BaNb2V2O11 crystallizes in the trigonal R-3m space group. Ba(1) is bonded to six equivalent O(2) and six equivalent O(3) atoms to form BaO12 cuboctahedra that share edges with six equivalent Ba(1)O12 cuboctahedra, edges with six equivalent V(1)O4 tetrahedra, and faces with two equivalent Nb(1)O6 octahedra. Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form NbO6 octahedra that share corners with three equivalent Nb(1)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and  a faceface with one Ba(1)O12 cuboctahedra. The corner-sharing octahedra are not tilted. V(1) is bonded to one O(3) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Nb(1)O6 octahedra and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 24°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ba(1), one Nb(1), and one V(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Ba(1) and one V(1) atom.
BaNb2V2O11 crystallizes in the trigonal R-3m space group. Ba(1) is bonded to six equivalent O(2) and six equivalent O(3) atoms to form BaO12 cuboctahedra that share edges with six equivalent Ba(1)O12 cuboctahedra, edges with six equivalent V(1)O4 tetrahedra, and faces with two equivalent Nb(1)O6 octahedra. All Ba(1)-O(2) bond lengths are 2.90 Å. All Ba(1)-O(3) bond lengths are 3.28 Å. Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form NbO6 octahedra that share corners with three equivalent Nb(1)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and  a faceface with one Ba(1)O12 cuboctahedra. The corner-sharing octahedra are not tilted. All Nb(1)-O(1) bond lengths are 1.93 Å. All Nb(1)-O(2) bond lengths are 2.08 Å. V(1) is bonded to one O(3) and three equivalent O(2) atoms to form VO4 tetrahedra that share corners with three equivalent Nb(1)O6 octahedra and edges with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 24°. The V(1)-O(3) bond length is 1.68 Å. All V(1)-O(2) bond lengths are 1.76 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Nb(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ba(1), one Nb(1), and one V(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to three equivalent Ba(1) and one V(1) atom.