V4AlN3 is MAX Phase-like structured and 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 three equivalent N(1) and three equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing VN6 pentagonal pyramids. In the second V site, V(2) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent N(2) atoms. Al(1) is bonded to six equivalent V(2) and six equivalent Al(1) atoms to form AlAl6V6 cuboctahedra that share corners with six equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent N(2)V6 octahedra, edges with six equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent N(2)V6 octahedra, and faces with six equivalent Al(1)Al6V6 cuboctahedra. The corner-sharing octahedral tilt angles are 16°. There are two inequivalent N sites. In the first N site, N(1) is bonded to six equivalent V(1) atoms to form a mixture of corner, face, and edge-sharing NV6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the second N site, N(2) is bonded to three equivalent V(1) and three equivalent V(2) atoms to form NV6 octahedra that share corners with three equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent N(1)V6 octahedra, edges with three equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent N(2)V6 octahedra, and  a faceface with one N(1)V6 octahedra. The corner-sharing octahedral tilt angles are 46°.
V4AlN3 is MAX Phase-like structured and 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 three equivalent N(1) and three equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing VN6 pentagonal pyramids. All V(1)-N(1) bond lengths are 2.07 Å. All V(1)-N(2) bond lengths are 2.06 Å. In the second V site, V(2) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent N(2) atoms. All V(2)-Al(1) bond lengths are 2.68 Å. All V(2)-N(2) bond lengths are 2.03 Å. Al(1) is bonded to six equivalent V(2) and six equivalent Al(1) atoms to form AlAl6V6 cuboctahedra that share corners with six equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent N(2)V6 octahedra, edges with six equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent N(2)V6 octahedra, and faces with six equivalent Al(1)Al6V6 cuboctahedra. The corner-sharing octahedral tilt angles are 16°. All Al(1)-Al(1) bond lengths are 2.80 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to six equivalent V(1) atoms to form a mixture of corner, face, and edge-sharing NV6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the second N site, N(2) is bonded to three equivalent V(1) and three equivalent V(2) atoms to form NV6 octahedra that share corners with three equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent N(1)V6 octahedra, edges with three equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent N(2)V6 octahedra, and  a faceface with one N(1)V6 octahedra. The corner-sharing octahedral tilt angles are 46°.