DOE OSTI2020
BaV13O18 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with twenty-four VO6 octahedra and faces with eight VO6 octahedra. The corner-sharing octahedra tilt angles range from 39–53°. There are a spread of Ba–O bond distances ranging from 3.01–3.22 Å. There are seven inequivalent V+2.62+ sites. In the first V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, corners with three VO6 octahedra, and edges with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 6–10°. There are a spread of V–O bond distances ranging from 2.05–2.15 Å. In the second V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, corners with three VO6 octahedra, and edges with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 8–9°. There are a spread of V–O bond distances ranging from 2.10–2.21 Å. In the third V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, corners with three VO6 octahedra, and edges with nine VO6 octahedra. The corner-sharing octahedra tilt angles range from 9–12°. There are a spread of V–O bond distances ranging from 2.01–2.17 Å. In the fourth V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one BaO12 cuboctahedra, corners with four VO6 octahedra, edges with eight VO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 4–14°. There are a spread of V–O bond distances ranging from 2.05–2.19 Å. In the fifth V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one BaO12 cuboctahedra, corners with four VO6 octahedra, edges with eight VO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 4–12°. There are a spread of V–O bond distances ranging from 1.98–2.14 Å. In the sixth V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one BaO12 cuboctahedra, corners with four VO6 octahedra, edges with eight VO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 6–14°. There are a spread of V–O bond distances ranging from 2.01–2.17 Å. In the seventh V+2.62+ site, V+2.62+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six VO6 octahedra, edges with six VO6 octahedra, and faces with two equivalent BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 6–8°. There are four shorter (2.17 Å) and two longer (2.20 Å) V–O bond lengths. There are nine inequivalent O2- sites. In the first O2- site, O2- is bonded to five V+2.62+ atoms to form a mixture of corner and edge-sharing OV5 square pyramids. In the second O2- site, O2- is bonded to five V+2.62+ atoms to form a mixture of corner and edge-sharing OV5 square pyramids. In the third O2- site, O2- is bonded to five V+2.62+ atoms to form a mixture of corner and edge-sharing OV5 square pyramids. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ba2+ and four V+2.62+ atoms.