Li6NBr3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. In the second Li site, Li(2) is bonded in a 1-coordinate geometry to one N(1), one Br(2), and three equivalent Br(1) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. N(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form NLi6 octahedra that share corners with six equivalent Br(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 25-40°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and three equivalent Li(2) atoms. In the second Br site, Br(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form BrLi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 25-40°.
Li6NBr3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. The Li(1)-N(1) bond length is 1.93 Å. The Li(1)-Br(2) bond length is 2.81 Å. There is one shorter (2.61 Å) and one longer (2.72 Å) Li(1)-Br(1) bond length. In the second Li site, Li(2) is bonded in a 1-coordinate geometry to one N(1), one Br(2), and three equivalent Br(1) atoms. The Li(2)-N(1) bond length is 1.91 Å. The Li(2)-Br(2) bond length is 2.62 Å. There are a spread of Li(2)-Br(1) bond distances ranging from 2.66-3.18 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. The Li(3)-N(1) bond length is 1.93 Å. The Li(3)-Br(2) bond length is 2.76 Å. There is one shorter (2.61 Å) and one longer (2.84 Å) Li(3)-Br(1) bond length. N(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form NLi6 octahedra that share corners with six equivalent Br(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 25-40°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and three equivalent Li(2) atoms. In the second Br site, Br(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form BrLi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 25-40°.