MgV2Mn2(BiO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted MgO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 11°. V(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Bi(1)O5 square pyramid,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with three equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 11°. Bi(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(4) atoms to form distorted BiO5 square pyramids that share  a cornercorner with one Mn(1)O6 octahedra,  an edgeedge with one Mg(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 42°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Mn(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one Mn(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one Mn(1) atom. In the fourth O site, O(4) is bonded to two equivalent Mn(1) and two equivalent Bi(1) atoms to form edge-sharing OMn2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one Mn(1), and one Bi(1) atom.
MgV2Mn2(BiO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted MgO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 11°. Both Mg(1)-O(2) bond lengths are 2.03 Å. Both Mg(1)-O(3) bond lengths are 2.16 Å. Both Mg(1)-O(5) bond lengths are 2.11 Å. V(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The V(1)-O(1) bond length is 1.80 Å. The V(1)-O(2) bond length is 1.95 Å. The V(1)-O(3) bond length is 1.77 Å. The V(1)-O(5) bond length is 1.93 Å. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Bi(1)O5 square pyramid,  an edgeedge with one Mg(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with three equivalent Bi(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 11°. The Mn(1)-O(1) bond length is 2.23 Å. The Mn(1)-O(2) bond length is 2.46 Å. The Mn(1)-O(3) bond length is 2.17 Å. The Mn(1)-O(5) bond length is 2.14 Å. There is one shorter (2.17 Å) and one longer (2.25 Å) Mn(1)-O(4) bond length. Bi(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(4) atoms to form distorted BiO5 square pyramids that share  a cornercorner with one Mn(1)O6 octahedra,  an edgeedge with one Mg(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 42°. The Bi(1)-O(1) bond length is 2.33 Å. The Bi(1)-O(2) bond length is 2.33 Å. The Bi(1)-O(5) bond length is 2.49 Å. There is one shorter (2.13 Å) and one longer (2.33 Å) Bi(1)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Mn(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one Mn(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one Mn(1) atom. In the fourth O site, O(4) is bonded to two equivalent Mn(1) and two equivalent Bi(1) atoms to form edge-sharing OMn2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one Mn(1), and one Bi(1) atom.