DOE OSTI2020
Li6VSn3(PO4)6 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six 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 2.13–2.47 Å. In the second Li1+ site, Li1+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.04–2.62 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one SnO6 octahedra. There are a spread of Li–O bond distances ranging from 2.11–2.47 Å. In the fourth Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.97–2.53 Å. In the fifth Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.00–2.61 Å. In the sixth Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 2.01–2.55 Å. V4+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of V–O bond distances ranging from 2.14–2.24 Å. There are three inequivalent Sn+2.67+ sites. In the first Sn+2.67+ site, Sn+2.67+ is bonded to six O2- atoms to form SnO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Sn–O bond distances ranging from 2.01–2.09 Å. In the second Sn+2.67+ site, Sn+2.67+ is bonded to six O2- atoms to form SnO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one LiO6 octahedra. There are a spread of Sn–O bond distances ranging from 2.03–2.13 Å. In the third Sn+2.67+ site, Sn+2.67+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Sn–O bond distances ranging from 2.39–2.52 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 a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 22–52°. There are a spread of P–O bond distances ranging from 1.53–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 21–50°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 23–52°. There are a spread of P–O bond distances ranging from 1.52–1.59 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 26–47°. There are a spread of P–O bond distances ranging from 1.54–1.56 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 13–42°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one VO6 octahedra, and corners with two SnO6 octahedra. The corner-sharing octahedra tilt angles range from 17–47°. There are a spread of P–O bond distances ranging from 1.54–1.56 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted linear geometry to one Sn+2.67+ and one P5+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Sn+2.67+ and one P5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V4+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the tenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Sn+2.67+ and one P5+ atom. In the eleventh O2- site, O2- is bonded to three Li1+, one V4+, and one P5+ atom to form distorted face-sharing OLi3VP trigonal bipyramids. In the twelfth O2- site, O2- is bonded in a linear geometry to one Sn+2.67+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+, one V4+, and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V4+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the eighteenth O2- site, O2- is bonded to three Li1+, one V4+, and one P5+ atom to form distorted face-sharing OLi3VP trigonal bipyramids. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Sn+2.67+, and one P5+ atom. In the twenty-first O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the twenty-second O2- site, O2- is bonded to three Li1+, one V4+, and one P5+ atom to form distorted face-sharing OLi3VP trigonal bipyramids. In the twenty-third O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom. In the twenty-fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, one Sn+2.67+, and one P5+ atom.