Li6Sb3S 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 Sb(1), two equivalent Sb(2), and one S(1) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. In the third Li site, Li(3) is bonded in a 1-coordinate geometry to one Sb(1), one Sb(2), and one S(1) atom. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form distorted SbLi6 octahedra that share corners with six equivalent S(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 26-58°. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one Li(3), two equivalent Li(1), and two equivalent Li(2) atoms. S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form SLi6 octahedra that share corners with six equivalent Sb(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 26-58°.
Li6Sb3S 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 Sb(1), two equivalent Sb(2), and one S(1) atom. The Li(1)-Sb(1) bond length is 2.75 Å. There is one shorter (2.85 Å) and one longer (3.13 Å) Li(1)-Sb(2) bond length. The Li(1)-S(1) bond length is 2.32 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Sb(1), two equivalent Sb(2), and one S(1) atom. The Li(2)-Sb(1) bond length is 2.95 Å. There is one shorter (2.94 Å) and one longer (3.00 Å) Li(2)-Sb(2) bond length. The Li(2)-S(1) bond length is 2.39 Å. In the third Li site, Li(3) is bonded in a 1-coordinate geometry to one Sb(1), one Sb(2), and one S(1) atom. The Li(3)-Sb(1) bond length is 2.80 Å. The Li(3)-Sb(2) bond length is 2.92 Å. The Li(3)-S(1) bond length is 2.32 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form distorted SbLi6 octahedra that share corners with six equivalent S(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 26-58°. In the second Sb site, Sb(2) is bonded in a 5-coordinate geometry to one Li(3), two equivalent Li(1), and two equivalent Li(2) atoms. S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form SLi6 octahedra that share corners with six equivalent Sb(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 26-58°.