Ca3GdAl8 is Hexagonal Laves-derived structured and crystallizes in the trigonal R3m space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 12-coordinate geometry to one Ca(3), three equivalent Ca(2), three equivalent Al(1), three equivalent Al(4), and six equivalent Al(2) atoms. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Ca(1), one Gd(1), three equivalent Al(2), three equivalent Al(4), and six equivalent Al(1) atoms. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to one Ca(1), three equivalent Gd(1), three equivalent Al(1), three equivalent Al(3), and six equivalent Al(2) atoms. Gd(1) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(3), three equivalent Al(2), three equivalent Al(3), and six equivalent Al(1) atoms. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), two equivalent Gd(1), one Al(3), one Al(4), and four equivalent Al(1) atoms to form AlCa4Gd2Al6 cuboctahedra that share corners with two equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with two equivalent Al(4)Ca6Al6 cuboctahedra, corners with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with ten equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with two equivalent Al(1)Ca4Gd2Al6 cuboctahedra, edges with four equivalent Al(2)Ca5GdAl6 cuboctahedra, faces with three equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with three equivalent Al(4)Ca6Al6 cuboctahedra, faces with four equivalent Al(2)Ca5GdAl6 cuboctahedra, and faces with eight equivalent Al(1)Ca4Gd2Al6 cuboctahedra. In the second Al site, Al(2) is bonded to one Ca(2), two equivalent Ca(1), two equivalent Ca(3), one Gd(1), one Al(3), one Al(4), and four equivalent Al(2) atoms to form AlCa5GdAl6 cuboctahedra that share corners with two equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with two equivalent Al(4)Ca6Al6 cuboctahedra, corners with four equivalent Al(2)Ca5GdAl6 cuboctahedra, corners with ten equivalent Al(1)Ca4Gd2Al6 cuboctahedra, edges with two equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, faces with three equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with three equivalent Al(4)Ca6Al6 cuboctahedra, faces with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with eight equivalent Al(2)Ca5GdAl6 cuboctahedra. In the third Al site, Al(3) is bonded to three equivalent Ca(3), three equivalent Gd(1), three equivalent Al(1), and three equivalent Al(2) atoms to form AlCa3Gd3Al6 cuboctahedra that share corners with six equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with six equivalent Al(2)Ca5GdAl6 cuboctahedra, corners with six equivalent Al(4)Ca6Al6 cuboctahedra, edges with six equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with nine equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with nine equivalent Al(2)Ca5GdAl6 cuboctahedra. In the fourth Al site, Al(4) is bonded to three equivalent Ca(1), three equivalent Ca(2), three equivalent Al(1), and three equivalent Al(2) atoms to form AlCa6Al6 cuboctahedra that share corners with six equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with six equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with six equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with six equivalent Al(4)Ca6Al6 cuboctahedra, faces with nine equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with nine equivalent Al(2)Ca5GdAl6 cuboctahedra.
Ca3GdAl8 is Hexagonal Laves-derived structured and crystallizes in the trigonal R3m space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 12-coordinate geometry to one Ca(3), three equivalent Ca(2), three equivalent Al(1), three equivalent Al(4), and six equivalent Al(2) atoms. The Ca(1)-Ca(3) bond length is 3.44 Å. All Ca(1)-Ca(2) bond lengths are 3.47 Å. All Ca(1)-Al(1) bond lengths are 3.31 Å. All Ca(1)-Al(4) bond lengths are 3.33 Å. All Ca(1)-Al(2) bond lengths are 3.32 Å. In the second Ca site, Ca(2) is bonded in a 16-coordinate geometry to three equivalent Ca(1), one Gd(1), three equivalent Al(2), three equivalent Al(4), and six equivalent Al(1) atoms. The Ca(2)-Gd(1) bond length is 3.44 Å. All Ca(2)-Al(2) bond lengths are 3.31 Å. All Ca(2)-Al(4) bond lengths are 3.33 Å. All Ca(2)-Al(1) bond lengths are 3.32 Å. In the third Ca site, Ca(3) is bonded in a 16-coordinate geometry to one Ca(1), three equivalent Gd(1), three equivalent Al(1), three equivalent Al(3), and six equivalent Al(2) atoms. All Ca(3)-Gd(1) bond lengths are 3.47 Å. All Ca(3)-Al(1) bond lengths are 3.30 Å. All Ca(3)-Al(3) bond lengths are 3.33 Å. All Ca(3)-Al(2) bond lengths are 3.32 Å. Gd(1) is bonded in a 16-coordinate geometry to one Ca(2), three equivalent Ca(3), three equivalent Al(2), three equivalent Al(3), and six equivalent Al(1) atoms. All Gd(1)-Al(2) bond lengths are 3.30 Å. All Gd(1)-Al(3) bond lengths are 3.33 Å. All Gd(1)-Al(1) bond lengths are 3.32 Å. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one Ca(1), one Ca(3), two equivalent Ca(2), two equivalent Gd(1), one Al(3), one Al(4), and four equivalent Al(1) atoms to form AlCa4Gd2Al6 cuboctahedra that share corners with two equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with two equivalent Al(4)Ca6Al6 cuboctahedra, corners with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with ten equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with two equivalent Al(1)Ca4Gd2Al6 cuboctahedra, edges with four equivalent Al(2)Ca5GdAl6 cuboctahedra, faces with three equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with three equivalent Al(4)Ca6Al6 cuboctahedra, faces with four equivalent Al(2)Ca5GdAl6 cuboctahedra, and faces with eight equivalent Al(1)Ca4Gd2Al6 cuboctahedra. The Al(1)-Al(3) bond length is 2.81 Å. The Al(1)-Al(4) bond length is 2.82 Å. All Al(1)-Al(1) bond lengths are 2.84 Å. In the second Al site, Al(2) is bonded to one Ca(2), two equivalent Ca(1), two equivalent Ca(3), one Gd(1), one Al(3), one Al(4), and four equivalent Al(2) atoms to form AlCa5GdAl6 cuboctahedra that share corners with two equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with two equivalent Al(4)Ca6Al6 cuboctahedra, corners with four equivalent Al(2)Ca5GdAl6 cuboctahedra, corners with ten equivalent Al(1)Ca4Gd2Al6 cuboctahedra, edges with two equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, faces with three equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with three equivalent Al(4)Ca6Al6 cuboctahedra, faces with four equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with eight equivalent Al(2)Ca5GdAl6 cuboctahedra. The Al(2)-Al(3) bond length is 2.82 Å. The Al(2)-Al(4) bond length is 2.83 Å. There are two shorter (2.83 Å) and two longer (2.84 Å) Al(2)-Al(2) bond lengths. In the third Al site, Al(3) is bonded to three equivalent Ca(3), three equivalent Gd(1), three equivalent Al(1), and three equivalent Al(2) atoms to form AlCa3Gd3Al6 cuboctahedra that share corners with six equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with six equivalent Al(2)Ca5GdAl6 cuboctahedra, corners with six equivalent Al(4)Ca6Al6 cuboctahedra, edges with six equivalent Al(3)Ca3Gd3Al6 cuboctahedra, faces with nine equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with nine equivalent Al(2)Ca5GdAl6 cuboctahedra. In the fourth Al site, Al(4) is bonded to three equivalent Ca(1), three equivalent Ca(2), three equivalent Al(1), and three equivalent Al(2) atoms to form AlCa6Al6 cuboctahedra that share corners with six equivalent Al(3)Ca3Gd3Al6 cuboctahedra, corners with six equivalent Al(1)Ca4Gd2Al6 cuboctahedra, corners with six equivalent Al(2)Ca5GdAl6 cuboctahedra, edges with six equivalent Al(4)Ca6Al6 cuboctahedra, faces with nine equivalent Al(1)Ca4Gd2Al6 cuboctahedra, and faces with nine equivalent Al(2)Ca5GdAl6 cuboctahedra.