Li2In2GeS6 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form LiS4 trigonal pyramids that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, and corners with three equivalent In(2)S4 tetrahedra. In the second Li site, Li(2) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form LiS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, corners with three equivalent In(2)S4 tetrahedra, and corners with two equivalent Li(1)S4 trigonal pyramids. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form InS4 tetrahedra that share corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, and corners with three equivalent Li(1)S4 trigonal pyramids. In the second In site, In(2) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form InS4 tetrahedra that share corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, and corners with three equivalent Li(1)S4 trigonal pyramids. Ge(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, and corners with two equivalent Li(1)S4 trigonal pyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SLi2In2 tetrahedra. In the second S site, S(2) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SLi2In2 tetrahedra. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(2), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(1), and one Ge(1) atom. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(2), and one Ge(1) atom.
Li2In2GeS6 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form LiS4 trigonal pyramids that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, and corners with three equivalent In(2)S4 tetrahedra. The Li(1)-S(1) bond length is 2.58 Å. The Li(1)-S(2) bond length is 2.60 Å. The Li(1)-S(4) bond length is 2.70 Å. The Li(1)-S(5) bond length is 2.56 Å. In the second Li site, Li(2) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form LiS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, corners with three equivalent In(2)S4 tetrahedra, and corners with two equivalent Li(1)S4 trigonal pyramids. The Li(2)-S(1) bond length is 2.58 Å. The Li(2)-S(2) bond length is 2.60 Å. The Li(2)-S(3) bond length is 2.55 Å. The Li(2)-S(6) bond length is 2.59 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form InS4 tetrahedra that share corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, and corners with three equivalent Li(1)S4 trigonal pyramids. The In(1)-S(1) bond length is 2.50 Å. The In(1)-S(2) bond length is 2.51 Å. The In(1)-S(3) bond length is 2.54 Å. The In(1)-S(5) bond length is 2.52 Å. In the second In site, In(2) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form InS4 tetrahedra that share corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Li(2)S4 tetrahedra, and corners with three equivalent Li(1)S4 trigonal pyramids. The In(2)-S(1) bond length is 2.51 Å. The In(2)-S(2) bond length is 2.52 Å. The In(2)-S(4) bond length is 2.53 Å. The In(2)-S(6) bond length is 2.51 Å. Ge(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, and corners with two equivalent Li(1)S4 trigonal pyramids. The Ge(1)-S(3) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.21 Å. The Ge(1)-S(5) bond length is 2.23 Å. The Ge(1)-S(6) bond length is 2.22 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SLi2In2 tetrahedra. In the second S site, S(2) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SLi2In2 tetrahedra. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(2), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(1), and one Ge(1) atom. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(2), and one Ge(1) atom.