RbV(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(1), one O(12), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(2), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-53°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-45°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-43°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one Rb(1), one Rb(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Rb(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one V(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Rb(1), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Rb(2), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Rb(1), one V(1), and one P(3) atom.
RbV(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(1), one O(12), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. The Rb(1)-O(1) bond length is 3.36 Å. The Rb(1)-O(12) bond length is 2.93 Å. The Rb(1)-O(3) bond length is 2.97 Å. The Rb(1)-O(4) bond length is 3.28 Å. The Rb(1)-O(5) bond length is 3.30 Å. The Rb(1)-O(6) bond length is 2.75 Å. The Rb(1)-O(8) bond length is 3.37 Å. The Rb(1)-O(9) bond length is 2.77 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(3), two equivalent O(6), and two equivalent O(9) atoms. Both Rb(2)-O(10) bond lengths are 3.06 Å. Both Rb(2)-O(3) bond lengths are 3.00 Å. Both Rb(2)-O(6) bond lengths are 3.15 Å. Both Rb(2)-O(9) bond lengths are 2.98 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(2), one O(4), one O(5), and one O(7) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The V(1)-O(10) bond length is 1.90 Å. The V(1)-O(12) bond length is 1.90 Å. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(4) bond length is 1.95 Å. The V(1)-O(5) bond length is 1.87 Å. The V(1)-O(7) bond length is 1.87 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Both V(2)-O(1) bond lengths are 1.95 Å. Both V(2)-O(11) bond lengths are 1.86 Å. Both V(2)-O(8) bond lengths are 1.92 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-53°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-45°. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.49 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-43°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(11) bond length is 1.58 Å. The P(3)-O(12) bond length is 1.57 Å. The P(3)-O(9) bond length is 1.49 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one Rb(1), one Rb(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Rb(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Rb(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one V(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Rb(1), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Rb(2), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Rb(1), one V(1), and one P(3) atom.