Materials Data on Li4FeCu3(PO4)4 by Materials Project

Li4FeCu3(PO4)4 is Hausmannite-derived structured and crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with four CuO6 pentagonal pyramids, corners with two PO4 tetrahedra, an edgeedge with one FeO6 octahedra, an edgeedge with one CuO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with two PO4 tetrahedra. There are a spread of Li–O bond distances ranging from 2.08–2.33 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with two equivalent CuO6 octahedra, corners with two PO4 tetrahedra, edges with two equivalent LiO6 octahedra, edges with two CuO6 pentagonal pyramids, and edges with two PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 55–71°. There are a spread of Li–O bond distances ranging from 2.08–2.24 Å. Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with four equivalent LiO6 octahedra, corners with four equivalent CuO6 pentagonal pyramids, corners with four PO4 tetrahedra, edges with two equivalent LiO6 octahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 55–68°. There are a spread of Fe–O bond distances ranging from 1.98–2.12 Å. There are three inequivalent Cu+1.67+ sites. In the first Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with four equivalent LiO6 octahedra, corners with four equivalent CuO6 pentagonal pyramids, corners with four PO4 tetrahedra, edges with two equivalent LiO6 octahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 57–71°. There are a spread of Cu–O bond distances ranging from 2.06–2.33 Å. In the second Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent LiO6 octahedra, corners with four equivalent FeO6 octahedra, corners with four PO4 tetrahedra, edges with two equivalent LiO6 octahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–75°. There are a spread of Cu–O bond distances ranging from 2.00–2.45 Å. In the third Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent LiO6 octahedra, corners with four equivalent CuO6 octahedra, corners with four PO4 tetrahedra, edges with two equivalent LiO6 octahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–70°. There are a spread of Cu–O bond distances ranging from 2.04–2.37 Å. There are four 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 FeO6 octahedra, corners with two equivalent LiO6 octahedra, corners with two equivalent CuO6 octahedra, a cornercorner with one CuO6 pentagonal pyramid, edges with two equivalent LiO6 octahedra, and an edgeedge with one CuO6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 50–56°. There are a spread of P–O bond distances ranging from 1.54–1.59 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one FeO6 octahedra, corners with two equivalent LiO6 octahedra, corners with three CuO6 pentagonal pyramids, an edgeedge with one FeO6 octahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedra tilt angles range from 51–60°. There is two shorter (1.54 Å) and two longer (1.57 Å) P–O bond length. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CuO6 octahedra, corners with two equivalent LiO6 octahedra, corners with three CuO6 pentagonal pyramids, an edgeedge with one CuO6 octahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedra tilt angles range from 56–60°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one CuO6 octahedra, corners with two equivalent LiO6 octahedra, corners with two equivalent FeO6 octahedra, a cornercorner with one CuO6 pentagonal pyramid, edges with two equivalent LiO6 octahedra, and an edgeedge with one CuO6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 49–58°. There are a spread of P–O bond distances ranging from 1.54–1.58 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Li1+, one Fe3+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Cu+1.67+, and one P5+ atom. In the third O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one P5+ atom to form distorted corner-sharing OLi2CuP tetrahedra. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li1+, one Cu+1.67+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Fe3+, one Cu+1.67+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Li1+, one Cu+1.67+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to two equivalent Li1+, one Cu+1.67+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Cu+1.67+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li1+, one Fe3+, and one P5+ atom. In the tenth O2- site, O2- is bonded to two equivalent Li1+, one Cu+1.67+, and one P5+ atom to form distorted corner-sharing OLi2CuP trigonal pyramids. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Fe3+, one Cu+1.67+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li1+, one Cu+1.67+, and one P5+ atom.