MgVBiO6 crystallizes in the monoclinic P2_1/m space group. Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted MgO5 square pyramids that share corners with three equivalent V(1)O4 tetrahedra. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with three equivalent Mg(1)O5 square pyramids. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Mg(1) and one V(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1) and two equivalent Bi(1) atoms.
MgVBiO6 crystallizes in the monoclinic P2_1/m space group. Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted MgO5 square pyramids that share corners with three equivalent V(1)O4 tetrahedra. The Mg(1)-O(1) bond length is 1.98 Å. Both Mg(1)-O(3) bond lengths are 1.99 Å. Both Mg(1)-O(4) bond lengths are 2.18 Å. V(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with three equivalent Mg(1)O5 square pyramids. The V(1)-O(1) bond length is 1.69 Å. The V(1)-O(2) bond length is 1.90 Å. Both V(1)-O(3) bond lengths are 1.71 Å. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(4) atoms. The Bi(1)-O(2) bond length is 2.06 Å. There are two shorter (2.12 Å) and two longer (2.18 Å) Bi(1)-O(4) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Mg(1) and one V(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1) and two equivalent Bi(1) atoms.