MgV2Bi2(PbO5)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form distorted MgO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one V(2)O4 tetrahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O4 tetrahedra. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  an edgeedge with one Mg(1)O4 tetrahedra. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted pentagonal planar geometry to one O(1), one O(2), one O(3), one O(5), and one O(8) atom. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(5) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(8), and one O(9) atom. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(7) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form distorted edge-sharing OBi2Pb2 tetrahedra. In the second O site, O(2) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Mg(1), one V(2), one Pb(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Pb(2), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one V(2), one Pb(1), one Pb(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Mg(1), one V(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Bi(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom.
MgV2Bi2(PbO5)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form distorted MgO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and  an edgeedge with one V(2)O4 tetrahedra. The Mg(1)-O(10) bond length is 1.96 Å. The Mg(1)-O(3) bond length is 2.02 Å. The Mg(1)-O(6) bond length is 1.96 Å. The Mg(1)-O(7) bond length is 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Mg(1)O4 tetrahedra. The V(1)-O(10) bond length is 1.81 Å. The V(1)-O(4) bond length is 1.83 Å. The V(1)-O(6) bond length is 1.80 Å. The V(1)-O(8) bond length is 1.86 Å. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  an edgeedge with one Mg(1)O4 tetrahedra. The V(2)-O(3) bond length is 1.91 Å. The V(2)-O(5) bond length is 1.88 Å. The V(2)-O(7) bond length is 1.85 Å. The V(2)-O(9) bond length is 1.72 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted pentagonal planar geometry to one O(1), one O(2), one O(3), one O(5), and one O(8) atom. The Pb(1)-O(1) bond length is 2.60 Å. The Pb(1)-O(2) bond length is 2.60 Å. The Pb(1)-O(3) bond length is 2.43 Å. The Pb(1)-O(5) bond length is 2.67 Å. The Pb(1)-O(8) bond length is 2.32 Å. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(4), and one O(5) atom. The Pb(2)-O(1) bond length is 2.44 Å. The Pb(2)-O(2) bond length is 2.33 Å. The Pb(2)-O(4) bond length is 2.66 Å. The Pb(2)-O(5) bond length is 2.46 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(8), and one O(9) atom. The Bi(1)-O(1) bond length is 2.43 Å. The Bi(1)-O(2) bond length is 2.21 Å. The Bi(1)-O(3) bond length is 2.49 Å. The Bi(1)-O(5) bond length is 2.34 Å. The Bi(1)-O(8) bond length is 2.37 Å. The Bi(1)-O(9) bond length is 2.68 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(7) atom. The Bi(2)-O(1) bond length is 2.19 Å. The Bi(2)-O(10) bond length is 2.56 Å. The Bi(2)-O(2) bond length is 2.32 Å. The Bi(2)-O(4) bond length is 2.27 Å. The Bi(2)-O(6) bond length is 2.81 Å. The Bi(2)-O(7) bond length is 2.45 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form distorted edge-sharing OBi2Pb2 tetrahedra. In the second O site, O(2) is bonded to one Pb(1), one Pb(2), one Bi(1), and one Bi(2) atom to form edge-sharing OBi2Pb2 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Mg(1), one V(2), one Pb(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(1), one Pb(2), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one V(2), one Pb(1), one Pb(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Mg(1), one V(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Bi(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one Pb(1), and one Bi(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2) and one Bi(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom.