BaV6O11 crystallizes in the orthorhombic Cmcm space group. Ba(1) is bonded to two equivalent O(3), two equivalent O(5), four equivalent O(2), and four equivalent O(4) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(1)O12 cuboctahedra, edges with two equivalent V(4)O6 octahedra, edges with four equivalent V(3)O6 octahedra, edges with three equivalent V(1)O5 trigonal bipyramids, and faces with six equivalent V(2)O6 octahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form VO5 trigonal bipyramids that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with six equivalent V(2)O6 octahedra, and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the second V site, V(2) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, faces with three equivalent Ba(1)O12 cuboctahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ba(1)O12 cuboctahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. In the fourth V site, V(4) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ba(1)O12 cuboctahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are five inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Ba(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Ba(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Ba(1), one V(2), one V(3), and one V(4) atom. In the fourth O site, O(5) is bonded in a 3-coordinate geometry to one Ba(1), one V(2), and two equivalent V(3) atoms. In the fifth O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(3) atoms.
BaV6O11 crystallizes in the orthorhombic Cmcm space group. Ba(1) is bonded to two equivalent O(3), two equivalent O(5), four equivalent O(2), and four equivalent O(4) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(1)O12 cuboctahedra, edges with two equivalent V(4)O6 octahedra, edges with four equivalent V(3)O6 octahedra, edges with three equivalent V(1)O5 trigonal bipyramids, and faces with six equivalent V(2)O6 octahedra. Both Ba(1)-O(3) bond lengths are 2.91 Å. Both Ba(1)-O(5) bond lengths are 2.80 Å. There are two shorter (2.91 Å) and two longer (2.92 Å) Ba(1)-O(2) bond lengths. All Ba(1)-O(4) bond lengths are 2.80 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form VO5 trigonal bipyramids that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with six equivalent V(2)O6 octahedra, and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 42-56°. The V(1)-O(3) bond length is 1.85 Å. Both V(1)-O(1) bond lengths are 2.18 Å. Both V(1)-O(2) bond lengths are 1.85 Å. In the second V site, V(2) is bonded to one O(3), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, faces with three equivalent Ba(1)O12 cuboctahedra, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(5) bond length is 1.94 Å. Both V(2)-O(2) bond lengths are 2.04 Å. Both V(2)-O(4) bond lengths are 1.94 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ba(1)O12 cuboctahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. Both V(3)-O(1) bond lengths are 2.03 Å. Both V(3)-O(4) bond lengths are 1.96 Å. Both V(3)-O(5) bond lengths are 1.96 Å. In the fourth V site, V(4) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ba(1)O12 cuboctahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. Both V(4)-O(1) bond lengths are 2.03 Å. All V(4)-O(4) bond lengths are 1.96 Å. There are five inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Ba(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Ba(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(4) is bonded in a 3-coordinate geometry to one Ba(1), one V(2), one V(3), and one V(4) atom. In the fourth O site, O(5) is bonded in a 3-coordinate geometry to one Ba(1), one V(2), and two equivalent V(3) atoms. In the fifth O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one V(1), one V(4), and two equivalent V(3) atoms.