Ba2V2O5 crystallizes in the tetragonal P4/mmm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. In the second Ba site, Ba(2) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with four equivalent Ba(2)O12 cuboctahedra, and faces with eight equivalent V(1)O5 square pyramids. V(1) is bonded to one O(2) and four equivalent O(1) atoms to form VO5 square pyramids that share corners with five equivalent V(1)O5 square pyramids and faces with four equivalent Ba(2)O12 cuboctahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded to four equivalent Ba(2) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OBa4V2 octahedra. The corner-sharing octahedra are not tilted.
Ba2V2O5 crystallizes in the tetragonal P4/mmm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. All Ba(1)-O(1) bond lengths are 2.77 Å. In the second Ba site, Ba(2) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with four equivalent Ba(2)O12 cuboctahedra, and faces with eight equivalent V(1)O5 square pyramids. All Ba(2)-O(2) bond lengths are 2.85 Å. All Ba(2)-O(1) bond lengths are 3.04 Å. V(1) is bonded to one O(2) and four equivalent O(1) atoms to form VO5 square pyramids that share corners with five equivalent V(1)O5 square pyramids and faces with four equivalent Ba(2)O12 cuboctahedra. The V(1)-O(2) bond length is 2.00 Å. All V(1)-O(1) bond lengths are 2.04 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded to four equivalent Ba(2) and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OBa4V2 octahedra. The corner-sharing octahedra are not tilted.