Al14Ca13 crystallizes in the monoclinic C2/m space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one Al(1), one Al(2), one Al(5), one Al(6), two equivalent Al(3), and two equivalent Al(4) atoms. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one Al(2), one Al(3), one Al(4), one Al(5), one Al(6), and two equivalent Al(1) atoms. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one Al(4), two equivalent Al(2), two equivalent Al(6), and four equivalent Al(1) atoms. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to one Al(3), one Al(4), two equivalent Al(5), two equivalent Al(6), and four equivalent Al(1) atoms. In the fifth Ca site, Ca(5) is bonded in a distorted square co-planar geometry to two equivalent Al(2) and two equivalent Al(5) atoms. There are six inequivalent Al sites. In the first Al site, Al(3) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(2), four equivalent Ca(1), one Al(4), and two equivalent Al(1) atoms. In the second Al site, Al(4) is bonded in a 11-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(2), four equivalent Ca(1), one Al(3), and two equivalent Al(5) atoms. In the third Al site, Al(5) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(4), one Al(5), and two equivalent Al(4) atoms. In the fourth Al site, Al(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), two equivalent Ca(4), two equivalent Al(1), and two equivalent Al(2) atoms to form a mixture of distorted edge and face-sharing AlCa8Al4 cuboctahedra. In the fifth Al site, Al(1) is bonded in a 10-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), two equivalent Ca(4), one Al(1), one Al(3), and one Al(6) atom. In the sixth Al site, Al(2) is bonded in a 9-coordinate geometry to one Ca(5), two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and two equivalent Al(6) atoms.
Al14Ca13 crystallizes in the monoclinic C2/m space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one Al(1), one Al(2), one Al(5), one Al(6), two equivalent Al(3), and two equivalent Al(4) atoms. The Ca(1)-Al(1) bond length is 3.23 Å. The Ca(1)-Al(2) bond length is 3.20 Å. The Ca(1)-Al(5) bond length is 3.30 Å. The Ca(1)-Al(6) bond length is 3.57 Å. There is one shorter (3.30 Å) and one longer (3.45 Å) Ca(1)-Al(3) bond length. There is one shorter (3.48 Å) and one longer (3.49 Å) Ca(1)-Al(4) bond length. In the second Ca site, Ca(2) is bonded in a 7-coordinate geometry to one Al(2), one Al(3), one Al(4), one Al(5), one Al(6), and two equivalent Al(1) atoms. The Ca(2)-Al(2) bond length is 3.26 Å. The Ca(2)-Al(3) bond length is 3.28 Å. The Ca(2)-Al(4) bond length is 3.49 Å. The Ca(2)-Al(5) bond length is 3.13 Å. The Ca(2)-Al(6) bond length is 3.51 Å. There is one shorter (3.13 Å) and one longer (3.26 Å) Ca(2)-Al(1) bond length. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one Al(4), two equivalent Al(2), two equivalent Al(6), and four equivalent Al(1) atoms. The Ca(3)-Al(4) bond length is 3.42 Å. There is one shorter (3.21 Å) and one longer (3.28 Å) Ca(3)-Al(2) bond length. Both Ca(3)-Al(6) bond lengths are 3.63 Å. There are two shorter (3.43 Å) and two longer (3.64 Å) Ca(3)-Al(1) bond lengths. In the fourth Ca site, Ca(4) is bonded in a 9-coordinate geometry to one Al(3), one Al(4), two equivalent Al(5), two equivalent Al(6), and four equivalent Al(1) atoms. The Ca(4)-Al(3) bond length is 3.48 Å. The Ca(4)-Al(4) bond length is 3.60 Å. Both Ca(4)-Al(5) bond lengths are 3.23 Å. Both Ca(4)-Al(6) bond lengths are 3.33 Å. There are two shorter (3.24 Å) and two longer (3.37 Å) Ca(4)-Al(1) bond lengths. In the fifth Ca site, Ca(5) is bonded in a distorted square co-planar geometry to two equivalent Al(2) and two equivalent Al(5) atoms. Both Ca(5)-Al(2) bond lengths are 3.34 Å. Both Ca(5)-Al(5) bond lengths are 3.49 Å. There are six inequivalent Al sites. In the first Al site, Al(3) is bonded in a 10-coordinate geometry to one Ca(4), two equivalent Ca(2), four equivalent Ca(1), one Al(4), and two equivalent Al(1) atoms. The Al(3)-Al(4) bond length is 2.83 Å. Both Al(3)-Al(1) bond lengths are 2.77 Å. In the second Al site, Al(4) is bonded in a 11-coordinate geometry to one Ca(3), one Ca(4), two equivalent Ca(2), four equivalent Ca(1), one Al(3), and two equivalent Al(5) atoms. Both Al(4)-Al(5) bond lengths are 2.74 Å. In the third Al site, Al(5) is bonded in a 10-coordinate geometry to one Ca(5), two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(4), one Al(5), and two equivalent Al(4) atoms. The Al(5)-Al(5) bond length is 2.84 Å. In the fourth Al site, Al(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), two equivalent Ca(4), two equivalent Al(1), and two equivalent Al(2) atoms to form a mixture of distorted edge and face-sharing AlCa8Al4 cuboctahedra. Both Al(6)-Al(1) bond lengths are 2.70 Å. Both Al(6)-Al(2) bond lengths are 2.68 Å. In the fifth Al site, Al(1) is bonded in a 10-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Ca(3), two equivalent Ca(4), one Al(1), one Al(3), and one Al(6) atom. The Al(1)-Al(1) bond length is 2.64 Å. In the sixth Al site, Al(2) is bonded in a 9-coordinate geometry to one Ca(5), two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and two equivalent Al(6) atoms.