CeV2O9I crystallizes in the orthorhombic Pbcm space group. Ce(1) is bonded in a 9-coordinate geometry to one O(2), one O(6), one O(7), two equivalent O(3), and four equivalent O(1) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted corner-sharing VO5 trigonal bipyramids. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(5) atoms. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(6) is bonded in a distorted linear geometry to one Ce(1) and one V(2) atom. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ce(1) and one I(1) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Ce(1) and one V(2) atom. In the sixth O site, O(2) is bonded in a linear geometry to one Ce(1) and one I(1) atom. In the seventh O site, O(3) is bonded in a 3-coordinate geometry to one Ce(1), one V(1), and one I(1) atom. I(1) is bonded in a 3-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms.
CeV2O9I crystallizes in the orthorhombic Pbcm space group. Ce(1) is bonded in a 9-coordinate geometry to one O(2), one O(6), one O(7), two equivalent O(3), and four equivalent O(1) atoms. The Ce(1)-O(2) bond length is 2.36 Å. The Ce(1)-O(6) bond length is 2.32 Å. The Ce(1)-O(7) bond length is 2.60 Å. Both Ce(1)-O(3) bond lengths are 2.42 Å. There are two shorter (2.50 Å) and two longer (2.74 Å) Ce(1)-O(1) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted corner-sharing VO5 trigonal bipyramids. The V(1)-O(5) bond length is 1.97 Å. Both V(1)-O(3) bond lengths are 1.73 Å. Both V(1)-O(4) bond lengths are 1.95 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(5) atoms. The V(2)-O(4) bond length is 2.01 Å. The V(2)-O(6) bond length is 1.70 Å. The V(2)-O(7) bond length is 1.69 Å. Both V(2)-O(5) bond lengths are 1.93 Å. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the third O site, O(6) is bonded in a distorted linear geometry to one Ce(1) and one V(2) atom. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Ce(1) and one I(1) atom. The O(1)-I(1) bond length is 1.86 Å. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Ce(1) and one V(2) atom. In the sixth O site, O(2) is bonded in a linear geometry to one Ce(1) and one I(1) atom. The O(2)-I(1) bond length is 1.82 Å. In the seventh O site, O(3) is bonded in a 3-coordinate geometry to one Ce(1), one V(1), and one I(1) atom. The O(3)-I(1) bond length is 2.58 Å. I(1) is bonded in a 3-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms.