Al(V4Sn)3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 14-coordinate geometry to one V(1), one V(2), four equivalent V(3), four equivalent V(4), two equivalent Al(1), and two equivalent Sn(2) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one V(1), one V(2), two equivalent Sn(1), and two equivalent Sn(2) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent V(3), two equivalent V(4), one Al(1), one Sn(1), and two equivalent Sn(2) atoms. In the fourth V site, V(4) is bonded in a 14-coordinate geometry to two equivalent V(4), four equivalent V(1), four equivalent V(3), two equivalent Al(1), and two equivalent Sn(2) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to two equivalent V(5), two equivalent Sn(1), and two equivalent Sn(2) atoms. Al(1) is bonded to four equivalent V(1), four equivalent V(3), and four equivalent V(4) atoms to form AlV12 cuboctahedra that share edges with two equivalent Sn(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Sn(2)V12 cuboctahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form SnV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Sn(1)V12 cuboctahedra, and faces with eight equivalent Sn(2)V12 cuboctahedra. In the second Sn site, Sn(2) is bonded to two equivalent V(1), two equivalent V(2), two equivalent V(4), two equivalent V(5), and four equivalent V(3) atoms to form SnV12 cuboctahedra that share edges with six equivalent Sn(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Sn(1)V12 cuboctahedra.
Al(V4Sn)3 crystallizes in the orthorhombic Pmmm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 14-coordinate geometry to one V(1), one V(2), four equivalent V(3), four equivalent V(4), two equivalent Al(1), and two equivalent Sn(2) atoms. The V(1)-V(1) bond length is 2.31 Å. The V(1)-V(2) bond length is 2.52 Å. All V(1)-V(3) bond lengths are 2.98 Å. All V(1)-V(4) bond lengths are 3.01 Å. Both V(1)-Al(1) bond lengths are 2.71 Å. Both V(1)-Sn(2) bond lengths are 2.77 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one V(1), one V(2), two equivalent Sn(1), and two equivalent Sn(2) atoms. The V(2)-V(2) bond length is 2.47 Å. Both V(2)-Sn(1) bond lengths are 2.75 Å. Both V(2)-Sn(2) bond lengths are 2.74 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to two equivalent V(1), two equivalent V(3), two equivalent V(4), one Al(1), one Sn(1), and two equivalent Sn(2) atoms. There is one shorter (2.37 Å) and one longer (2.53 Å) V(3)-V(3) bond length. Both V(3)-V(4) bond lengths are 2.92 Å. The V(3)-Al(1) bond length is 2.65 Å. The V(3)-Sn(1) bond length is 2.80 Å. Both V(3)-Sn(2) bond lengths are 2.76 Å. In the fourth V site, V(4) is bonded in a 14-coordinate geometry to two equivalent V(4), four equivalent V(1), four equivalent V(3), two equivalent Al(1), and two equivalent Sn(2) atoms. There is one shorter (2.28 Å) and one longer (2.62 Å) V(4)-V(4) bond length. Both V(4)-Al(1) bond lengths are 2.70 Å. Both V(4)-Sn(2) bond lengths are 2.77 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to two equivalent V(5), two equivalent Sn(1), and two equivalent Sn(2) atoms. There is one shorter (2.40 Å) and one longer (2.50 Å) V(5)-V(5) bond length. Both V(5)-Sn(1) bond lengths are 2.75 Å. Both V(5)-Sn(2) bond lengths are 2.75 Å. Al(1) is bonded to four equivalent V(1), four equivalent V(3), and four equivalent V(4) atoms to form AlV12 cuboctahedra that share edges with two equivalent Sn(1)V12 cuboctahedra, edges with four equivalent Al(1)V12 cuboctahedra, and faces with eight equivalent Sn(2)V12 cuboctahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to four equivalent V(2), four equivalent V(3), and four equivalent V(5) atoms to form SnV12 cuboctahedra that share edges with two equivalent Al(1)V12 cuboctahedra, edges with four equivalent Sn(1)V12 cuboctahedra, and faces with eight equivalent Sn(2)V12 cuboctahedra. In the second Sn site, Sn(2) is bonded to two equivalent V(1), two equivalent V(2), two equivalent V(4), two equivalent V(5), and four equivalent V(3) atoms to form SnV12 cuboctahedra that share edges with six equivalent Sn(2)V12 cuboctahedra, faces with four equivalent Al(1)V12 cuboctahedra, and faces with four equivalent Sn(1)V12 cuboctahedra.