RbV3O8 crystallizes in the monoclinic P2_1/m space group. Rb(1) is bonded in a 10-coordinate geometry to one O(3), one O(4), four equivalent O(1), and four equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(5) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), 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 120 degrees geometry to two equivalent Rb(1), one V(1), and one V(2) atom. 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 one Rb(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Rb(1), one V(2), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms.
RbV3O8 crystallizes in the monoclinic P2_1/m space group. Rb(1) is bonded in a 10-coordinate geometry to one O(3), one O(4), four equivalent O(1), and four equivalent O(2) atoms. The Rb(1)-O(3) bond length is 2.91 Å. The Rb(1)-O(4) bond length is 2.86 Å. There are two shorter (3.17 Å) and two longer (3.40 Å) Rb(1)-O(1) bond lengths. There are two shorter (2.96 Å) and two longer (3.17 Å) Rb(1)-O(2) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(5) atoms. The V(1)-O(1) bond length is 1.76 Å. The V(1)-O(2) bond length is 1.61 Å. The V(1)-O(4) bond length is 1.86 Å. There is one shorter (1.94 Å) and one longer (1.98 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(5) atoms. The V(2)-O(3) bond length is 1.61 Å. The V(2)-O(4) bond length is 2.35 Å. Both V(2)-O(1) bond lengths are 1.92 Å. Both V(2)-O(5) bond lengths are 1.87 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Rb(1), one V(1), and one V(2) atom. 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 one Rb(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Rb(1), one V(2), and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms.