Ca(WO2)2 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. W(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and three equivalent W(1) atoms to form distorted OCa2W3 square pyramids that share corners with four equivalent O(3)Ca2W4 octahedra, corners with two equivalent O(1)Ca2W3 square pyramids, corners with five equivalent O(2)Ca2W2 tetrahedra, edges with three equivalent O(3)Ca2W4 octahedra, edges with five equivalent O(1)Ca2W3 square pyramids, and  an edgeedge with one O(2)Ca2W2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-43°. In the second O site, O(2) is bonded to two equivalent Ca(1) and two equivalent W(1) atoms to form OCa2W2 tetrahedra that share corners with ten equivalent O(1)Ca2W3 square pyramids, corners with two equivalent O(2)Ca2W2 tetrahedra, edges with four equivalent O(3)Ca2W4 octahedra, and edges with two equivalent O(1)Ca2W3 square pyramids. In the third O site, O(3) is bonded to two equivalent Ca(1) and four equivalent W(1) atoms to form OCa2W4 octahedra that share corners with two equivalent O(3)Ca2W4 octahedra, corners with eight equivalent O(1)Ca2W3 square pyramids, edges with two equivalent O(3)Ca2W4 octahedra, edges with six equivalent O(1)Ca2W3 square pyramids, and edges with four equivalent O(2)Ca2W2 tetrahedra. The corner-sharing octahedral tilt angles are 50°.
Ca(WO2)2 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. Both Ca(1)-O(2) bond lengths are 2.28 Å. Both Ca(1)-O(3) bond lengths are 2.90 Å. All Ca(1)-O(1) bond lengths are 2.55 Å. W(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. The W(1)-O(2) bond length is 2.15 Å. Both W(1)-O(3) bond lengths are 2.28 Å. There are two shorter (2.18 Å) and one longer (2.21 Å) W(1)-O(1) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and three equivalent W(1) atoms to form distorted OCa2W3 square pyramids that share corners with four equivalent O(3)Ca2W4 octahedra, corners with two equivalent O(1)Ca2W3 square pyramids, corners with five equivalent O(2)Ca2W2 tetrahedra, edges with three equivalent O(3)Ca2W4 octahedra, edges with five equivalent O(1)Ca2W3 square pyramids, and  an edgeedge with one O(2)Ca2W2 tetrahedra. The corner-sharing octahedral tilt angles range from 8-43°. In the second O site, O(2) is bonded to two equivalent Ca(1) and two equivalent W(1) atoms to form OCa2W2 tetrahedra that share corners with ten equivalent O(1)Ca2W3 square pyramids, corners with two equivalent O(2)Ca2W2 tetrahedra, edges with four equivalent O(3)Ca2W4 octahedra, and edges with two equivalent O(1)Ca2W3 square pyramids. In the third O site, O(3) is bonded to two equivalent Ca(1) and four equivalent W(1) atoms to form OCa2W4 octahedra that share corners with two equivalent O(3)Ca2W4 octahedra, corners with eight equivalent O(1)Ca2W3 square pyramids, edges with two equivalent O(3)Ca2W4 octahedra, edges with six equivalent O(1)Ca2W3 square pyramids, and edges with four equivalent O(2)Ca2W2 tetrahedra. The corner-sharing octahedral tilt angles are 50°.