Al23V4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Al(3) and six equivalent Al(4) atoms to form VAl12 cuboctahedra that share corners with six equivalent V(2)Al10V2 cuboctahedra, edges with six equivalent Al(1)Al9V3 cuboctahedra, and edges with twelve equivalent Al(5)Al10V2 cuboctahedra. In the second V site, V(2) is bonded to two equivalent V(2), two equivalent Al(1), two equivalent Al(2), two equivalent Al(4), and four equivalent Al(5) atoms to form distorted VAl10V2 cuboctahedra that share corners with two equivalent V(2)Al10V2 cuboctahedra, corners with two equivalent V(1)Al12 cuboctahedra, corners with four equivalent Al(5)Al10V2 cuboctahedra, edges with four equivalent Al(5)Al10V2 cuboctahedra, faces with two equivalent V(2)Al10V2 cuboctahedra, faces with two equivalent Al(1)Al9V3 cuboctahedra, and faces with six equivalent Al(5)Al10V2 cuboctahedra. There are five inequivalent Al sites. In the first Al site, Al(1) is bonded to three equivalent V(2), three equivalent Al(3), three equivalent Al(4), and three equivalent Al(5) atoms to form distorted AlAl9V3 cuboctahedra that share corners with six equivalent Al(5)Al10V2 cuboctahedra, edges with three equivalent V(1)Al12 cuboctahedra, edges with three equivalent Al(5)Al10V2 cuboctahedra,  a faceface with one Al(1)Al9V3 cuboctahedra, faces with three equivalent V(2)Al10V2 cuboctahedra, and faces with six equivalent Al(5)Al10V2 cuboctahedra. In the second Al site, Al(5) is bonded to two equivalent V(2), one Al(1), two equivalent Al(2), two equivalent Al(3), two equivalent Al(4), and three equivalent Al(5) atoms to form distorted AlAl10V2 cuboctahedra that share corners with two equivalent V(2)Al10V2 cuboctahedra, corners with two equivalent Al(5)Al10V2 cuboctahedra, corners with two equivalent Al(1)Al9V3 cuboctahedra,  an edgeedge with one Al(1)Al9V3 cuboctahedra, edges with two equivalent V(2)Al10V2 cuboctahedra, edges with two equivalent V(1)Al12 cuboctahedra, faces with two equivalent Al(1)Al9V3 cuboctahedra, faces with three equivalent V(2)Al10V2 cuboctahedra, and faces with seven equivalent Al(5)Al10V2 cuboctahedra. In the third Al site, Al(2) is bonded in a 12-coordinate geometry to two equivalent V(2), two equivalent Al(2), four equivalent Al(4), and four equivalent Al(5) atoms. In the fourth Al site, Al(3) is bonded in a 11-coordinate geometry to one V(1), one Al(1), two equivalent Al(5), three equivalent Al(4), and four equivalent Al(3) atoms. In the fifth Al site, Al(4) is bonded in a 12-coordinate geometry to one V(1), one V(2), one Al(1), two equivalent Al(2), two equivalent Al(4), two equivalent Al(5), and three equivalent Al(3) atoms.
Al23V4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent Al(3) and six equivalent Al(4) atoms to form VAl12 cuboctahedra that share corners with six equivalent V(2)Al10V2 cuboctahedra, edges with six equivalent Al(1)Al9V3 cuboctahedra, and edges with twelve equivalent Al(5)Al10V2 cuboctahedra. All V(1)-Al(3) bond lengths are 2.82 Å. All V(1)-Al(4) bond lengths are 2.57 Å. In the second V site, V(2) is bonded to two equivalent V(2), two equivalent Al(1), two equivalent Al(2), two equivalent Al(4), and four equivalent Al(5) atoms to form distorted VAl10V2 cuboctahedra that share corners with two equivalent V(2)Al10V2 cuboctahedra, corners with two equivalent V(1)Al12 cuboctahedra, corners with four equivalent Al(5)Al10V2 cuboctahedra, edges with four equivalent Al(5)Al10V2 cuboctahedra, faces with two equivalent V(2)Al10V2 cuboctahedra, faces with two equivalent Al(1)Al9V3 cuboctahedra, and faces with six equivalent Al(5)Al10V2 cuboctahedra. Both V(2)-V(2) bond lengths are 2.60 Å. Both V(2)-Al(1) bond lengths are 2.73 Å. Both V(2)-Al(2) bond lengths are 2.52 Å. Both V(2)-Al(4) bond lengths are 2.58 Å. All V(2)-Al(5) bond lengths are 2.77 Å. There are five inequivalent Al sites. In the first Al site, Al(1) is bonded to three equivalent V(2), three equivalent Al(3), three equivalent Al(4), and three equivalent Al(5) atoms to form distorted AlAl9V3 cuboctahedra that share corners with six equivalent Al(5)Al10V2 cuboctahedra, edges with three equivalent V(1)Al12 cuboctahedra, edges with three equivalent Al(5)Al10V2 cuboctahedra,  a faceface with one Al(1)Al9V3 cuboctahedra, faces with three equivalent V(2)Al10V2 cuboctahedra, and faces with six equivalent Al(5)Al10V2 cuboctahedra. All Al(1)-Al(3) bond lengths are 2.94 Å. All Al(1)-Al(4) bond lengths are 2.75 Å. All Al(1)-Al(5) bond lengths are 2.87 Å. In the second Al site, Al(5) is bonded to two equivalent V(2), one Al(1), two equivalent Al(2), two equivalent Al(3), two equivalent Al(4), and three equivalent Al(5) atoms to form distorted AlAl10V2 cuboctahedra that share corners with two equivalent V(2)Al10V2 cuboctahedra, corners with two equivalent Al(5)Al10V2 cuboctahedra, corners with two equivalent Al(1)Al9V3 cuboctahedra,  an edgeedge with one Al(1)Al9V3 cuboctahedra, edges with two equivalent V(2)Al10V2 cuboctahedra, edges with two equivalent V(1)Al12 cuboctahedra, faces with two equivalent Al(1)Al9V3 cuboctahedra, faces with three equivalent V(2)Al10V2 cuboctahedra, and faces with seven equivalent Al(5)Al10V2 cuboctahedra. Both Al(5)-Al(2) bond lengths are 2.78 Å. Both Al(5)-Al(3) bond lengths are 2.83 Å. Both Al(5)-Al(4) bond lengths are 2.87 Å. There is one shorter (2.83 Å) and two longer (2.87 Å) Al(5)-Al(5) bond lengths. In the third Al site, Al(2) is bonded in a 12-coordinate geometry to two equivalent V(2), two equivalent Al(2), four equivalent Al(4), and four equivalent Al(5) atoms. Both Al(2)-Al(2) bond lengths are 2.88 Å. All Al(2)-Al(4) bond lengths are 2.80 Å. In the fourth Al site, Al(3) is bonded in a 11-coordinate geometry to one V(1), one Al(1), two equivalent Al(5), three equivalent Al(4), and four equivalent Al(3) atoms. There is one shorter (2.72 Å) and two longer (2.83 Å) Al(3)-Al(4) bond lengths. There are two shorter (2.81 Å) and two longer (2.95 Å) Al(3)-Al(3) bond lengths. In the fifth Al site, Al(4) is bonded in a 12-coordinate geometry to one V(1), one V(2), one Al(1), two equivalent Al(2), two equivalent Al(4), two equivalent Al(5), and three equivalent Al(3) atoms. Both Al(4)-Al(4) bond lengths are 2.85 Å.