Al3(V3C2)4 crystallizes in the hexagonal P6_3/mcm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent C(2) and three equivalent C(1) atoms to form a mixture of corner and edge-sharing VC5 square pyramids. In the second V site, V(2) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent C(1) atoms. In the third V site, V(3) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent C(1) atoms. Al(1) is bonded to two equivalent V(2), four equivalent V(3), and six equivalent Al(1) atoms to form AlAl6V6 cuboctahedra that share corners with six equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent C(1)V6 octahedra, edges with six equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent C(1)V6 octahedra, and faces with six equivalent Al(1)Al6V6 cuboctahedra. The corner-sharing octahedral tilt angles range from 18-21°. There are two inequivalent C sites. In the first C site, C(2) is bonded to six equivalent V(1) atoms to form a mixture of corner and edge-sharing CV6 octahedra. The corner-sharing octahedral tilt angles are 6°. In the second C site, C(1) is bonded to one V(2), two equivalent V(3), and three equivalent V(1) atoms to form CV6 octahedra that share corners with three equivalent Al(1)Al6V6 cuboctahedra, corners with two equivalent C(2)V6 octahedra, edges with three equivalent Al(1)Al6V6 cuboctahedra, edges with two equivalent C(2)V6 octahedra, and edges with six equivalent C(1)V6 octahedra. The corner-sharing octahedral tilt angles are 6°.
Al3(V3C2)4 crystallizes in the hexagonal P6_3/mcm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent C(2) and three equivalent C(1) atoms to form a mixture of corner and edge-sharing VC5 square pyramids. Both V(1)-C(2) bond lengths are 2.04 Å. There is one shorter (1.97 Å) and two longer (2.10 Å) V(1)-C(1) bond lengths. In the second V site, V(2) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent C(1) atoms. All V(2)-Al(1) bond lengths are 2.75 Å. All V(2)-C(1) bond lengths are 1.98 Å. In the third V site, V(3) is bonded in a 3-coordinate geometry to three equivalent Al(1) and three equivalent C(1) atoms. All V(3)-Al(1) bond lengths are 2.71 Å. All V(3)-C(1) bond lengths are 2.02 Å. Al(1) is bonded to two equivalent V(2), four equivalent V(3), and six equivalent Al(1) atoms to form AlAl6V6 cuboctahedra that share corners with six equivalent Al(1)Al6V6 cuboctahedra, corners with six equivalent C(1)V6 octahedra, edges with six equivalent Al(1)Al6V6 cuboctahedra, edges with six equivalent C(1)V6 octahedra, and faces with six equivalent Al(1)Al6V6 cuboctahedra. The corner-sharing octahedral tilt angles range from 18-21°. There are two shorter (2.87 Å) and four longer (2.93 Å) Al(1)-Al(1) bond lengths. There are two inequivalent C sites. In the first C site, C(2) is bonded to six equivalent V(1) atoms to form a mixture of corner and edge-sharing CV6 octahedra. The corner-sharing octahedral tilt angles are 6°. In the second C site, C(1) is bonded to one V(2), two equivalent V(3), and three equivalent V(1) atoms to form CV6 octahedra that share corners with three equivalent Al(1)Al6V6 cuboctahedra, corners with two equivalent C(2)V6 octahedra, edges with three equivalent Al(1)Al6V6 cuboctahedra, edges with two equivalent C(2)V6 octahedra, and edges with six equivalent C(1)V6 octahedra. The corner-sharing octahedral tilt angles are 6°.