MgV2(BiO5)2 crystallizes in the monoclinic P2_1 space group. Mg(1) is bonded to one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form MgO6 octahedra that share  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent Mg(1)O6 octahedra, and  an edgeedge with one Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. In the second V site, V(2) is bonded to one O(10), one O(2), one O(6), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O6 octahedra and corners with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-53°. 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(10), one O(2), one O(4), one O(6), and one O(8) atom. In the second Bi site, Bi(2) is bonded to one O(3), one O(4), one O(5), one O(7), one O(8), and one O(9) atom to form distorted BiO6 octahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Bi(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(2) and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Mg(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one V(1) and one Bi(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mg(1), one V(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Mg(1), one Bi(1), and one Bi(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a water-like geometry to one V(2) and one Bi(1) atom.
MgV2(BiO5)2 crystallizes in the monoclinic P2_1 space group. Mg(1) is bonded to one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form MgO6 octahedra that share  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles are 45°. The Mg(1)-O(3) bond length is 2.10 Å. The Mg(1)-O(4) bond length is 2.08 Å. The Mg(1)-O(6) bond length is 2.06 Å. The Mg(1)-O(7) bond length is 2.20 Å. The Mg(1)-O(8) bond length is 2.16 Å. The Mg(1)-O(9) bond length is 2.30 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent Mg(1)O6 octahedra, and  an edgeedge with one Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. The V(1)-O(1) bond length is 1.75 Å. The V(1)-O(3) bond length is 1.78 Å. The V(1)-O(5) bond length is 1.70 Å. The V(1)-O(7) bond length is 1.80 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(6), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O6 octahedra and corners with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-53°. The V(2)-O(10) bond length is 1.74 Å. The V(2)-O(2) bond length is 1.76 Å. The V(2)-O(6) bond length is 1.71 Å. The V(2)-O(9) bond length is 1.81 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(10), one O(2), one O(4), one O(6), and one O(8) atom. The Bi(1)-O(1) bond length is 2.29 Å. The Bi(1)-O(10) bond length is 2.36 Å. The Bi(1)-O(2) bond length is 2.20 Å. The Bi(1)-O(4) bond length is 2.18 Å. The Bi(1)-O(6) bond length is 2.70 Å. The Bi(1)-O(8) bond length is 2.15 Å. In the second Bi site, Bi(2) is bonded to one O(3), one O(4), one O(5), one O(7), one O(8), and one O(9) atom to form distorted BiO6 octahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and  an edgeedge with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 45°. The Bi(2)-O(3) bond length is 2.45 Å. The Bi(2)-O(4) bond length is 2.14 Å. The Bi(2)-O(5) bond length is 2.33 Å. The Bi(2)-O(7) bond length is 2.32 Å. The Bi(2)-O(8) bond length is 2.16 Å. The Bi(2)-O(9) bond length is 2.26 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Bi(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(2) and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Mg(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one V(1) and one Bi(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mg(1), one V(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Bi(2) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Mg(1), one Bi(1), and one Bi(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one Bi(2) atom. In the tenth O site, O(10) is bonded in a water-like geometry to one V(2) and one Bi(1) atom.