Li14Mn2S9 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 Mn(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 Mn(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 Mn(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 Mn(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 Mn(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. Mn(1) is bonded to one S(2) and three equivalent S(1) atoms to form MnS4 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 Mn(1) atom to form a mixture of distorted edge and corner-sharing SLi6Mn hexagonal pyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Mn(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.
Li14Mn2S9 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 Mn(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 Mn(1)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. The Li(1)-S(1) bond length is 2.48 Å. The Li(1)-S(3) bond length is 2.51 Å. There is one shorter (2.44 Å) and one longer (2.57 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 Mn(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 Mn(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 2.40-2.51 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 Mn(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 2.49 Å. All Li(3)-S(1) bond lengths are 2.44 Å. Mn(1) is bonded to one S(2) and three equivalent S(1) atoms to form MnS4 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 Mn(1)-S(2) bond length is 2.39 Å. All Mn(1)-S(1) bond lengths are 2.39 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 Mn(1) atom to form a mixture of distorted edge and corner-sharing SLi6Mn hexagonal pyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Mn(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.