Ba5V5O14 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to nine equivalent O(1) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(3), three equivalent O(1), and six equivalent O(2) atoms. In the third Ba site, Ba(3) is bonded to six equivalent O(2) atoms to form distorted BaO6 cuboctahedra that share corners with six equivalent V(2)O4 tetrahedra and faces with two equivalent V(3)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form face-sharing VO6 octahedra. In the second V site, V(2) is bonded to one O(3) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Ba(3)O6 cuboctahedra and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra,  a faceface with one Ba(3)O6 cuboctahedra, and  a faceface with one V(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), three equivalent Ba(1), one V(1), and one V(3) atom to form a mixture of distorted corner, edge, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-62°. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ba(3), two equivalent Ba(2), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ba(2) and one V(2) atom.
Ba5V5O14 crystallizes in the trigonal P-3m1 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to nine equivalent O(1) atoms. There are three shorter (2.79 Å) and six longer (2.98 Å) Ba(1)-O(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one O(3), three equivalent O(1), and six equivalent O(2) atoms. The Ba(2)-O(3) bond length is 2.83 Å. All Ba(2)-O(1) bond lengths are 2.66 Å. All Ba(2)-O(2) bond lengths are 3.03 Å. In the third Ba site, Ba(3) is bonded to six equivalent O(2) atoms to form distorted BaO6 cuboctahedra that share corners with six equivalent V(2)O4 tetrahedra and faces with two equivalent V(3)O6 octahedra. All Ba(3)-O(2) bond lengths are 2.83 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form face-sharing VO6 octahedra. All V(1)-O(1) bond lengths are 2.01 Å. In the second V site, V(2) is bonded to one O(3) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Ba(3)O6 cuboctahedra and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. The V(2)-O(3) bond length is 1.72 Å. All V(2)-O(2) bond lengths are 1.78 Å. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra,  a faceface with one Ba(3)O6 cuboctahedra, and  a faceface with one V(1)O6 octahedra. All V(3)-O(1) bond lengths are 2.07 Å. All V(3)-O(2) bond lengths are 2.15 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), three equivalent Ba(1), one V(1), and one V(3) atom to form a mixture of distorted corner, edge, and face-sharing OBa4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-62°. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ba(3), two equivalent Ba(2), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ba(2) and one V(2) atom.