Bi2WO6 crystallizes in the monoclinic C2/m space group. W(1) is bonded to one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form distorted WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-78°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with four equivalent W(1)O6 octahedra and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-78°. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(2), two equivalent O(4), two equivalent O(5), and three equivalent O(1) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form OBi4 tetrahedra that share corners with two equivalent O(3)Bi2W2 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(2) and three equivalent Bi(1) atoms to form OBi4 tetrahedra that share corners with two equivalent O(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, corners with four equivalent O(3)Bi2W2 tetrahedra,  an edgeedge with one O(3)Bi2W2 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent W(1) and two equivalent Bi(1) atoms to form OBi2W2 tetrahedra that share corners with two equivalent O(3)Bi2W2 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, corners with four equivalent O(2)Bi4 tetrahedra,  an edgeedge with one O(3)Bi2W2 tetrahedra, and  an edgeedge with one O(2)Bi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one W(1) and two equivalent Bi(2) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one W(1) and two equivalent Bi(2) atoms. In the sixth O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms.
Bi2WO6 crystallizes in the monoclinic C2/m space group. W(1) is bonded to one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form distorted WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-78°. The W(1)-O(4) bond length is 1.78 Å. The W(1)-O(5) bond length is 1.83 Å. There is one shorter (1.99 Å) and one longer (2.18 Å) W(1)-O(3) bond length. Both W(1)-O(6) bond lengths are 1.91 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with four equivalent W(1)O6 octahedra and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-78°. The Bi(1)-O(1) bond length is 2.34 Å. Both Bi(1)-O(3) bond lengths are 2.52 Å. There is one shorter (2.30 Å) and two longer (2.36 Å) Bi(1)-O(2) bond lengths. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(2), two equivalent O(4), two equivalent O(5), and three equivalent O(1) atoms. The Bi(2)-O(2) bond length is 2.43 Å. Both Bi(2)-O(4) bond lengths are 2.67 Å. Both Bi(2)-O(5) bond lengths are 2.71 Å. There is one shorter (2.29 Å) and two longer (2.30 Å) Bi(2)-O(1) bond lengths. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form OBi4 tetrahedra that share corners with two equivalent O(3)Bi2W2 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(2) and three equivalent Bi(1) atoms to form OBi4 tetrahedra that share corners with two equivalent O(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, corners with four equivalent O(3)Bi2W2 tetrahedra,  an edgeedge with one O(3)Bi2W2 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the third O site, O(3) is bonded to two equivalent W(1) and two equivalent Bi(1) atoms to form OBi2W2 tetrahedra that share corners with two equivalent O(3)Bi2W2 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, corners with four equivalent O(2)Bi4 tetrahedra,  an edgeedge with one O(3)Bi2W2 tetrahedra, and  an edgeedge with one O(2)Bi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one W(1) and two equivalent Bi(2) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one W(1) and two equivalent Bi(2) atoms. In the sixth O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms.