Bi2WO6 crystallizes in the orthorhombic Pca2_1 space group. W(1) is bonded to one O(1), one O(5), one O(6), and two equivalent O(2) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Bi(2)O5 square pyramids and corners with two equivalent W(1)O5 trigonal bipyramids. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(5), and two equivalent O(6) atoms. In the second Bi site, Bi(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent O(6)Bi2WO tetrahedra, corners with two equivalent W(1)O5 trigonal bipyramids, and edges with two equivalent Bi(2)O5 square pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one W(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent W(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to two equivalent Bi(2) and one O(6) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one W(1) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded to one W(1), two equivalent Bi(1), and one O(4) atom to form distorted OBi2WO tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids and corners with two equivalent O(6)Bi2WO tetrahedra.
Bi2WO6 crystallizes in the orthorhombic Pca2_1 space group. W(1) is bonded to one O(1), one O(5), one O(6), and two equivalent O(2) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Bi(2)O5 square pyramids and corners with two equivalent W(1)O5 trigonal bipyramids. The W(1)-O(1) bond length is 1.94 Å. The W(1)-O(5) bond length is 2.09 Å. The W(1)-O(6) bond length is 2.20 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) W(1)-O(2) bond length. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(5), and two equivalent O(6) atoms. The Bi(1)-O(2) bond length is 2.77 Å. The Bi(1)-O(3) bond length is 2.09 Å. There is one shorter (2.29 Å) and one longer (2.31 Å) Bi(1)-O(5) bond length. There is one shorter (2.59 Å) and one longer (2.70 Å) Bi(1)-O(6) bond length. In the second Bi site, Bi(2) is bonded to one O(3), two equivalent O(1), and two equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent O(6)Bi2WO tetrahedra, corners with two equivalent W(1)O5 trigonal bipyramids, and edges with two equivalent Bi(2)O5 square pyramids. The Bi(2)-O(3) bond length is 2.06 Å. There is one shorter (2.46 Å) and one longer (2.49 Å) Bi(2)-O(1) bond length. There is one shorter (2.37 Å) and one longer (2.40 Å) Bi(2)-O(4) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one W(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent W(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to two equivalent Bi(2) and one O(6) atom. The O(4)-O(6) bond length is 1.49 Å. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one W(1) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded to one W(1), two equivalent Bi(1), and one O(4) atom to form distorted OBi2WO tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids and corners with two equivalent O(6)Bi2WO tetrahedra.