RbV4O10 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a body-centered cubic geometry to 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 in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(5) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a single-bond geometry to two equivalent Rb(1) and one V(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to two equivalent Rb(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms.
RbV4O10 crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a body-centered cubic geometry to four equivalent O(2) and four equivalent O(3) atoms. All Rb(1)-O(2) bond lengths are 2.98 Å. All Rb(1)-O(3) bond lengths are 2.99 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms. The V(1)-O(2) bond length is 1.64 Å. The V(1)-O(5) bond length is 2.08 Å. There is one shorter (1.81 Å) and one longer (2.44 Å) V(1)-O(1) bond length. Both V(1)-O(4) bond lengths are 1.93 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), and two equivalent O(5) atoms. The V(2)-O(1) bond length is 1.88 Å. The V(2)-O(3) bond length is 1.63 Å. The V(2)-O(4) bond length is 2.00 Å. Both V(2)-O(5) bond lengths are 1.94 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a single-bond geometry to two equivalent Rb(1) and one V(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to two equivalent Rb(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms.