Rb2V2Mn(O3Cl)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(4), two equivalent O(5), one Cl(2), one Cl(4), and two equivalent Cl(1) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(2), one O(5), one O(6), two equivalent O(4), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)Cl4O2 octahedra and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)Cl4O2 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 29°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3), one Cl(1), one Cl(3), and two equivalent Cl(2) atoms to form distorted MnCl4O2 octahedra that share corners with two equivalent Mn(1)Cl4O2 octahedra, corners with two equivalent Mn(2)Cl4O2 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second Mn site, Mn(2) is bonded to two equivalent O(6), one Cl(1), one Cl(3), and two equivalent Cl(4) atoms to form distorted MnCl4O2 octahedra that share corners with two equivalent Mn(1)Cl4O2 octahedra, corners with two equivalent Mn(2)Cl4O2 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a single-bond geometry to one Rb(2), two equivalent Rb(1), and one V(2) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Rb(2), one V(2), and one Mn(2) atom. In the third O site, O(1) is bonded in a 2-coordinate geometry to one Rb(1), one V(1), and one V(2) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), one V(1), and one V(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Rb(1), one V(1), and one Mn(1) atom. In the sixth O site, O(4) is bonded in a single-bond geometry to one Rb(1), two equivalent Rb(2), and one V(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one Mn(1), and one Mn(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ClRb4Mn2 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third Cl site, Cl(3) is bonded in a 6-coordinate geometry to four equivalent Rb(2), one Mn(1), and one Mn(2) atom. In the fourth Cl site, Cl(4) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ClRb4Mn2 octahedra. The corner-sharing octahedral tilt angles are 4°.
Rb2V2Mn(O3Cl)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one O(1), one O(3), one O(4), two equivalent O(5), one Cl(2), one Cl(4), and two equivalent Cl(1) atoms. The Rb(1)-O(1) bond length is 3.14 Å. The Rb(1)-O(3) bond length is 3.59 Å. The Rb(1)-O(4) bond length is 3.15 Å. There is one shorter (3.19 Å) and one longer (3.34 Å) Rb(1)-O(5) bond length. The Rb(1)-Cl(2) bond length is 3.42 Å. The Rb(1)-Cl(4) bond length is 3.77 Å. There is one shorter (3.64 Å) and one longer (3.67 Å) Rb(1)-Cl(1) bond length. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one O(2), one O(5), one O(6), two equivalent O(4), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. The Rb(2)-O(2) bond length is 3.17 Å. The Rb(2)-O(5) bond length is 3.22 Å. The Rb(2)-O(6) bond length is 3.56 Å. There is one shorter (3.20 Å) and one longer (3.39 Å) Rb(2)-O(4) bond length. The Rb(2)-Cl(2) bond length is 3.74 Å. The Rb(2)-Cl(4) bond length is 3.39 Å. There is one shorter (3.61 Å) and one longer (3.65 Å) Rb(2)-Cl(3) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)Cl4O2 octahedra and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The V(1)-O(1) bond length is 1.81 Å. The V(1)-O(2) bond length is 1.82 Å. The V(1)-O(3) bond length is 1.70 Å. The V(1)-O(4) bond length is 1.65 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)Cl4O2 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 29°. The V(2)-O(1) bond length is 1.82 Å. The V(2)-O(2) bond length is 1.81 Å. The V(2)-O(5) bond length is 1.65 Å. The V(2)-O(6) bond length is 1.70 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3), one Cl(1), one Cl(3), and two equivalent Cl(2) atoms to form distorted MnCl4O2 octahedra that share corners with two equivalent Mn(1)Cl4O2 octahedra, corners with two equivalent Mn(2)Cl4O2 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Mn(1)-O(3) bond lengths are 2.04 Å. The Mn(1)-Cl(1) bond length is 2.95 Å. The Mn(1)-Cl(3) bond length is 2.53 Å. Both Mn(1)-Cl(2) bond lengths are 2.81 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(6), one Cl(1), one Cl(3), and two equivalent Cl(4) atoms to form distorted MnCl4O2 octahedra that share corners with two equivalent Mn(1)Cl4O2 octahedra, corners with two equivalent Mn(2)Cl4O2 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Mn(2)-O(6) bond lengths are 2.03 Å. The Mn(2)-Cl(1) bond length is 2.52 Å. The Mn(2)-Cl(3) bond length is 2.98 Å. Both Mn(2)-Cl(4) bond lengths are 2.81 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a single-bond geometry to one Rb(2), two equivalent Rb(1), and one V(2) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Rb(2), one V(2), and one Mn(2) atom. In the third O site, O(1) is bonded in a 2-coordinate geometry to one Rb(1), one V(1), and one V(2) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one Rb(2), one V(1), and one V(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Rb(1), one V(1), and one Mn(1) atom. In the sixth O site, O(4) is bonded in a single-bond geometry to one Rb(1), two equivalent Rb(2), and one V(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Rb(1), one Mn(1), and one Mn(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ClRb4Mn2 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third Cl site, Cl(3) is bonded in a 6-coordinate geometry to four equivalent Rb(2), one Mn(1), and one Mn(2) atom. In the fourth Cl site, Cl(4) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ClRb4Mn2 octahedra. The corner-sharing octahedral tilt angles are 4°.