Rb(WO3)4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to four equivalent O(2) and eight equivalent O(3) atoms to form RbO12 cuboctahedra that share edges with four equivalent W(1)O6 octahedra, edges with eight equivalent W(3)O6 octahedra, and faces with two equivalent Rb(2)O12 cuboctahedra. In the second Rb site, Rb(2) is bonded to two equivalent O(1), two equivalent O(2), four equivalent O(3), and four equivalent O(4) atoms to form distorted RbO12 cuboctahedra that share edges with two equivalent W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, edges with eight equivalent W(3)O6 octahedra, and  a faceface with one Rb(1)O12 cuboctahedra. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(6), one O(9), and four equivalent O(3) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra, edges with two equivalent Rb(1)O12 cuboctahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. In the second W site, W(2) is bonded to one O(7), one O(9), and four equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. In the third W site, W(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra,  an edgeedge with one Rb(1)O12 cuboctahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. There are nine inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one Rb(1), one Rb(2), one W(1), and one W(3) atom. In the second O site, O(4) is bonded in a bent 150 degrees geometry to one Rb(2), one W(2), and one W(3) atom. In the third O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the fourth O site, O(9) is bonded in a linear geometry to one W(1) and one W(2) atom. In the fifth O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms. In the sixth O site, O(7) is bonded in a linear geometry to two equivalent W(2) atoms. In the seventh O site, O(8) is bonded in a linear geometry to two equivalent W(3) atoms. In the eighth O site, O(1) is bonded in a bent 150 degrees geometry to one Rb(2) and two equivalent W(3) atoms. In the ninth O site, O(2) is bonded in a bent 150 degrees geometry to one Rb(1), one Rb(2), and two equivalent W(3) atoms.
Rb(WO3)4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to four equivalent O(2) and eight equivalent O(3) atoms to form RbO12 cuboctahedra that share edges with four equivalent W(1)O6 octahedra, edges with eight equivalent W(3)O6 octahedra, and faces with two equivalent Rb(2)O12 cuboctahedra. All Rb(1)-O(2) bond lengths are 3.35 Å. All Rb(1)-O(3) bond lengths are 3.36 Å. In the second Rb site, Rb(2) is bonded to two equivalent O(1), two equivalent O(2), four equivalent O(3), and four equivalent O(4) atoms to form distorted RbO12 cuboctahedra that share edges with two equivalent W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, edges with eight equivalent W(3)O6 octahedra, and  a faceface with one Rb(1)O12 cuboctahedra. Both Rb(2)-O(1) bond lengths are 3.29 Å. Both Rb(2)-O(2) bond lengths are 3.44 Å. All Rb(2)-O(3) bond lengths are 3.45 Å. All Rb(2)-O(4) bond lengths are 3.29 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(6), one O(9), and four equivalent O(3) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra, edges with two equivalent Rb(1)O12 cuboctahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. The W(1)-O(6) bond length is 1.94 Å. The W(1)-O(9) bond length is 1.93 Å. All W(1)-O(3) bond lengths are 1.95 Å. In the second W site, W(2) is bonded to one O(7), one O(9), and four equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. The W(2)-O(7) bond length is 1.93 Å. The W(2)-O(9) bond length is 1.95 Å. All W(2)-O(4) bond lengths are 1.95 Å. In the third W site, W(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent W(3)O6 octahedra,  an edgeedge with one Rb(1)O12 cuboctahedra, and edges with two equivalent Rb(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-30°. The W(3)-O(1) bond length is 1.96 Å. The W(3)-O(2) bond length is 1.94 Å. The W(3)-O(3) bond length is 1.94 Å. The W(3)-O(4) bond length is 1.95 Å. The W(3)-O(5) bond length is 1.93 Å. The W(3)-O(8) bond length is 1.94 Å. There are nine inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one Rb(1), one Rb(2), one W(1), and one W(3) atom. In the second O site, O(4) is bonded in a bent 150 degrees geometry to one Rb(2), one W(2), and one W(3) atom. In the third O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the fourth O site, O(9) is bonded in a linear geometry to one W(1) and one W(2) atom. In the fifth O site, O(6) is bonded in a linear geometry to two equivalent W(1) atoms. In the sixth O site, O(7) is bonded in a linear geometry to two equivalent W(2) atoms. In the seventh O site, O(8) is bonded in a linear geometry to two equivalent W(3) atoms. In the eighth O site, O(1) is bonded in a bent 150 degrees geometry to one Rb(2) and two equivalent W(3) atoms. In the ninth O site, O(2) is bonded in a bent 150 degrees geometry to one Rb(1), one Rb(2), and two equivalent W(3) atoms.