V3AlO6 is beta indium sulfide-derived structured and crystallizes in the trigonal P-3m1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Al(1)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. In the third V site, V(3) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. In the fourth V site, V(4) is bonded to six equivalent O(6) atoms to form VO6 octahedra that share corners with six equivalent Al(2)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(5) atoms to form AlO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. In the second Al site, Al(2) is bonded to one O(3) and three equivalent O(6) atoms to form AlO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Al(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to three equivalent V(1) and one Al(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one Al(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(4), two equivalent V(1), and one Al(2) atom.
V3AlO6 is beta indium sulfide-derived structured and crystallizes in the trigonal P-3m1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Al(1)O4 tetrahedra, corners with three equivalent Al(2)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(1) bond length is 2.11 Å. The V(1)-O(3) bond length is 2.14 Å. Both V(1)-O(4) bond lengths are 1.93 Å. Both V(1)-O(6) bond lengths are 2.14 Å. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Al(1)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. Both V(2)-O(2) bond lengths are 1.95 Å. All V(2)-O(5) bond lengths are 2.13 Å. In the third V site, V(3) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent Al(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. All V(3)-O(4) bond lengths are 1.99 Å. All V(3)-O(5) bond lengths are 2.12 Å. In the fourth V site, V(4) is bonded to six equivalent O(6) atoms to form VO6 octahedra that share corners with six equivalent Al(2)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. All V(4)-O(6) bond lengths are 2.07 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1) and three equivalent O(5) atoms to form AlO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. The Al(1)-O(1) bond length is 1.81 Å. All Al(1)-O(5) bond lengths are 1.84 Å. In the second Al site, Al(2) is bonded to one O(3) and three equivalent O(6) atoms to form AlO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-57°. The Al(2)-O(3) bond length is 1.79 Å. All Al(2)-O(6) bond lengths are 1.84 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one Al(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(2) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to three equivalent V(1) and one Al(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one Al(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(4), two equivalent V(1), and one Al(2) atom.