Li6AsS5I crystallizes in the monoclinic Cc space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one S(1), one S(4), and one S(5) atom. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one S(2), one S(4), and one S(5) atom. In the third Li site, Li(3) is bonded to one S(1), one S(3), one S(4), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(4)S3I tetrahedra, and corners with three equivalent Li(6)S3I tetrahedra. In the fourth Li site, Li(4) is bonded to one S(2), one S(3), one S(4), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(3)S3I tetrahedra, and corners with three equivalent Li(6)S3I tetrahedra. In the fifth Li site, Li(5) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(4) atom. In the sixth Li site, Li(6) is bonded to one S(3), one S(4), one S(5), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(3)S3I tetrahedra, and corners with three equivalent Li(4)S3I tetrahedra. As(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form AsS4 tetrahedra that share corners with two equivalent Li(3)S3I tetrahedra, corners with two equivalent Li(4)S3I tetrahedra, and corners with two equivalent Li(6)S3I tetrahedra. There are five inequivalent S sites. In the first S site, S(3) is bonded to one Li(3), one Li(4), one Li(6), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(2)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 61-62°. In the second S site, S(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted corner-sharing SLi6 octahedra. In the third S site, S(5) is bonded to one Li(1), one Li(2), one Li(6), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(2)Li3As tetrahedra, and corners with two equivalent S(3)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. In the fourth S site, S(1) is bonded to one Li(1), one Li(3), one Li(5), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(2)Li3As tetrahedra, corners with two equivalent S(3)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the fifth S site, S(2) is bonded to one Li(2), one Li(4), one Li(5), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(3)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. I(1) is bonded in a trigonal planar geometry to one Li(3), one Li(4), and one Li(6) atom.
Li6AsS5I crystallizes in the monoclinic Cc space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one S(1), one S(4), and one S(5) atom. The Li(1)-S(1) bond length is 2.42 Å. The Li(1)-S(4) bond length is 2.37 Å. The Li(1)-S(5) bond length is 2.44 Å. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one S(2), one S(4), and one S(5) atom. The Li(2)-S(2) bond length is 2.44 Å. The Li(2)-S(4) bond length is 2.37 Å. The Li(2)-S(5) bond length is 2.42 Å. In the third Li site, Li(3) is bonded to one S(1), one S(3), one S(4), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(4)S3I tetrahedra, and corners with three equivalent Li(6)S3I tetrahedra. The Li(3)-S(1) bond length is 2.47 Å. The Li(3)-S(3) bond length is 2.53 Å. The Li(3)-S(4) bond length is 2.43 Å. The Li(3)-I(1) bond length is 2.94 Å. In the fourth Li site, Li(4) is bonded to one S(2), one S(3), one S(4), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(3)S3I tetrahedra, and corners with three equivalent Li(6)S3I tetrahedra. The Li(4)-S(2) bond length is 2.50 Å. The Li(4)-S(3) bond length is 2.54 Å. The Li(4)-S(4) bond length is 2.43 Å. The Li(4)-I(1) bond length is 2.91 Å. In the fifth Li site, Li(5) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(4) atom. The Li(5)-S(1) bond length is 2.43 Å. The Li(5)-S(2) bond length is 2.42 Å. The Li(5)-S(4) bond length is 2.35 Å. In the sixth Li site, Li(6) is bonded to one S(3), one S(4), one S(5), and one I(1) atom to form distorted LiS3I tetrahedra that share corners with two equivalent As(1)S4 tetrahedra, corners with three equivalent Li(3)S3I tetrahedra, and corners with three equivalent Li(4)S3I tetrahedra. The Li(6)-S(3) bond length is 2.54 Å. The Li(6)-S(4) bond length is 2.43 Å. The Li(6)-S(5) bond length is 2.49 Å. The Li(6)-I(1) bond length is 2.90 Å. As(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form AsS4 tetrahedra that share corners with two equivalent Li(3)S3I tetrahedra, corners with two equivalent Li(4)S3I tetrahedra, and corners with two equivalent Li(6)S3I tetrahedra. The As(1)-S(1) bond length is 2.20 Å. The As(1)-S(2) bond length is 2.20 Å. The As(1)-S(3) bond length is 2.18 Å. The As(1)-S(5) bond length is 2.19 Å. There are five inequivalent S sites. In the first S site, S(3) is bonded to one Li(3), one Li(4), one Li(6), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(2)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 61-62°. In the second S site, S(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form distorted corner-sharing SLi6 octahedra. In the third S site, S(5) is bonded to one Li(1), one Li(2), one Li(6), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(2)Li3As tetrahedra, and corners with two equivalent S(3)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. In the fourth S site, S(1) is bonded to one Li(1), one Li(3), one Li(5), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(2)Li3As tetrahedra, corners with two equivalent S(3)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the fifth S site, S(2) is bonded to one Li(2), one Li(4), one Li(5), and one As(1) atom to form SLi3As tetrahedra that share corners with three equivalent S(4)Li6 octahedra, corners with two equivalent S(1)Li3As tetrahedra, corners with two equivalent S(3)Li3As tetrahedra, and corners with two equivalent S(5)Li3As tetrahedra. The corner-sharing octahedral tilt angles range from 50-62°. I(1) is bonded in a trigonal planar geometry to one Li(3), one Li(4), and one Li(6) atom.