(1) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and four equivalent O(6) atoms. V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one I(1), and one I(2) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Cs(1) and one I(1) atom. In the third O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one I(1) atom. In the fifth O site, O(4) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent I(2) atoms. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the seventh O site, O(6) is bonded in a single-bond geometry to two equivalent Cs(1) and one V(1) atom. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one I(2) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), and one O(8) atom. In the second I site, I(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms to form distorted corner-sharing IO6 octahedra. The corner-sharing octahedral tilt angles are 45°.
CsV2O13I3 crystallizes in the orthorhombic Ima2 space group. Cs(1) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and four equivalent O(6) atoms. The Cs(1)-O(4) bond length is 3.02 Å. Both Cs(1)-O(1) bond lengths are 3.30 Å. Both Cs(1)-O(3) bond lengths are 3.21 Å. There are two shorter (3.28 Å) and two longer (3.40 Å) Cs(1)-O(6) bond lengths. V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. The V(1)-O(2) bond length is 1.85 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.84 Å. The V(1)-O(6) bond length is 1.64 Å. The V(1)-O(7) bond length is 2.03 Å. The V(1)-O(8) bond length is 2.36 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one I(1), and one I(2) atom. The O(8)-I(1) bond length is 1.85 Å. The O(8)-I(2) bond length is 2.60 Å. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Cs(1) and one I(1) atom. The O(1)-I(1) bond length is 1.81 Å. In the third O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent V(1) atoms. In the fourth O site, O(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one I(1) atom. The O(3)-I(1) bond length is 1.90 Å. In the fifth O site, O(4) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent I(2) atoms. There is one shorter (1.81 Å) and one longer (2.66 Å) O(4)-I(2) bond length. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the seventh O site, O(6) is bonded in a single-bond geometry to two equivalent Cs(1) and one V(1) atom. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(1) and one I(2) atom. The O(7)-I(2) bond length is 1.89 Å. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(1), one O(3), and one O(8) atom. In the second I site, I(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms to form distorted corner-sharing IO6 octahedra. The corner-sharing octahedral tilt angles are 45°.