DOE OSTI2020
LiCu4(PO4)3 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.99–2.22 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share corners with six CuO6 octahedra and corners with four PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 76–78°. There are a spread of Li–O bond distances ranging from 2.04–2.17 Å. In the third Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 2.06–2.24 Å. In the fourth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 2.04–2.18 Å. There are ten inequivalent Cu2+ sites. In the first Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with six PO4 tetrahedra and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.90–2.56 Å. In the second Cu2+ site, Cu2+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with six PO4 tetrahedra and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.92–2.35 Å. In the third Cu2+ site, Cu2+ is bonded to six O2- atoms to form CuO6 octahedra that share a cornercorner with one LiO4 tetrahedra, corners with six PO4 tetrahedra, and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.96–2.35 Å. In the fourth Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share a cornercorner with one LiO4 tetrahedra, corners with six PO4 tetrahedra, and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.94–2.57 Å. In the fifth Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with six PO4 tetrahedra and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.93–2.64 Å. In the sixth Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share a cornercorner with one LiO4 tetrahedra, corners with six PO4 tetrahedra, and edges with two equivalent CuO6 octahedra. There are a spread of Cu–O bond distances ranging from 1.90–2.59 Å. In the seventh Cu2+ site, Cu2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.98–2.20 Å. In the eighth Cu2+ site, Cu2+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.98–2.57 Å. In the ninth Cu2+ site, Cu2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.18 Å. In the tenth Cu2+ site, Cu2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.98–2.18 Å. There are twelve inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra and a cornercorner with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 46–57°. There are a spread of P–O bond distances ranging from 1.53–1.61 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra and a cornercorner with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 46–57°. There are a spread of P–O bond distances ranging from 1.54–1.59 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 48–57°. There are a spread of P–O bond distances ranging from 1.53–1.59 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra and corners with two equivalent LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–54°. There are a spread of P–O bond distances ranging from 1.54–1.59 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 48–57°. 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 corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 49–55°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the seventh P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 46–58°. There are a spread of P–O bond distances ranging from 1.52–1.62 Å. In the eighth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 45–56°. There are a spread of P–O bond distances ranging from 1.54–1.59 Å. In the ninth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 46–58°. There are a spread of P–O bond distances ranging from 1.53–1.61 Å. In the tenth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 46–55°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the eleventh P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 47–57°. There are a spread of P–O bond distances ranging from 1.55–1.58 Å. In the twelfth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with six CuO6 octahedra. The corner-sharing octahedra tilt angles range from 44–56°. There are a spread of P–O bond distances ranging from 1.51–1.59 Å. There are thirty-six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one P5+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one P5+ atom. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu2+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, two equivalent Cu2+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent Cu2+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+, three Cu2+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu2+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Cu2+ and one P5+ atom. In the ninth O2- site, O2- is bonded to one Li1+, two equivalent Cu2+, and one P5+ atom to form distorted corner-sharing OLiCu2P tetrahedra. In the tenth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, two equivalent Cu2+, and one P5+ atom. In the eleventh O2- site, O2- is bonded to one Li1+, two equivalent Cu2+, and one P5+ atom to form distorted corner-sharing OLiCu2P tetrahedra. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Cu2+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent Cu2+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded to one Li1+, two equivalent Cu2+, and one P5+ atom to form distorted OLiCu2P tetrahedra that share corners with three OLiCu2P tetrahedra and an edgeedge with one OCu3P tetrahedra. In the fifteenth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent Cu2+ and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu2+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu2+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Cu2+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cu2+ and one P5+ atom. In the twenty-first O2- site, O2- is bonded in a 3-coordinate geometry to two Cu2+ and one P5+ atom. In the twenty-second O2- site, O2- is bonded in a 2-coordinate geometry to three Cu2+ and one P5+ atom. In the twenty-third O2- site, O2- is bonded in a 2-coordinate geometry to three Cu2+ and one P5+ atom. In the twenty-fourth O2- site, O2- is bonded in a 2-coordinate geometry to three Cu2+ and one P5+ atom. In the twenty-fifth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Cu2+ and one P5+ atom. In the twenty-sixth O2- site, O2- is bonded to one Li1+, two equivalent Cu2+, and one P5+ atom to form distorted corner-sharing OLiCu2P tetrahedra. In the twenty-seventh O2- site, O2- is bonded to three Cu2+ and one P5+ atom to form a mixture of distorted edge and corner-sharing OCu3P tetrahedra. In the twenty-eighth O2- site, O2- is bonded to three Cu2+ and one P5+ atom to form distorted corner-sharing OCu3P tetrahedra. In the twenty-ninth O2- site, O2- is bonded to three Cu2+ and one P5+ atom to form distorted corner-sharing OCu3P tetrahedra. In the thirtieth O2- site, O2- is bonded in a distorted tetrahedral geometry to three Cu2+ and one P5+ atom. In the thirty-first O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Cu2+ and one P5+ atom. In the thirty-second O2- site, O2- is bonded to one Li1+, two equivalent Cu2+, and one P5+ atom to form distorted corner-sharing OLiCu2P tetrahedra. In the thirty-third O2- site, O2- is bonded in a 4-coordinate geometry to three Cu2+ and one P5+ atom. In the thirty-fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu2+ and one P5+ atom. In the thirty-fifth O2- site, O2- is bonded in a 3-coordinate geometry to two Cu2+ and one P5+ atom. In the thirty-sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two Cu2+ and one P5+ atom.