Rb2V(PO4)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(4), and four equivalent O(3) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form corner-sharing PO4 tetrahedra. There are five inequivalent O sites. In the first O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), two equivalent Rb(1), and one P(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one V(1), and one P(1) atom. In the third O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Rb(2) and two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a single-bond geometry to one Rb(1), one Rb(2), and one V(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Rb(2), one V(1), and one P(1) atom.
Rb2V(PO4)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(4), and four equivalent O(3) atoms. The Rb(1)-O(1) bond length is 3.38 Å. Both Rb(1)-O(4) bond lengths are 3.24 Å. There are two shorter (2.93 Å) and two longer (3.14 Å) Rb(1)-O(3) bond lengths. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one O(1), one O(5), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. The Rb(2)-O(1) bond length is 3.11 Å. The Rb(2)-O(5) bond length is 3.31 Å. Both Rb(2)-O(2) bond lengths are 3.52 Å. Both Rb(2)-O(3) bond lengths are 2.90 Å. Both Rb(2)-O(4) bond lengths are 3.35 Å. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. The V(1)-O(1) bond length is 1.64 Å. Both V(1)-O(2) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.99 Å. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form corner-sharing PO4 tetrahedra. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.64 Å. There are five inequivalent O sites. In the first O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), two equivalent Rb(1), and one P(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one V(1), and one P(1) atom. In the third O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Rb(2) and two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a single-bond geometry to one Rb(1), one Rb(2), and one V(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Rb(2), one V(1), and one P(1) atom.