BaCa(WO2)4 crystallizes in the trigonal P-31m space group. Ba(1) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted BaO12 cuboctahedra that share edges with six equivalent Ba(1)O12 cuboctahedra, edges with twelve equivalent W(1)O4 trigonal pyramids, and faces with two equivalent Ca(1)O6 octahedra. Ca(1) is bonded to six equivalent O(1) atoms to form CaO6 octahedra that share corners with twelve equivalent W(1)O4 trigonal pyramids and faces with two equivalent Ba(1)O12 cuboctahedra. W(1) is bonded to one O(2) and three equivalent O(1) atoms to form WO4 trigonal pyramids that share corners with three equivalent Ca(1)O6 octahedra, corners with four equivalent W(1)O4 trigonal pyramids, and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 62°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ca(1), and two equivalent W(1) atoms to form a mixture of distorted edge and corner-sharing OBaCaW2 tetrahedra. In the second O site, O(2) is bonded in a linear geometry to three equivalent Ba(1) and two equivalent W(1) atoms.
BaCa(WO2)4 crystallizes in the trigonal P-31m space group. Ba(1) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted BaO12 cuboctahedra that share edges with six equivalent Ba(1)O12 cuboctahedra, edges with twelve equivalent W(1)O4 trigonal pyramids, and faces with two equivalent Ca(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 2.84 Å. All Ba(1)-O(2) bond lengths are 3.39 Å. Ca(1) is bonded to six equivalent O(1) atoms to form CaO6 octahedra that share corners with twelve equivalent W(1)O4 trigonal pyramids and faces with two equivalent Ba(1)O12 cuboctahedra. All Ca(1)-O(1) bond lengths are 2.36 Å. W(1) is bonded to one O(2) and three equivalent O(1) atoms to form WO4 trigonal pyramids that share corners with three equivalent Ca(1)O6 octahedra, corners with four equivalent W(1)O4 trigonal pyramids, and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 62°. The W(1)-O(2) bond length is 2.06 Å. All W(1)-O(1) bond lengths are 2.06 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ca(1), and two equivalent W(1) atoms to form a mixture of distorted edge and corner-sharing OBaCaW2 tetrahedra. In the second O site, O(2) is bonded in a linear geometry to three equivalent Ba(1) and two equivalent W(1) atoms.