DOE OSTI2020
Ba3V4(PO4)6 crystallizes in the monoclinic P2_1 space group. The structure is three-dimensional. there are three inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Ba–O bond distances ranging from 2.78–3.21 Å. In the second Ba2+ site, Ba2+ is bonded in a 3-coordinate geometry to thirteen O2- atoms. There are a spread of Ba–O bond distances ranging from 2.76–3.45 Å. In the third Ba2+ site, Ba2+ is bonded in a 6-coordinate geometry to eleven O2- atoms. There are a spread of Ba–O bond distances ranging from 2.81–3.25 Å. There are four inequivalent V3+ sites. In the first V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of V–O bond distances ranging from 2.01–2.06 Å. In the second V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of V–O bond distances ranging from 2.01–2.04 Å. In the third V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of V–O bond distances ranging from 1.99–2.11 Å. In the fourth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of V–O bond distances ranging from 1.99–2.12 Å. There are six inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 18–48°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 16–45°. There are a spread of P–O bond distances ranging from 1.54–1.56 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 22–51°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 14–51°. There is three shorter (1.54 Å) and one longer (1.56 Å) P–O bond length. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 17–53°. There are a spread of P–O bond distances ranging from 1.54–1.56 Å. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 12–48°. There is three shorter (1.54 Å) and one longer (1.57 Å) P–O bond length. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one V3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ba2+, one V3+, and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted linear geometry to one Ba2+, one V3+, and one P5+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one V3+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one V3+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one V3+ and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Ba2+, one V3+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+, one V3+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ba2+, one V3+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ba2+, one V3+, and one P5+ atom. In the twenty-first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to three Ba2+, one V3+, and one P5+ atom. In the twenty-second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two equivalent Ba2+, one V3+, and one P5+ atom. In the twenty-third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to three Ba2+, one V3+, and one P5+ atom. In the twenty-fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Ba2+, one V3+, and one P5+ atom.