DOE OSTI2020
Li4V2Si(PO6)2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are sixteen inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.07–2.74 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one SiO4 tetrahedra, corners with five PO4 tetrahedra, and faces with two VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.09–2.35 Å. In the third Li1+ site, Li1+ is bonded in a 5-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.05–2.81 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one SiO4 tetrahedra, corners with five PO4 tetrahedra, and faces with two VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.09–2.36 Å. In the fifth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.06–2.76 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.09–2.71 Å. In the seventh Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.06–2.79 Å. In the eighth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.09–2.72 Å. In the ninth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.05–2.78 Å. In the tenth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.06–2.74 Å. In the eleventh Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.07–2.75 Å. In the twelfth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.04–2.78 Å. In the thirteenth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three SiO4 tetrahedra, corners with three PO4 tetrahedra, and faces with two VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.10–2.33 Å. In the fourteenth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.06–2.75 Å. In the fifteenth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three SiO4 tetrahedra, corners with three PO4 tetrahedra, and faces with two VO6 octahedra. There are a spread of Li–O bond distances ranging from 2.10–2.33 Å. In the sixteenth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.07–2.75 Å. There are eight inequivalent V3+ sites. In the first V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one SiO4 tetrahedra, corners with five PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.92–2.09 Å. In the second V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three SiO4 tetrahedra, corners with three PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.10 Å. In the third V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share a cornercorner with one SiO4 tetrahedra, corners with five PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.92–2.09 Å. In the fourth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two SiO4 tetrahedra, corners with four PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.09 Å. In the fifth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three SiO4 tetrahedra, corners with three PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.11 Å. In the sixth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two SiO4 tetrahedra, corners with four PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.08 Å. In the seventh V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two SiO4 tetrahedra, corners with four PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.10 Å. In the eighth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two SiO4 tetrahedra, corners with four PO4 tetrahedra, and a faceface with one LiO6 octahedra. There are a spread of V–O bond distances ranging from 1.94–2.10 Å. There are four inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 31–45°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–44°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. In the third Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–44°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. In the fourth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 31–45°. There are a spread of Si–O bond distances ranging from 1.63–1.66 Å. There are eight inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–45°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–47°. There are a spread of P–O bond distances ranging from 1.53–1.56 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–45°. 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 two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–46°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–47°. There is two shorter (1.53 Å) and two longer (1.57 Å) P–O bond length. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 30–46°. There are a spread of P–O bond distances ranging from 1.53–1.56 Å. In the seventh P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 29–43°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. In the eighth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two LiO6 octahedra and corners with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 29–43°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. There are forty-eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one Si4+ atom. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one Si4+ atom. In the tenth O2- site, O2- is bonded in a 5-coordinate geometry to three Li1+, one V3+, and one Si4+ atom. In the eleventh O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a 5-coordinate geometry to three Li1+, one V3+, and one Si4+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one Si4+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded to three Li1+, one V3+, and one Si4+ atom to form distorted corner-sharing OLi3VSi trigonal bipyramids. In the eighteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one Si4+ atom. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the twenty-first O2- site, O2- is bonded in a 5-coordinate geometry to three Li1+, one V3+, and one Si4+ atom. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the twenty-third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one Si4+ atom. In the twenty-fourth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the twenty-fifth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the twenty-sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the twenty-seventh O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, one V3+, and one P5+ atom. In the twenty-eighth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+, one V3+, and one P5+ atom. In the twenty-ninth O2- site, O2- is bonded in a 3-coordinate geometry