Materials Data on Li4Cr5Fe3O16 by Materials Project

Abstract

Li4Cr5Fe3O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with five FeO6 octahedra and corners with seven CrO6 octahedra. The corner-sharing octahedra tilt angles range from 56–64°. There are a spread of Li–O bond distances ranging from 1.96–1.99 Å. In the second Li1+ site, Li1+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.77–1.99 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 trigonal pyramids that share a cornercorner with one FeO6 octahedra, corners with five CrO6 octahedra, an edgeedge with one CrO6 octahedra, and edges with two equivalent FeO6 octahedra. The corner-sharing octahedra tilt angles range from 60–65°. There are a spread of Li–O bond distances ranging from 1.77–1.97 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four FeO6 octahedra and corners with eight CrO6 octahedra. The corner-sharing octahedra tilt angles range from 58–64°. There is three shorter (1.97 Å) and one longer (2.02 Å) Li–O bond length. There are four inequivalent Cr+3.80+ sites. In the first Cr+3.80+ site, Cr+3.80+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, edges with two equivalent FeO6 octahedra, and edges with three CrO6 octahedra. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Cr–O bond distances ranging from 1.90–1.98 Å. In the second Cr+3.80+ site, Cr+3.80+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with four equivalent FeO6 octahedra, corners with three equivalent LiO4 tetrahedra, corners with three equivalent LiO4 trigonal pyramids, an edgeedge with one FeO6 octahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedra tilt angles range from 48–53°. There are a spread of Cr–O bond distances ranging from 2.00–2.06 Å. In the third Cr+3.80+ site, Cr+3.80+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, an edgeedge with one CrO6 octahedra, edges with four equivalent FeO6 octahedra, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedral tilt angles are 48°. There are a spread of Cr–O bond distances ranging from 1.91–1.98 Å. In the fourth Cr+3.80+ site, Cr+3.80+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with four equivalent CrO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one CrO6 octahedra, and edges with two equivalent FeO6 octahedra. The corner-sharing octahedra tilt angles range from 49–54°. There are a spread of Cr–O bond distances ranging from 2.01–2.14 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, and edges with five CrO6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Fe–O bond distances ranging from 1.96–2.09 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent CrO6 octahedra, corners with three LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, edges with three CrO6 octahedra, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Fe–O bond distances ranging from 1.96–2.10 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Cr+3.80+, and one Fe3+ atom. In the second O2- site, O2- is bonded to one Li1+ and three Cr+3.80+ atoms to form distorted OLiCr3 tetrahedra that share corners with two equivalent OLiCr2Fe tetrahedra, corners with five OLiCr3 trigonal pyramids, and edges with three OLiCr2Fe trigonal pyramids. In the third O2- site, O2- is bonded to one Li1+, two equivalent Cr+3.80+, and one Fe3+ atom to form distorted OLiCr2Fe trigonal pyramids that share corners with three equivalent OLiCr2Fe tetrahedra, corners with four OLiCr3 trigonal pyramids, an edgeedge with one OLiCr3 tetrahedra, and edges with two equivalent OLiCr2Fe trigonal pyramids. In the fourth O2- site, O2- is bonded to one Li1+, two equivalent Cr+3.80+, and one Fe3+ atom to form distorted OLiCr2Fe tetrahedra that share corners with two equivalent OLiCr3 tetrahedra, corners with seven OLiCr2Fe trigonal pyramids, and an edgeedge with one OLiCr3 trigonal pyramid. In the fifth O2- site, O2- is bonded to one Li1+, one Cr+3.80+, and two equivalent Fe3+ atoms to form distorted corner-sharing OLiCrFe2 tetrahedra. In the sixth O2- site, O2- is bonded to one Li1+, two Cr+3.80+, and one Fe3+ atom to form distorted OLiCr2Fe trigonal pyramids that share corners with three OLiCr3 tetrahedra, corners with three OLiCr3 trigonal pyramids, an edgeedge with one OLiCr3 tetrahedra, and edges with two OLiCr2Fe trigonal pyramids. In the seventh O2- site, O2- is bonded to one Li1+ and three Cr+3.80+ atoms to form distorted OLiCr3 trigonal pyramids that share corners with three OLiCr3 tetrahedra, corners with six OLiCr2Fe trigonal pyramids, and an edgeedge with one OLiCr2Fe tetrahedra. In the eighth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Cr+3.80+, and two equivalent Fe3+ atoms. In the ninth O2- site, O2- is bonded to one Li1+, two Cr+3.80+, and one Fe3+ atom to form distorted OLiCr2Fe trigonal pyramids that share corners with two equivalent OLiCrFe2 tetrahedra, corners with three OLiCr3 trigonal pyramids, and edges with two OLiCr2Fe trigonal pyramids. In the tenth O2- site, O2- is bonded to one Li1+, one Cr+3.80+, and two equivalent Fe3+ atoms to form distorted OLiCrFe2 trigonal pyramids that share corners with four OLiCr3 tetrahedra, corners with two equivalent OLiCr2Fe trigonal pyramids, and edges with two equivalent OLiCr2Fe trigonal pyramids. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Cr+3.80+, and one Fe3+ atom. In the twelfth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Cr+3.80+, and two equivalent Fe3+ atoms.