Li6NI3 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. In the second Li site, Li(2) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. In the third Li site, Li(3) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. In the fourth Li site, Li(4) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. In the fifth Li site, Li(5) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(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 I(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-36°. There are two inequivalent I sites. In the first I site, I(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 I site, I(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form ILi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-36°.
Li6NI3 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. The Li(1)-N(1) bond length is 1.94 Å. The Li(1)-I(2) bond length is 2.96 Å. Both Li(1)-I(1) bond lengths are 2.96 Å. In the second Li site, Li(2) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. The Li(2)-N(1) bond length is 1.92 Å. The Li(2)-I(2) bond length is 2.87 Å. There is one shorter (3.29 Å) and one longer (3.30 Å) Li(2)-I(1) bond length. In the third Li site, Li(3) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. The Li(3)-N(1) bond length is 1.93 Å. The Li(3)-I(2) bond length is 2.98 Å. Both Li(3)-I(1) bond lengths are 3.02 Å. In the fourth Li site, Li(4) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. The Li(4)-N(1) bond length is 1.93 Å. The Li(4)-I(2) bond length is 3.01 Å. Both Li(4)-I(1) bond lengths are 2.94 Å. In the fifth Li site, Li(5) is bonded in a distorted single-bond geometry to one N(1), one I(2), and two equivalent I(1) atoms. The Li(5)-N(1) bond length is 1.93 Å. The Li(5)-I(2) bond length is 3.09 Å. Both Li(5)-I(1) bond lengths are 2.99 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 I(2)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-36°. There are two inequivalent I sites. In the first I site, I(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 I site, I(2) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and two equivalent Li(2) atoms to form ILi6 octahedra that share corners with six equivalent N(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 4-36°.