Rb4MgV4O10 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(7), one O(9), and two equivalent O(5) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(8), one O(9), and two equivalent O(6) atoms. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to one Mg(1), one O(1), one O(10), one O(3), one O(8), one O(9), two equivalent O(5), and two equivalent O(7) atoms. In the fourth Rb site, Rb(4) is bonded in a 10-coordinate geometry to one Mg(1), one O(10), one O(2), one O(4), one O(7), one O(9), two equivalent O(6), and two equivalent O(8) atoms. Mg(1) is bonded in a square co-planar geometry to one Rb(3), one Rb(4), one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form corner-sharing VO6 octahedra. In the second V site, V(2) is bonded in a square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the third V site, V(3) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. In the fourth V site, V(4) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Rb(4), one Mg(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(2), one Rb(3), one Mg(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Rb(4), one Mg(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to two equivalent Rb(1), two equivalent Rb(3), one V(1), and one V(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to two equivalent Rb(2), two equivalent Rb(4), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(4), two equivalent Rb(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), two equivalent Rb(4), and one V(3) atom. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), one V(3), and one V(4) atom.
Rb4MgV4O10 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(7), one O(9), and two equivalent O(5) atoms. The Rb(1)-O(1) bond length is 2.91 Å. The Rb(1)-O(10) bond length is 3.28 Å. The Rb(1)-O(2) bond length is 3.01 Å. The Rb(1)-O(3) bond length is 3.00 Å. The Rb(1)-O(4) bond length is 2.97 Å. The Rb(1)-O(7) bond length is 2.94 Å. The Rb(1)-O(9) bond length is 3.01 Å. There is one shorter (2.90 Å) and one longer (2.92 Å) Rb(1)-O(5) bond length. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(8), one O(9), and two equivalent O(6) atoms. The Rb(2)-O(1) bond length is 2.96 Å. The Rb(2)-O(10) bond length is 3.05 Å. The Rb(2)-O(2) bond length is 2.94 Å. The Rb(2)-O(3) bond length is 3.01 Å. The Rb(2)-O(4) bond length is 2.95 Å. The Rb(2)-O(8) bond length is 2.97 Å. The Rb(2)-O(9) bond length is 3.32 Å. There is one shorter (2.90 Å) and one longer (2.92 Å) Rb(2)-O(6) bond length. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to one Mg(1), one O(1), one O(10), one O(3), one O(8), one O(9), two equivalent O(5), and two equivalent O(7) atoms. The Rb(3)-Mg(1) bond length is 2.89 Å. The Rb(3)-O(1) bond length is 3.33 Å. The Rb(3)-O(10) bond length is 2.85 Å. The Rb(3)-O(3) bond length is 3.29 Å. The Rb(3)-O(8) bond length is 2.70 Å. The Rb(3)-O(9) bond length is 2.96 Å. There is one shorter (2.89 Å) and one longer (3.39 Å) Rb(3)-O(5) bond length. There is one shorter (2.94 Å) and one longer (3.20 Å) Rb(3)-O(7) bond length. In the fourth Rb site, Rb(4) is bonded in a 10-coordinate geometry to one Mg(1), one O(10), one O(2), one O(4), one O(7), one O(9), two equivalent O(6), and two equivalent O(8) atoms. The Rb(4)-Mg(1) bond length is 2.90 Å. The Rb(4)-O(10) bond length is 2.93 Å. The Rb(4)-O(2) bond length is 3.36 Å. The Rb(4)-O(4) bond length is 3.33 Å. The Rb(4)-O(7) bond length is 2.75 Å. The Rb(4)-O(9) bond length is 2.82 Å. There is one shorter (2.88 Å) and one longer (3.41 Å) Rb(4)-O(6) bond length. There is one shorter (2.88 Å) and one longer (3.30 Å) Rb(4)-O(8) bond length. Mg(1) is bonded in a square co-planar geometry to one Rb(3), one Rb(4), one O(1), one O(2), one O(3), and one O(4) atom. The Mg(1)-O(1) bond length is 1.99 Å. The Mg(1)-O(2) bond length is 1.97 Å. The Mg(1)-O(3) bond length is 1.97 Å. The Mg(1)-O(4) bond length is 2.00 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form corner-sharing VO6 octahedra. The V(1)-O(1) bond length is 2.35 Å. The V(1)-O(2) bond length is 2.11 Å. The V(1)-O(3) bond length is 2.10 Å. The V(1)-O(4) bond length is 2.33 Å. The V(1)-O(5) bond length is 2.04 Å. The V(1)-O(6) bond length is 2.19 Å. In the second V site, V(2) is bonded in a square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. The V(2)-O(1) bond length is 1.91 Å. The V(2)-O(2) bond length is 2.09 Å. The V(2)-O(3) bond length is 2.09 Å. The V(2)-O(4) bond length is 1.91 Å. In the third V site, V(3) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. The V(3)-O(10) bond length is 1.86 Å. The V(3)-O(5) bond length is 1.86 Å. The V(3)-O(8) bond length is 1.72 Å. The V(3)-O(9) bond length is 1.84 Å. In the fourth V site, V(4) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. The V(4)-O(10) bond length is 1.87 Å. The V(4)-O(6) bond length is 1.82 Å. The V(4)-O(7) bond length is 1.72 Å. The V(4)-O(9) bond length is 1.89 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Rb(4), one Mg(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Rb(1), one Rb(2), one Rb(3), one Mg(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(2), one Rb(4), one Mg(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to two equivalent Rb(1), two equivalent Rb(3), one V(1), and one V(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to two equivalent Rb(2), two equivalent Rb(4), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(4), two equivalent Rb(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), two equivalent Rb(4), and one V(3) atom. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one Rb(1), one Rb(2), one Rb(3), one Rb(4), one V(3), and one V(4) atom.