Cs2MgV2Mn(O3Br)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 1-coordinate geometry to one O(3), two equivalent Br(1), and two equivalent Br(2) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to one Mg(1), one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent Br(1), and two equivalent Br(2) atoms. Mg(1) is bonded in a 4-coordinate geometry to one Cs(2), one O(4), one O(5), and two equivalent O(1) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the second V site, V(2) is bonded in a rectangular see-saw-like geometry to one O(4), one O(5), and two equivalent O(1) atoms. Mn(1) is bonded in a 2-coordinate geometry to one O(2), one O(5), two equivalent Br(1), and two equivalent Br(2) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cs(2), one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Cs(2), one V(1), and one Mn(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Cs(2), one Mg(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Mn(1) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing BrCs4Mn2 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(1) atoms.
Cs2MgV2Mn(O3Br)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 1-coordinate geometry to one O(3), two equivalent Br(1), and two equivalent Br(2) atoms. The Cs(1)-O(3) bond length is 2.98 Å. There is one shorter (3.67 Å) and one longer (3.76 Å) Cs(1)-Br(1) bond length. Both Cs(1)-Br(2) bond lengths are 3.60 Å. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to one Mg(1), one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent Br(1), and two equivalent Br(2) atoms. The Cs(2)-Mg(1) bond length is 3.48 Å. The Cs(2)-O(4) bond length is 3.20 Å. Both Cs(2)-O(1) bond lengths are 3.67 Å. Both Cs(2)-O(2) bond lengths are 3.75 Å. Both Cs(2)-O(3) bond lengths are 3.82 Å. There is one shorter (3.58 Å) and one longer (3.86 Å) Cs(2)-Br(1) bond length. Both Cs(2)-Br(2) bond lengths are 3.73 Å. Mg(1) is bonded in a 4-coordinate geometry to one Cs(2), one O(4), one O(5), and two equivalent O(1) atoms. The Mg(1)-O(4) bond length is 1.88 Å. The Mg(1)-O(5) bond length is 2.16 Å. Both Mg(1)-O(1) bond lengths are 2.03 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. The V(1)-O(2) bond length is 1.78 Å. The V(1)-O(3) bond length is 1.70 Å. Both V(1)-O(1) bond lengths are 1.97 Å. In the second V site, V(2) is bonded in a rectangular see-saw-like geometry to one O(4), one O(5), and two equivalent O(1) atoms. The V(2)-O(4) bond length is 1.77 Å. The V(2)-O(5) bond length is 1.79 Å. Both V(2)-O(1) bond lengths are 1.93 Å. Mn(1) is bonded in a 2-coordinate geometry to one O(2), one O(5), two equivalent Br(1), and two equivalent Br(2) atoms. The Mn(1)-O(2) bond length is 1.99 Å. The Mn(1)-O(5) bond length is 2.07 Å. Both Mn(1)-Br(1) bond lengths are 2.94 Å. There is one shorter (2.73 Å) and one longer (3.36 Å) Mn(1)-Br(2) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cs(2), one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent Cs(2), one V(1), and one Mn(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Cs(2), one Mg(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Mn(1) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing BrCs4Mn2 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Mn(1) atoms.