Li5P(S2Cl)2 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2), two equivalent S(1), and two equivalent Cl(1) atoms to form distorted LiS3Cl2 trigonal bipyramids that share corners with three equivalent Li(2)S2Cl2 tetrahedra, corners with three equivalent P(1)S4 tetrahedra, corners with five equivalent Li(1)S3Cl2 trigonal bipyramids, and edges with four equivalent Li(1)S3Cl2 trigonal bipyramids. In the second Li site, Li(2) is bonded to two equivalent S(2) and two equivalent Cl(1) atoms to form LiS2Cl2 tetrahedra that share corners with two equivalent P(1)S4 tetrahedra and corners with twelve equivalent Li(1)S3Cl2 trigonal bipyramids. P(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form PS4 tetrahedra that share corners with two equivalent Li(2)S2Cl2 tetrahedra and corners with twelve equivalent Li(1)S3Cl2 trigonal bipyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one P(1) atom. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form corner-sharing SLi3P tetrahedra. Cl(1) is bonded in a 5-coordinate geometry to one Li(2) and four equivalent Li(1) atoms.
Li5P(S2Cl)2 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(2), two equivalent S(1), and two equivalent Cl(1) atoms to form distorted LiS3Cl2 trigonal bipyramids that share corners with three equivalent Li(2)S2Cl2 tetrahedra, corners with three equivalent P(1)S4 tetrahedra, corners with five equivalent Li(1)S3Cl2 trigonal bipyramids, and edges with four equivalent Li(1)S3Cl2 trigonal bipyramids. The Li(1)-S(2) bond length is 2.53 Å. There is one shorter (2.52 Å) and one longer (2.76 Å) Li(1)-S(1) bond length. There is one shorter (2.38 Å) and one longer (2.74 Å) Li(1)-Cl(1) bond length. In the second Li site, Li(2) is bonded to two equivalent S(2) and two equivalent Cl(1) atoms to form LiS2Cl2 tetrahedra that share corners with two equivalent P(1)S4 tetrahedra and corners with twelve equivalent Li(1)S3Cl2 trigonal bipyramids. Both Li(2)-S(2) bond lengths are 2.49 Å. Both Li(2)-Cl(1) bond lengths are 2.33 Å. P(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form PS4 tetrahedra that share corners with two equivalent Li(2)S2Cl2 tetrahedra and corners with twelve equivalent Li(1)S3Cl2 trigonal bipyramids. Both P(1)-S(1) bond lengths are 2.07 Å. Both P(1)-S(2) bond lengths are 2.06 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one P(1) atom. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form corner-sharing SLi3P tetrahedra. Cl(1) is bonded in a 5-coordinate geometry to one Li(2) and four equivalent Li(1) atoms.