CaCu3(WO3)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent W(3)O6 octahedra, and faces with two equivalent W(4)O6 octahedra. There are four inequivalent W sites. In the first W site, W(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. In the third W site, W(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. In the fourth W site, W(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one W(2), one W(4), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the second O site, O(2) is bonded to one Ca(1), one W(1), one W(3), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the third O site, O(3) is bonded to one Ca(1), one W(2), one W(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the fourth O site, O(4) is bonded to one Ca(1), one W(3), one W(4), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the fifth O site, O(5) is bonded to one Ca(1), one W(1), one W(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the sixth O site, O(6) is bonded to one Ca(1), one W(1), one W(4), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra.
CaCu3(WO3)4 crystallizes in the triclinic P-1 space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent W(3)O6 octahedra, and faces with two equivalent W(4)O6 octahedra. Both Ca(1)-O(1) bond lengths are 2.68 Å. Both Ca(1)-O(2) bond lengths are 2.68 Å. Both Ca(1)-O(3) bond lengths are 2.68 Å. Both Ca(1)-O(4) bond lengths are 2.69 Å. Both Ca(1)-O(5) bond lengths are 2.69 Å. Both Ca(1)-O(6) bond lengths are 2.66 Å. There are four inequivalent W sites. In the first W site, W(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. Both W(1)-O(2) bond lengths are 2.04 Å. Both W(1)-O(5) bond lengths are 2.05 Å. Both W(1)-O(6) bond lengths are 1.96 Å. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. Both W(2)-O(1) bond lengths are 2.04 Å. Both W(2)-O(3) bond lengths are 1.96 Å. Both W(2)-O(5) bond lengths are 2.05 Å. In the third W site, W(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. Both W(3)-O(2) bond lengths are 2.05 Å. Both W(3)-O(3) bond lengths are 2.13 Å. Both W(3)-O(4) bond lengths are 2.05 Å. In the fourth W site, W(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-39°. Both W(4)-O(1) bond lengths are 2.06 Å. Both W(4)-O(4) bond lengths are 2.05 Å. Both W(4)-O(6) bond lengths are 2.12 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Cu(1)-O(3) bond lengths are 2.11 Å. Both Cu(1)-O(6) bond lengths are 2.12 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(2)-O(1) bond lengths are 2.07 Å. Both Cu(2)-O(2) bond lengths are 2.10 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Cu(3)-O(4) bond lengths are 2.07 Å. Both Cu(3)-O(5) bond lengths are 2.07 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one W(2), one W(4), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the second O site, O(2) is bonded to one Ca(1), one W(1), one W(3), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the third O site, O(3) is bonded to one Ca(1), one W(2), one W(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the fourth O site, O(4) is bonded to one Ca(1), one W(3), one W(4), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the fifth O site, O(5) is bonded to one Ca(1), one W(1), one W(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra. In the sixth O site, O(6) is bonded to one Ca(1), one W(1), one W(4), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuW2 tetrahedra.