DOE OSTI2020
Li4NbMn3Fe2(PO4)6 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four 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 2.07–2.62 Å. In the second 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 1.95–2.82 Å. In the third 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 1.97–2.84 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 1.97–2.81 Å. Nb2+ is bonded to six O2- atoms to form distorted NbO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one FeO6 octahedra. There are a spread of Nb–O bond distances ranging from 2.00–2.17 Å. There are three inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 2.06–2.26 Å. In the second Mn2+ site, Mn2+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 2.09–2.32 Å. In the third Mn2+ site, Mn2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.08–2.32 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form distorted FeO6 octahedra that share corners with six PO4 tetrahedra, a faceface with one NbO6 octahedra, and a faceface with one MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.09–2.35 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form distorted FeO6 octahedra that share corners with six PO4 tetrahedra and a faceface with one MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.10–2.27 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 NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 27–56°. 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 a cornercorner with one NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 34–50°. There are a spread of P–O bond distances ranging from 1.51–1.63 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 23–48°. There are a spread of P–O bond distances ranging from 1.51–1.62 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 21–50°. There are a spread of P–O bond distances ranging from 1.51–1.61 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 24–57°. There is three shorter (1.54 Å) and one longer (1.60 Å) P–O bond length. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one NbO6 octahedra, corners with two MnO6 octahedra, and corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 27–55°. There are a spread of P–O bond distances ranging from 1.54–1.59 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mn2+ and one P5+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Mn2+ and one P5+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Mn2+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+, one Nb2+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Fe3+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Mn2+, one Fe3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Mn2+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Nb2+, one Fe3+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a bent 150 degrees geometry to one Mn2+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+, one Nb2+, and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+, one Nb2+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Nb2+, one Fe3+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+, one Mn2+, one Fe3+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Mn2+, and one P5+ atom. In the twenty-first O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Mn2+, and one P5+ atom. In the twenty-second O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Nb2+, one Fe3+, and one P5+ atom. In the twenty-third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Mn2+, and one P5+ atom. In the twenty-fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Mn2+, and one P5+ atom.