Hg4GeS6 crystallizes in the monoclinic Cc space group. There are four inequivalent Hg sites. In the first Hg site, Hg(1) is bonded to one S(2), one S(3), one S(5), and one S(6) atom to form distorted HgS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(2)S4 tetrahedra, corners with two equivalent Hg(4)S4 trigonal pyramids, and corners with three equivalent Hg(3)S4 trigonal pyramids. In the second Hg site, Hg(2) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form HgS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(1)S4 tetrahedra, corners with two equivalent Hg(3)S4 trigonal pyramids, and corners with three equivalent Hg(4)S4 trigonal pyramids. In the third Hg site, Hg(3) is bonded to one S(2), one S(3), one S(4), and one S(6) atom to form HgS4 trigonal pyramids that share corners with two equivalent Hg(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(1)S4 tetrahedra, and corners with three equivalent Hg(4)S4 trigonal pyramids. In the fourth Hg site, Hg(4) is bonded to one S(1), one S(3), one S(4), and one S(6) atom to form HgS4 trigonal pyramids that share corners with two equivalent Hg(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(2)S4 tetrahedra, and corners with three equivalent Hg(3)S4 trigonal pyramids. Ge(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form GeS4 tetrahedra that share corners with two equivalent Hg(1)S4 tetrahedra, corners with two equivalent Hg(2)S4 tetrahedra, corners with two equivalent Hg(3)S4 trigonal pyramids, and corners with two equivalent Hg(4)S4 trigonal pyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Hg(2), one Hg(4), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Hg(1), one Hg(3), and one Ge(1) atom. In the third S site, S(3) is bonded to one Hg(1), one Hg(2), one Hg(3), and one Hg(4) atom to form corner-sharing SHg4 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Hg(3), one Hg(4), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one Hg(1), one Hg(2), and one Ge(1) atom. In the sixth S site, S(6) is bonded to one Hg(1), one Hg(2), one Hg(3), and one Hg(4) atom to form corner-sharing SHg4 tetrahedra.
Hg4GeS6 crystallizes in the monoclinic Cc space group. There are four inequivalent Hg sites. In the first Hg site, Hg(1) is bonded to one S(2), one S(3), one S(5), and one S(6) atom to form distorted HgS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(2)S4 tetrahedra, corners with two equivalent Hg(4)S4 trigonal pyramids, and corners with three equivalent Hg(3)S4 trigonal pyramids. The Hg(1)-S(2) bond length is 2.62 Å. The Hg(1)-S(3) bond length is 2.55 Å. The Hg(1)-S(5) bond length is 2.74 Å. The Hg(1)-S(6) bond length is 2.71 Å. In the second Hg site, Hg(2) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form HgS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(1)S4 tetrahedra, corners with two equivalent Hg(3)S4 trigonal pyramids, and corners with three equivalent Hg(4)S4 trigonal pyramids. The Hg(2)-S(1) bond length is 2.60 Å. The Hg(2)-S(3) bond length is 2.73 Å. The Hg(2)-S(5) bond length is 2.59 Å. The Hg(2)-S(6) bond length is 2.56 Å. In the third Hg site, Hg(3) is bonded to one S(2), one S(3), one S(4), and one S(6) atom to form HgS4 trigonal pyramids that share corners with two equivalent Hg(2)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(1)S4 tetrahedra, and corners with three equivalent Hg(4)S4 trigonal pyramids. The Hg(3)-S(2) bond length is 2.73 Å. The Hg(3)-S(3) bond length is 2.58 Å. The Hg(3)-S(4) bond length is 2.63 Å. The Hg(3)-S(6) bond length is 2.58 Å. In the fourth Hg site, Hg(4) is bonded to one S(1), one S(3), one S(4), and one S(6) atom to form HgS4 trigonal pyramids that share corners with two equivalent Hg(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with three equivalent Hg(2)S4 tetrahedra, and corners with three equivalent Hg(3)S4 trigonal pyramids. The Hg(4)-S(1) bond length is 2.78 Å. The Hg(4)-S(3) bond length is 2.60 Å. The Hg(4)-S(4) bond length is 2.59 Å. The Hg(4)-S(6) bond length is 2.65 Å. Ge(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form GeS4 tetrahedra that share corners with two equivalent Hg(1)S4 tetrahedra, corners with two equivalent Hg(2)S4 tetrahedra, corners with two equivalent Hg(3)S4 trigonal pyramids, and corners with two equivalent Hg(4)S4 trigonal pyramids. The Ge(1)-S(1) bond length is 2.22 Å. The Ge(1)-S(2) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.25 Å. The Ge(1)-S(5) bond length is 2.23 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Hg(2), one Hg(4), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Hg(1), one Hg(3), and one Ge(1) atom. In the third S site, S(3) is bonded to one Hg(1), one Hg(2), one Hg(3), and one Hg(4) atom to form corner-sharing SHg4 tetrahedra. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Hg(3), one Hg(4), and one Ge(1) atom. In the fifth S site, S(5) is bonded in a trigonal non-coplanar geometry to one Hg(1), one Hg(2), and one Ge(1) atom. In the sixth S site, S(6) is bonded to one Hg(1), one Hg(2), one Hg(3), and one Hg(4) atom to form corner-sharing SHg4 tetrahedra.