DOE OSTI2020
Li6NBr3 is Sylvanite-like structured and crystallizes in the orthorhombic Ibca space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.96 Å. There are a spread of Li–Br bond distances ranging from 2.57–2.88 Å. In the second Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.95 Å. There are a spread of Li–Br bond distances ranging from 2.54–2.76 Å. In the third Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.97 Å. There are a spread of Li–Br bond distances ranging from 2.59–2.93 Å. In the fourth Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.95 Å. There are a spread of Li–Br bond distances ranging from 2.60–2.81 Å. In the fifth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.95 Å. There are a spread of Li–Br bond distances ranging from 2.53–2.85 Å. In the sixth Li1+ site, Li1+ is bonded in a distorted rectangular see-saw-like geometry to one N3- and three Br1- atoms. The Li–N bond length is 1.96 Å. There are a spread of Li–Br bond distances ranging from 2.59–2.83 Å. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded to six Li1+ atoms to form NLi6 octahedra that share corners with two equivalent BrLi6 octahedra and edges with four BrLi6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the second N3- site, N3- is bonded to six Li1+ atoms to form NLi6 octahedra that share corners with four BrLi6 octahedra and edges with two equivalent BrLi6 octahedra. The corner-sharing octahedra tilt angles range from 40–42°. There are five inequivalent Br1- sites. In the first Br1- site, Br1- is bonded to six Li1+ atoms to form distorted BrLi6 octahedra that share corners with two equivalent NLi6 octahedra, edges with two equivalent NLi6 octahedra, and edges with two equivalent BrLi6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the second Br1- site, Br1- is bonded in a 6-coordinate geometry to six Li1+ atoms. In the third Br1- site, Br1- is bonded in a 6-coordinate geometry to six Li1+ atoms. In the fourth Br1- site, Br1- is bonded to six Li1+ atoms to form distorted BrLi6 octahedra that share corners with two equivalent NLi6 octahedra, corners with two equivalent BrLi6 octahedra, and edges with two equivalent NLi6 octahedra. The corner-sharing octahedra tilt angles range from 42–78°. In the fifth Br1- site, Br1- is bonded to six Li1+ atoms to form distorted BrLi6 octahedra that share corners with two equivalent NLi6 octahedra, corners with two equivalent BrLi6 octahedra, edges with two equivalent NLi6 octahedra, and edges with two equivalent BrLi6 octahedra. The corner-sharing octahedra tilt angles range from 40–78°.