Gd2W2O9 crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(8) atom. In the second Gd site, Gd(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(3), two equivalent O(5), and two equivalent O(8) atoms. In the third Gd site, Gd(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(5), and two equivalent O(8) atoms. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(2), two equivalent O(10), and two equivalent O(11) atoms to form corner-sharing WO5 trigonal bipyramids. In the second W site, W(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 32-37°. In the third W site, W(3) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(9) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 35-42°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(3), and one W(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Gd(1) and one W(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(2), and one W(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent W(2) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one W(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one W(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one W(2) and one W(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Gd(1), one Gd(2), and one Gd(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to two equivalent W(3) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one W(1) atom. In the eleventh O site, O(11) is bonded in a linear geometry to two equivalent W(1) atoms.
Gd2W2O9 crystallizes in the orthorhombic C222_1 space group. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(8) atom. The Gd(1)-O(1) bond length is 2.39 Å. The Gd(1)-O(10) bond length is 2.81 Å. The Gd(1)-O(2) bond length is 2.41 Å. The Gd(1)-O(3) bond length is 2.37 Å. The Gd(1)-O(5) bond length is 2.34 Å. The Gd(1)-O(8) bond length is 2.12 Å. In the second Gd site, Gd(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(3), two equivalent O(5), and two equivalent O(8) atoms. Both Gd(2)-O(10) bond lengths are 2.48 Å. Both Gd(2)-O(3) bond lengths are 2.53 Å. Both Gd(2)-O(5) bond lengths are 2.63 Å. Both Gd(2)-O(8) bond lengths are 2.28 Å. In the third Gd site, Gd(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(5), and two equivalent O(8) atoms. Both Gd(3)-O(1) bond lengths are 2.49 Å. Both Gd(3)-O(10) bond lengths are 2.53 Å. Both Gd(3)-O(5) bond lengths are 2.69 Å. Both Gd(3)-O(8) bond lengths are 2.26 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(2), two equivalent O(10), and two equivalent O(11) atoms to form corner-sharing WO5 trigonal bipyramids. The W(1)-O(2) bond length is 1.83 Å. Both W(1)-O(10) bond lengths are 1.90 Å. Both W(1)-O(11) bond lengths are 1.89 Å. In the second W site, W(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 32-37°. The W(2)-O(1) bond length is 1.86 Å. The W(2)-O(3) bond length is 1.86 Å. The W(2)-O(4) bond length is 2.00 Å. The W(2)-O(5) bond length is 1.93 Å. The W(2)-O(6) bond length is 2.05 Å. The W(2)-O(7) bond length is 2.04 Å. In the third W site, W(3) is bonded to two equivalent O(6), two equivalent O(7), and two equivalent O(9) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 35-42°. Both W(3)-O(6) bond lengths are 1.92 Å. Both W(3)-O(7) bond lengths are 1.94 Å. Both W(3)-O(9) bond lengths are 1.94 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(3), and one W(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Gd(1) and one W(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Gd(1), one Gd(2), and one W(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to two equivalent W(2) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one W(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one W(2) and one W(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one W(2) and one W(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Gd(1), one Gd(2), and one Gd(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to two equivalent W(3) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one W(1) atom. In the eleventh O site, O(11) is bonded in a linear geometry to two equivalent W(1) atoms.