Materials Data on Li4Mn3O7 by Materials Project

Li4Mn3O7 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are five inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three equivalent LiO6 octahedra, corners with three equivalent MnO6 octahedra, edges with three equivalent MnO6 octahedra, and edges with nine LiO6 octahedra. The corner-sharing octahedra tilt angles range from 3–11°. There are a spread of Li–O bond distances ranging from 2.00–2.51 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six MnO6 octahedra, edges with six equivalent LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 5–7°. There are a spread of Li–O bond distances ranging from 2.13–2.26 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six MnO6 octahedra, edges with six equivalent LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 5–7°. There are a spread of Li–O bond distances ranging from 2.15–2.25 Å. In the fourth Li1+ site, Li1+ is bonded to six equivalent O2- atoms to form LiO6 octahedra that share corners with six equivalent MnO6 octahedra, edges with six equivalent LiO6 octahedra, and edges with six equivalent MnO6 octahedra. The corner-sharing octahedra tilt angles range from 6–7°. There are four shorter (2.16 Å) and two longer (2.24 Å) Li–O bond lengths. In the fifth Li1+ site, Li1+ is bonded to six equivalent O2- atoms to form a mixture of edge and corner-sharing LiO6 octahedra. The corner-sharing octahedra tilt angles range from 3–6°. There are four shorter (2.07 Å) and two longer (2.30 Å) Li–O bond lengths. There are three inequivalent Mn+3.33+ sites. In the first Mn+3.33+ site, Mn+3.33+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO6 octahedra, edges with six LiO6 octahedra, and edges with six equivalent MnO6 octahedra. The corner-sharing octahedra tilt angles range from 5–11°. There are a spread of Mn–O bond distances ranging from 1.95–2.31 Å. In the second Mn+3.33+ site, Mn+3.33+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO6 octahedra, edges with six LiO6 octahedra, and edges with six equivalent MnO6 octahedra. The corner-sharing octahedra tilt angles range from 5–7°. There are a spread of Mn–O bond distances ranging from 1.96–2.32 Å. In the third Mn+3.33+ site, Mn+3.33+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO6 octahedra, edges with six LiO6 octahedra, and edges with six equivalent MnO6 octahedra. The corner-sharing octahedra tilt angles range from 5–7°. There are four shorter (1.97 Å) and two longer (2.32 Å) Mn–O bond lengths. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles are 0°. In the second O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles are 0°. In the third O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedra tilt angles range from 0–1°. In the fourth O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form distorted OLi3Mn3 octahedra that share corners with six OLi6 octahedra and edges with twelve OLi3Mn3 octahedra. The corner-sharing octahedra tilt angles range from 1–12°. In the fifth O2- site, O2- is bonded to six Li1+ atoms to form a mixture of edge and corner-sharing OLi6 octahedra. The corner-sharing octahedra tilt angles range from 0–12°. In the sixth O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedra tilt angles range from 1–4°. In the seventh O2- site, O2- is bonded to three equivalent Li1+ and three equivalent Mn+3.33+ atoms to form a mixture of edge and corner-sharing OLi3Mn3 octahedra. The corner-sharing octahedral tilt angles are 0°.