BaVCuAlO5 crystallizes in the orthorhombic Pmm2 space group. Ba(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(5) atoms. V(1) is bonded in a 5-coordinate geometry to one O(5), two equivalent O(1), and two equivalent O(2) atoms. Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(4) atoms. Al(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1) and two equivalent Al(1) atoms to form distorted OAl2V2 tetrahedra that share corners with two equivalent O(3)Ba2Al2Cu2 octahedra, corners with four equivalent O(1)Al2V2 tetrahedra,  an edgeedge with one O(3)Ba2Al2Cu2 octahedra, and edges with four equivalent O(2)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 5°. In the second O site, O(2) is bonded to two equivalent V(1) and two equivalent Al(1) atoms to form distorted OAl2V2 tetrahedra that share corners with four equivalent O(3)Ba2Al2Cu2 octahedra, corners with four equivalent O(2)Al2V2 tetrahedra, and edges with four equivalent O(1)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 73°. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent Cu(1), and two equivalent Al(1) atoms to form distorted OBa2Al2Cu2 octahedra that share corners with two equivalent O(3)Ba2Al2Cu2 octahedra, corners with two equivalent O(1)Al2V2 tetrahedra, corners with four equivalent O(2)Al2V2 tetrahedra, edges with two equivalent O(3)Ba2Al2Cu2 octahedra, and  an edgeedge with one O(1)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 5°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Cu(1), and two equivalent Al(1) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to four equivalent Ba(1) and one V(1) atom.
BaVCuAlO5 crystallizes in the orthorhombic Pmm2 space group. Ba(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(5) atoms. Both Ba(1)-O(3) bond lengths are 2.83 Å. Both Ba(1)-O(4) bond lengths are 2.88 Å. All Ba(1)-O(5) bond lengths are 2.81 Å. V(1) is bonded in a 5-coordinate geometry to one O(5), two equivalent O(1), and two equivalent O(2) atoms. The V(1)-O(5) bond length is 1.85 Å. Both V(1)-O(1) bond lengths are 2.02 Å. Both V(1)-O(2) bond lengths are 1.97 Å. Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(4) atoms. Both Cu(1)-O(3) bond lengths are 1.91 Å. Both Cu(1)-O(4) bond lengths are 1.85 Å. Al(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Al(1)-O(1) bond lengths are 2.16 Å. Both Al(1)-O(2) bond lengths are 2.21 Å. Both Al(1)-O(3) bond lengths are 2.29 Å. Both Al(1)-O(4) bond lengths are 2.34 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1) and two equivalent Al(1) atoms to form distorted OAl2V2 tetrahedra that share corners with two equivalent O(3)Ba2Al2Cu2 octahedra, corners with four equivalent O(1)Al2V2 tetrahedra,  an edgeedge with one O(3)Ba2Al2Cu2 octahedra, and edges with four equivalent O(2)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 5°. In the second O site, O(2) is bonded to two equivalent V(1) and two equivalent Al(1) atoms to form distorted OAl2V2 tetrahedra that share corners with four equivalent O(3)Ba2Al2Cu2 octahedra, corners with four equivalent O(2)Al2V2 tetrahedra, and edges with four equivalent O(1)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 73°. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent Cu(1), and two equivalent Al(1) atoms to form distorted OBa2Al2Cu2 octahedra that share corners with two equivalent O(3)Ba2Al2Cu2 octahedra, corners with two equivalent O(1)Al2V2 tetrahedra, corners with four equivalent O(2)Al2V2 tetrahedra, edges with two equivalent O(3)Ba2Al2Cu2 octahedra, and  an edgeedge with one O(1)Al2V2 tetrahedra. The corner-sharing octahedral tilt angles are 5°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Cu(1), and two equivalent Al(1) atoms. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to four equivalent Ba(1) and one V(1) atom.