Li6NBr3 crystallizes in the monoclinic Cm space group. There are five 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 two 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. In the fourth Li site, Li(4) is bonded in a distorted single-bond geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. In the fifth Li site, Li(5) is bonded in a distorted single-bond geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. N(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form NLi6 octahedra that share corners with six equivalent Br(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 11-38°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms. In the second Br site, Br(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form BrLi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 11-38°.
Li6NBr3 crystallizes in the monoclinic Cm space group. There are five 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 1.98 Å. The Li(1)-Br(2) bond length is 2.71 Å. Both Li(1)-Br(1) bond lengths are 2.72 Å. In the second Li site, Li(2) is bonded in a 1-coordinate geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. The Li(2)-N(1) bond length is 1.93 Å. The Li(2)-Br(2) bond length is 2.56 Å. There is one shorter (3.00 Å) and one longer (3.03 Å) Li(2)-Br(1) bond length. 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 1.95 Å. The Li(3)-Br(2) bond length is 2.74 Å. Both Li(3)-Br(1) bond lengths are 2.84 Å. In the fourth Li site, Li(4) is bonded in a distorted single-bond geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. The Li(4)-N(1) bond length is 1.95 Å. The Li(4)-Br(2) bond length is 2.79 Å. Both Li(4)-Br(1) bond lengths are 2.70 Å. In the fifth Li site, Li(5) is bonded in a distorted single-bond geometry to one N(1), one Br(2), and two equivalent Br(1) atoms. The Li(5)-N(1) bond length is 1.93 Å. The Li(5)-Br(2) bond length is 2.96 Å. Both Li(5)-Br(1) bond lengths are 2.79 Å. N(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form NLi6 octahedra that share corners with six equivalent Br(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 11-38°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms. In the second Br site, Br(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form BrLi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 11-38°.