CaW5O7 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(3), and three equivalent O(1) atoms. In the second W site, W(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the third W site, W(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form distorted edge-sharing WO6 octahedra. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 6-coordinate geometry to one Ca(1), one W(3), two equivalent W(1), and two equivalent W(2) atoms. In the second O site, O(4) is bonded to two equivalent Ca(1) and two equivalent W(2) atoms to form OCa2W2 tetrahedra that share corners with eight equivalent O(2)Ca2W3 square pyramids, corners with two equivalent O(4)Ca2W2 tetrahedra, and edges with two equivalent O(2)Ca2W3 square pyramids. In the third O site, O(1) is bonded in a 6-coordinate geometry to one W(2), two equivalent W(3), and three equivalent W(1) atoms. In the fourth O site, O(2) is bonded to two equivalent Ca(1), one W(1), and two equivalent W(2) atoms to form distorted OCa2W3 square pyramids that share corners with two equivalent O(2)Ca2W3 square pyramids, corners with four equivalent O(4)Ca2W2 tetrahedra, edges with three equivalent O(2)Ca2W3 square pyramids, and  an edgeedge with one O(4)Ca2W2 tetrahedra.
CaW5O7 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. Both Ca(1)-O(3) bond lengths are 2.34 Å. Both Ca(1)-O(4) bond lengths are 2.35 Å. All Ca(1)-O(2) bond lengths are 2.62 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(3), and three equivalent O(1) atoms. The W(1)-O(2) bond length is 2.24 Å. Both W(1)-O(3) bond lengths are 2.25 Å. There are two shorter (2.12 Å) and one longer (2.25 Å) W(1)-O(1) bond length. In the second W site, W(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles are 51°. The W(2)-O(1) bond length is 2.40 Å. The W(2)-O(4) bond length is 2.13 Å. Both W(2)-O(2) bond lengths are 2.19 Å. Both W(2)-O(3) bond lengths are 2.33 Å. In the third W site, W(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form distorted edge-sharing WO6 octahedra. Both W(3)-O(3) bond lengths are 2.73 Å. All W(3)-O(1) bond lengths are 2.83 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 6-coordinate geometry to one Ca(1), one W(3), two equivalent W(1), and two equivalent W(2) atoms. In the second O site, O(4) is bonded to two equivalent Ca(1) and two equivalent W(2) atoms to form OCa2W2 tetrahedra that share corners with eight equivalent O(2)Ca2W3 square pyramids, corners with two equivalent O(4)Ca2W2 tetrahedra, and edges with two equivalent O(2)Ca2W3 square pyramids. In the third O site, O(1) is bonded in a 6-coordinate geometry to one W(2), two equivalent W(3), and three equivalent W(1) atoms. In the fourth O site, O(2) is bonded to two equivalent Ca(1), one W(1), and two equivalent W(2) atoms to form distorted OCa2W3 square pyramids that share corners with two equivalent O(2)Ca2W3 square pyramids, corners with four equivalent O(4)Ca2W2 tetrahedra, edges with three equivalent O(2)Ca2W3 square pyramids, and  an edgeedge with one O(4)Ca2W2 tetrahedra.