DOE OSTI2020
LiCu3O3 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to five O2- atoms to form distorted corner-sharing LiO5 trigonal bipyramids. There are four shorter (2.04 Å) and one longer (2.11 Å) Li–O bond lengths. In the second Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with five equivalent LiO5 trigonal bipyramids and edges with four equivalent CuO5 square pyramids. There are four shorter (2.05 Å) and one longer (2.23 Å) Li–O bond lengths. There are five inequivalent Cu+1.67+ sites. In the first Cu+1.67+ site, Cu+1.67+ is bonded in a linear geometry to two O2- atoms. Both Cu–O bond lengths are 1.86 Å. In the second Cu+1.67+ site, Cu+1.67+ is bonded in a distorted square co-planar geometry to four O2- atoms. All Cu–O bond lengths are 1.98 Å. In the third Cu+1.67+ site, Cu+1.67+ is bonded in a distorted square co-planar geometry to four equivalent O2- atoms. All Cu–O bond lengths are 1.99 Å. In the fourth Cu+1.67+ site, Cu+1.67+ is bonded to five O2- atoms to form distorted CuO5 square pyramids that share corners with five equivalent CuO5 square pyramids and edges with four equivalent LiO5 trigonal bipyramids. There are four shorter (1.98 Å) and one longer (2.68 Å) Cu–O bond lengths. In the fifth Cu+1.67+ site, Cu+1.67+ is bonded in a rectangular see-saw-like geometry to four equivalent O2- atoms. All Cu–O bond lengths are 1.98 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded to two equivalent Li1+ and three Cu+1.67+ atoms to form distorted OLi2Cu3 trigonal bipyramids that share corners with two equivalent OLiCu4 square pyramids, corners with five OLi2Cu3 trigonal bipyramids, and edges with four equivalent OLi2Cu3 trigonal bipyramids. In the second O2- site, O2- is bonded to two equivalent Li1+ and three Cu+1.67+ atoms to form distorted OLi2Cu3 trigonal bipyramids that share corners with four OCu6 octahedra, corners with five OLi2Cu3 trigonal bipyramids, and edges with four equivalent OLi2Cu3 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 76–88°. In the third O2- site, O2- is bonded to six Cu+1.67+ atoms to form distorted OCu6 octahedra that share corners with four equivalent OCu6 octahedra, corners with eight equivalent OLi2Cu3 trigonal bipyramids, and edges with four equivalent OLi2Cu4 octahedra. The corner-sharing octahedral tilt angles are 0°. In the fourth O2- site, O2- is bonded to one Li1+ and four equivalent Cu+1.67+ atoms to form OLiCu4 square pyramids that share corners with four equivalent OLiCu4 square pyramids, corners with four equivalent OLi2Cu3 trigonal bipyramids, and edges with four equivalent OLiCu4 square pyramids. In the fifth O2- site, O2- is bonded to two equivalent Li1+ and four equivalent Cu+1.67+ atoms to form OLi2Cu4 octahedra that share corners with four equivalent OLi2Cu4 octahedra, corners with eight equivalent OLi2Cu3 trigonal bipyramids, and edges with four equivalent OCu6 octahedra. The corner-sharing octahedral tilt angles are 0°.