Li14Fe2S9 crystallizes in the trigonal P-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Fe(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with nine equivalent Li(1)S4 tetrahedra,  an edgeedge with one Li(3)S4 tetrahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra,  an edgeedge with one Li(3)S4 tetrahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. In the third Li site, Li(3) is bonded to one S(3) and three equivalent S(1) atoms to form LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra, corners with three equivalent Li(1)S4 tetrahedra, corners with three equivalent Fe(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, edges with three equivalent Li(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. Fe(1) is bonded to one S(2) and three equivalent S(1) atoms to form distorted FeS4 tetrahedra that share corners with three equivalent Li(1)S4 tetrahedra, corners with three equivalent Li(3)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, edges with three equivalent Li(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(3), four equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing SLi6Fe hexagonal pyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Fe(1) atom. In the third S site, S(3) is bonded in a body-centered cubic geometry to two equivalent Li(3) and six equivalent Li(1) atoms.
Li14Fe2S9 crystallizes in the trigonal P-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Fe(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with nine equivalent Li(1)S4 tetrahedra,  an edgeedge with one Li(3)S4 tetrahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. The Li(1)-S(1) bond length is 2.44 Å. The Li(1)-S(3) bond length is 2.54 Å. There is one shorter (2.51 Å) and one longer (2.53 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded to four equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Fe(1)S4 tetrahedra, corners with four equivalent Li(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra,  an edgeedge with one Li(3)S4 tetrahedra,  an edgeedge with one Fe(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. There are a spread of Li(2)-S(1) bond distances ranging from 2.46-2.51 Å. In the third Li site, Li(3) is bonded to one S(3) and three equivalent S(1) atoms to form LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra, corners with three equivalent Li(1)S4 tetrahedra, corners with three equivalent Fe(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, edges with three equivalent Li(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. The Li(3)-S(3) bond length is 2.47 Å. All Li(3)-S(1) bond lengths are 2.46 Å. Fe(1) is bonded to one S(2) and three equivalent S(1) atoms to form distorted FeS4 tetrahedra that share corners with three equivalent Li(1)S4 tetrahedra, corners with three equivalent Li(3)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, edges with three equivalent Li(1)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. The Fe(1)-S(2) bond length is 2.34 Å. All Fe(1)-S(1) bond lengths are 2.36 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(3), four equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing SLi6Fe hexagonal pyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Fe(1) atom. In the third S site, S(3) is bonded in a body-centered cubic geometry to two equivalent Li(3) and six equivalent Li(1) atoms.