CaCu3(MoO3)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 Mo(1)O6 octahedra, faces with two equivalent Mo(2)O6 octahedra, faces with two equivalent Mo(3)O6 octahedra, and faces with two equivalent Mo(4)O6 octahedra. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. In the second Mo site, Mo(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. In the third Mo site, Mo(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. In the fourth Mo site, Mo(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. 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 Mo(2), one Mo(4), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the second O site, O(2) is bonded to one Ca(1), one Mo(1), one Mo(3), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the third O site, O(3) is bonded to one Ca(1), one Mo(2), one Mo(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the fourth O site, O(4) is bonded to one Ca(1), one Mo(3), one Mo(4), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the fifth O site, O(5) is bonded to one Ca(1), one Mo(1), one Mo(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the sixth O site, O(6) is bonded to one Ca(1), one Mo(1), one Mo(4), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra.
CaCu3(MoO3)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 Mo(1)O6 octahedra, faces with two equivalent Mo(2)O6 octahedra, faces with two equivalent Mo(3)O6 octahedra, and faces with two equivalent Mo(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 2.68 Å. Both Ca(1)-O(6) bond lengths are 2.69 Å. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. Both Mo(1)-O(2) bond lengths are 2.06 Å. Both Mo(1)-O(5) bond lengths are 2.06 Å. Both Mo(1)-O(6) bond lengths are 2.06 Å. In the second Mo site, Mo(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. Both Mo(2)-O(1) bond lengths are 2.10 Å. Both Mo(2)-O(3) bond lengths are 2.02 Å. Both Mo(2)-O(5) bond lengths are 2.06 Å. In the third Mo site, Mo(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(4)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. Both Mo(3)-O(2) bond lengths are 2.06 Å. Both Mo(3)-O(3) bond lengths are 2.10 Å. Both Mo(3)-O(4) bond lengths are 2.02 Å. In the fourth Mo site, Mo(4) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra, and faces with two equivalent Ca(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 42°. Both Mo(4)-O(1) bond lengths are 2.02 Å. Both Mo(4)-O(4) bond lengths are 2.10 Å. Both Mo(4)-O(6) bond lengths are 2.06 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 2.00 Å. Both Cu(1)-O(6) bond lengths are 1.99 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 2.00 Å. Both Cu(2)-O(2) bond lengths are 1.99 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 2.00 Å. Both Cu(3)-O(5) bond lengths are 1.99 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Mo(2), one Mo(4), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the second O site, O(2) is bonded to one Ca(1), one Mo(1), one Mo(3), and one Cu(2) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the third O site, O(3) is bonded to one Ca(1), one Mo(2), one Mo(3), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the fourth O site, O(4) is bonded to one Ca(1), one Mo(3), one Mo(4), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the fifth O site, O(5) is bonded to one Ca(1), one Mo(1), one Mo(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra. In the sixth O site, O(6) is bonded to one Ca(1), one Mo(1), one Mo(4), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OCaCuMo2 tetrahedra.