Ca(CrAl10)2 crystallizes in the cubic Fd-3m space group. Ca(1) is bonded in a 16-coordinate geometry to four equivalent Al(3) and twelve equivalent Al(2) atoms. Cr(1) is bonded to six equivalent Al(1) and six equivalent Al(2) atoms to form CrAl12 cuboctahedra that share corners with six equivalent Cr(1)Al12 cuboctahedra, edges with eighteen equivalent Al(2)CaAl10Cr cuboctahedra, and faces with six equivalent Al(2)CaAl10Cr cuboctahedra. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a 12-coordinate geometry to two equivalent Cr(1), four equivalent Al(1), and six equivalent Al(2) atoms. In the second Al site, Al(3) is bonded in a linear geometry to two equivalent Ca(1) and twelve equivalent Al(2) atoms. In the third Al site, Al(2) is bonded to one Ca(1), one Cr(1), two equivalent Al(3), three equivalent Al(1), and five equivalent Al(2) atoms to form distorted AlCaAl10Cr cuboctahedra that share corners with fifteen equivalent Al(2)CaAl10Cr cuboctahedra, edges with two equivalent Al(2)CaAl10Cr cuboctahedra, edges with three equivalent Cr(1)Al12 cuboctahedra,  a faceface with one Cr(1)Al12 cuboctahedra, and faces with fifteen equivalent Al(2)CaAl10Cr cuboctahedra.
Ca(CrAl10)2 crystallizes in the cubic Fd-3m space group. Ca(1) is bonded in a 16-coordinate geometry to four equivalent Al(3) and twelve equivalent Al(2) atoms. All Ca(1)-Al(3) bond lengths are 3.13 Å. All Ca(1)-Al(2) bond lengths are 3.20 Å. Cr(1) is bonded to six equivalent Al(1) and six equivalent Al(2) atoms to form CrAl12 cuboctahedra that share corners with six equivalent Cr(1)Al12 cuboctahedra, edges with eighteen equivalent Al(2)CaAl10Cr cuboctahedra, and faces with six equivalent Al(2)CaAl10Cr cuboctahedra. All Cr(1)-Al(1) bond lengths are 2.56 Å. All Cr(1)-Al(2) bond lengths are 2.79 Å. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded in a 12-coordinate geometry to two equivalent Cr(1), four equivalent Al(1), and six equivalent Al(2) atoms. All Al(1)-Al(1) bond lengths are 2.81 Å. There are two shorter (2.70 Å) and four longer (2.83 Å) Al(1)-Al(2) bond lengths. In the second Al site, Al(3) is bonded in a linear geometry to two equivalent Ca(1) and twelve equivalent Al(2) atoms. All Al(3)-Al(2) bond lengths are 3.09 Å. In the third Al site, Al(2) is bonded to one Ca(1), one Cr(1), two equivalent Al(3), three equivalent Al(1), and five equivalent Al(2) atoms to form distorted AlCaAl10Cr cuboctahedra that share corners with fifteen equivalent Al(2)CaAl10Cr cuboctahedra, edges with two equivalent Al(2)CaAl10Cr cuboctahedra, edges with three equivalent Cr(1)Al12 cuboctahedra,  a faceface with one Cr(1)Al12 cuboctahedra, and faces with fifteen equivalent Al(2)CaAl10Cr cuboctahedra. There are a spread of Al(2)-Al(2) bond distances ranging from 2.70-2.90 Å.