Materials Data on NaV6O11 by Materials Project
NaV6O11 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na1+ is bonded to twelve O2- atoms to form NaO12 cuboctahedra that share corners with six equivalent NaO12 cuboctahedra, edges with six equivalent VO6 octahedra, edges with three equivalent VO5 trigonal bipyramids, and faces with six equivalent VO6 octahedra. There are six shorter (2.87 Å) and six longer (2.94 Å) Na–O bond lengths. There are three inequivalent V+3.50+ sites. In the first V+3.50+ site, V+3.50+ is bonded to five O2- atoms to form VO5 trigonal bipyramids that share corners with twelve VO6 octahedra and edges with three equivalent NaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 42–56°. There are three shorter (1.89 Å) and two longer (2.26 Å) V–O bond lengths. In the second V+3.50+ site, V+3.50+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six equivalent VO6 octahedra, corners with three equivalent VO5 trigonal bipyramids, faces with three equivalent NaO12 cuboctahedra, and a faceface with one VO6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are three shorter (2.03 Å) and three longer (2.04 Å) V–O bond lengths. In the third V+3.50+ site, V+3.50+ is bonded to six O2- atoms to form VO6 octahedra that share corners with four equivalent VO6 octahedra, corners with two equivalent VO5 trigonal bipyramids, edges with two equivalent NaO12 cuboctahedra, and edges with four equivalent VO6 octahedra. The corner-sharing octahedral tilt angles are 53°. There is four shorter (1.94 Å) and two longer (2.03 Å) V–O bond length. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+ and three V+3.50+ atoms. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four V+3.50+ atoms. In the third O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent Na1+ and three V+3.50+ atoms.