W3O8 crystallizes in the orthorhombic Pbam space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 3-55°. In the second W site, W(2) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 5-46°. In the third W site, W(3) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(8) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(7) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(8) is bonded in a linear geometry to two equivalent W(3) atoms. In the fourth O site, O(1) is bonded in a bent 150 degrees geometry to one W(2) and one W(3) atom. In the fifth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one W(2) and two equivalent W(1) atoms. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to one W(1) and one W(3) atom. In the seventh O site, O(4) is bonded in a trigonal planar geometry to one W(1), one W(2), and one W(3) atom. In the eighth O site, O(5) is bonded in a bent 150 degrees geometry to one W(2) and one W(3) atom.
W3O8 crystallizes in the orthorhombic Pbam space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 3-55°. The W(1)-O(3) bond length is 1.97 Å. The W(1)-O(4) bond length is 2.07 Å. There is one shorter (2.06 Å) and one longer (2.07 Å) W(1)-O(2) bond length. Both W(1)-O(6) bond lengths are 1.93 Å. In the second W site, W(2) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 5-46°. The W(2)-O(1) bond length is 2.00 Å. The W(2)-O(2) bond length is 2.05 Å. The W(2)-O(4) bond length is 2.20 Å. The W(2)-O(5) bond length is 1.99 Å. Both W(2)-O(7) bond lengths are 1.93 Å. In the third W site, W(3) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(8) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. The W(3)-O(1) bond length is 1.92 Å. The W(3)-O(3) bond length is 1.91 Å. The W(3)-O(4) bond length is 2.09 Å. The W(3)-O(5) bond length is 1.90 Å. Both W(3)-O(8) bond lengths are 1.93 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(7) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(8) is bonded in a linear geometry to two equivalent W(3) atoms. In the fourth O site, O(1) is bonded in a bent 150 degrees geometry to one W(2) and one W(3) atom. In the fifth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one W(2) and two equivalent W(1) atoms. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to one W(1) and one W(3) atom. In the seventh O site, O(4) is bonded in a trigonal planar geometry to one W(1), one W(2), and one W(3) atom. In the eighth O site, O(5) is bonded in a bent 150 degrees geometry to one W(2) and one W(3) atom.