Rb3V5O14 crystallizes in the trigonal P31m space group. Rb(1) is bonded in a 10-coordinate geometry to one O(2), two equivalent O(4), three 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(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(4) and three equivalent O(1) atoms to form corner-sharing VO4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 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 distorted bent 150 degrees geometry to one Rb(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Rb(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to three equivalent Rb(1) and one V(2) atom.
Rb3V5O14 crystallizes in the trigonal P31m space group. Rb(1) is bonded in a 10-coordinate geometry to one O(2), two equivalent O(4), three equivalent O(3), and four equivalent O(1) atoms. The Rb(1)-O(2) bond length is 3.00 Å. Both Rb(1)-O(4) bond lengths are 2.92 Å. There are two shorter (3.14 Å) and one longer (3.30 Å) Rb(1)-O(3) bond length. There are two shorter (3.01 Å) and two longer (3.12 Å) Rb(1)-O(1) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(2)O4 tetrahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The V(1)-O(3) bond length is 1.62 Å. Both V(1)-O(1) bond lengths are 1.92 Å. Both V(1)-O(2) bond lengths are 1.82 Å. In the second V site, V(2) is bonded to one O(4) and three equivalent O(1) atoms to form corner-sharing VO4 tetrahedra. The V(2)-O(4) bond length is 1.64 Å. All V(2)-O(1) bond lengths are 1.75 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 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 distorted bent 150 degrees geometry to one Rb(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Rb(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to three equivalent Rb(1) and one V(2) atom.