Ag2In2GeS6 crystallizes in the monoclinic Cc space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form distorted AgS4 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 Ag(2)S4 trigonal pyramids. In the second Ag site, Ag(2) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form AgS4 trigonal pyramids that share corners with two equivalent Ag(1)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. 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 Ag(1)S4 tetrahedra, and corners with three equivalent Ag(2)S4 trigonal pyramids. In the second In site, In(2) is bonded to one S(1), one S(3), 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 Ag(1)S4 tetrahedra, and corners with three equivalent Ag(2)S4 trigonal pyramids. Ge(1) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Ag(1)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, and corners with two equivalent Ag(2)S4 trigonal pyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ag(1), one Ag(2), one In(1), and one In(2) atom to form corner-sharing SIn2Ag2 tetrahedra. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Ag(1), one In(1), and one Ge(1) atom. In the third S site, S(3) is bonded to one Ag(1), one Ag(2), one In(1), and one In(2) atom to form corner-sharing SIn2Ag2 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Ag(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 Ag(2), 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 Ag(2), one In(2), and one Ge(1) atom.
Ag2In2GeS6 crystallizes in the monoclinic Cc space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form distorted AgS4 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 Ag(2)S4 trigonal pyramids. The Ag(1)-S(1) bond length is 2.66 Å. The Ag(1)-S(2) bond length is 2.73 Å. The Ag(1)-S(3) bond length is 2.59 Å. The Ag(1)-S(4) bond length is 2.65 Å. In the second Ag site, Ag(2) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form AgS4 trigonal pyramids that share corners with two equivalent Ag(1)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 Ag(2)-S(1) bond length is 2.62 Å. The Ag(2)-S(3) bond length is 2.62 Å. The Ag(2)-S(5) bond length is 2.59 Å. The Ag(2)-S(6) bond length is 2.76 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 Ag(1)S4 tetrahedra, and corners with three equivalent Ag(2)S4 trigonal pyramids. The In(1)-S(1) bond length is 2.53 Å. The In(1)-S(2) bond length is 2.55 Å. The In(1)-S(3) bond length is 2.52 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(3), 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 Ag(1)S4 tetrahedra, and corners with three equivalent Ag(2)S4 trigonal pyramids. The In(2)-S(1) bond length is 2.52 Å. The In(2)-S(3) bond length is 2.53 Å. The In(2)-S(4) bond length is 2.51 Å. The In(2)-S(6) bond length is 2.53 Å. Ge(1) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Ag(1)S4 tetrahedra, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, and corners with two equivalent Ag(2)S4 trigonal pyramids. The Ge(1)-S(2) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.22 Å. The Ge(1)-S(5) bond length is 2.24 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 Ag(1), one Ag(2), one In(1), and one In(2) atom to form corner-sharing SIn2Ag2 tetrahedra. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Ag(1), one In(1), and one Ge(1) atom. In the third S site, S(3) is bonded to one Ag(1), one Ag(2), one In(1), and one In(2) atom to form corner-sharing SIn2Ag2 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Ag(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 Ag(2), 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 Ag(2), one In(2), and one Ge(1) atom.