Cd3ZnGeS6 crystallizes in the monoclinic Cc space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form distorted CdS4 trigonal pyramids that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Cd(2)S4 tetrahedra, and corners with three equivalent Cd(3)S4 tetrahedra. In the second Cd site, Cd(2) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form CdS4 tetrahedra that share corners with two equivalent Cd(3)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, and corners with three equivalent Cd(1)S4 trigonal pyramids. In the third Cd site, Cd(3) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form CdS4 tetrahedra that share corners with two equivalent Cd(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, and corners with three equivalent Cd(1)S4 trigonal pyramids. Zn(1) is bonded to one S(1), one S(3), one S(4), and one S(6) atom to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Cd(2)S4 tetrahedra, corners with three equivalent Cd(3)S4 tetrahedra, and corners with two equivalent Cd(1)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 Cd(2)S4 tetrahedra, corners with two equivalent Cd(3)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with two equivalent Cd(1)S4 trigonal pyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Cd(1), one Cd(2), one Cd(3), and one Zn(1) atom to form corner-sharing SZnCd3 tetrahedra. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Cd(2), and one Ge(1) atom. In the third S site, S(3) is bonded to one Cd(1), one Cd(2), one Cd(3), and one Zn(1) atom to form distorted corner-sharing SZnCd3 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Zn(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Cd(1), one Cd(3), and one Ge(1) atom. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Cd(3), one Zn(1), and one Ge(1) atom.
Cd3ZnGeS6 crystallizes in the monoclinic Cc space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form distorted CdS4 trigonal pyramids that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Cd(2)S4 tetrahedra, and corners with three equivalent Cd(3)S4 tetrahedra. The Cd(1)-S(1) bond length is 2.59 Å. The Cd(1)-S(2) bond length is 2.69 Å. The Cd(1)-S(3) bond length is 2.65 Å. The Cd(1)-S(5) bond length is 2.61 Å. In the second Cd site, Cd(2) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form CdS4 tetrahedra that share corners with two equivalent Cd(3)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, and corners with three equivalent Cd(1)S4 trigonal pyramids. The Cd(2)-S(1) bond length is 2.60 Å. The Cd(2)-S(2) bond length is 2.59 Å. The Cd(2)-S(3) bond length is 2.59 Å. The Cd(2)-S(4) bond length is 2.61 Å. In the third Cd site, Cd(3) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form CdS4 tetrahedra that share corners with two equivalent Cd(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, and corners with three equivalent Cd(1)S4 trigonal pyramids. The Cd(3)-S(1) bond length is 2.59 Å. The Cd(3)-S(3) bond length is 2.58 Å. The Cd(3)-S(5) bond length is 2.57 Å. The Cd(3)-S(6) bond length is 2.67 Å. Zn(1) is bonded to one S(1), one S(3), one S(4), and one S(6) atom to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Cd(2)S4 tetrahedra, corners with three equivalent Cd(3)S4 tetrahedra, and corners with two equivalent Cd(1)S4 trigonal pyramids. The Zn(1)-S(1) bond length is 2.39 Å. The Zn(1)-S(3) bond length is 2.44 Å. The Zn(1)-S(4) bond length is 2.47 Å. The Zn(1)-S(6) bond length is 2.42 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 Cd(2)S4 tetrahedra, corners with two equivalent Cd(3)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with two equivalent Cd(1)S4 trigonal pyramids. The Ge(1)-S(2) bond length is 2.20 Å. The Ge(1)-S(4) bond length is 2.24 Å. The Ge(1)-S(5) bond length is 2.22 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 Cd(1), one Cd(2), one Cd(3), and one Zn(1) atom to form corner-sharing SZnCd3 tetrahedra. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Cd(2), and one Ge(1) atom. In the third S site, S(3) is bonded to one Cd(1), one Cd(2), one Cd(3), and one Zn(1) atom to form distorted corner-sharing SZnCd3 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Cd(2), one Zn(1), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Cd(1), one Cd(3), and one Ge(1) atom. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Cd(3), one Zn(1), and one Ge(1) atom.