Ba2V3AlO8 crystallizes in the orthorhombic Pmmm space group. Ba(1) is bonded in a 12-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(5), and four equivalent O(4) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(2)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. Al(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent V(1), and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent V(1), and two equivalent Al(1) atoms. In the third O site, O(3) is bonded in a distorted linear geometry to four equivalent Ba(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. In the fifth O site, O(5) is bonded to four equivalent Ba(1) and two equivalent V(2) atoms to form a mixture of distorted edge, corner, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°.
Ba2V3AlO8 crystallizes in the orthorhombic Pmmm space group. Ba(1) is bonded in a 12-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(5), and four equivalent O(4) atoms. Both Ba(1)-O(1) bond lengths are 3.30 Å. Both Ba(1)-O(2) bond lengths are 3.38 Å. Both Ba(1)-O(3) bond lengths are 2.82 Å. Both Ba(1)-O(5) bond lengths are 2.76 Å. All Ba(1)-O(4) bond lengths are 2.79 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(2)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. The V(1)-O(4) bond length is 1.90 Å. Both V(1)-O(1) bond lengths are 2.07 Å. Both V(1)-O(2) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. Both V(2)-O(3) bond lengths are 1.92 Å. Both V(2)-O(4) bond lengths are 2.25 Å. Both V(2)-O(5) bond lengths are 2.00 Å. Al(1) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. All Al(1)-O(1) bond lengths are 2.30 Å. All Al(1)-O(2) bond lengths are 2.35 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent V(1), and two equivalent Al(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent V(1), and two equivalent Al(1) atoms. In the third O site, O(3) is bonded in a distorted linear geometry to four equivalent Ba(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to four equivalent Ba(1), one V(1), and one V(2) atom to form a mixture of distorted edge, corner, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. In the fifth O site, O(5) is bonded to four equivalent Ba(1) and two equivalent V(2) atoms to form a mixture of distorted edge, corner, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°.