MgWBiO5 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form MgO6 octahedra that share corners with four equivalent W(1)O4 tetrahedra and  an edgeedge with one Mg(1)O6 octahedra. W(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form WO4 tetrahedra that share corners with four equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-57°. Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one W(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mg(1), one W(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one W(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and two equivalent Bi(1) atoms to form distorted edge-sharing OMg2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one W(1), and one Bi(1) atom.
MgWBiO5 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form MgO6 octahedra that share corners with four equivalent W(1)O4 tetrahedra and  an edgeedge with one Mg(1)O6 octahedra. The Mg(1)-O(1) bond length is 2.18 Å. The Mg(1)-O(2) bond length is 2.12 Å. The Mg(1)-O(3) bond length is 2.07 Å. The Mg(1)-O(5) bond length is 2.09 Å. There is one shorter (2.11 Å) and one longer (2.24 Å) Mg(1)-O(4) bond length. W(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form WO4 tetrahedra that share corners with four equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-57°. The W(1)-O(1) bond length is 1.87 Å. The W(1)-O(2) bond length is 1.84 Å. The W(1)-O(3) bond length is 1.90 Å. The W(1)-O(5) bond length is 1.94 Å. Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. The Bi(1)-O(1) bond length is 2.51 Å. The Bi(1)-O(2) bond length is 2.68 Å. The Bi(1)-O(3) bond length is 2.54 Å. The Bi(1)-O(5) bond length is 2.27 Å. There is one shorter (2.22 Å) and one longer (2.23 Å) Bi(1)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one W(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mg(1), one W(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one W(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and two equivalent Bi(1) atoms to form distorted edge-sharing OMg2Bi2 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one W(1), and one Bi(1) atom.