K2Hg3Sn2S8 crystallizes in the orthorhombic Aea2 space group. K(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted see-saw-like geometry to one S(1), one S(2), and two equivalent S(4) atoms. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(3) atoms. Sn(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(2) is bonded to two equivalent K(1), one Hg(1), and one Sn(1) atom to form distorted SK2SnHg trigonal pyramids that share corners with three equivalent S(4)KSnHg2 tetrahedra, corners with two equivalent S(2)K2SnHg trigonal pyramids, corners with five equivalent S(3)K2SnHg trigonal pyramids, and  an edgeedge with one S(4)KSnHg2 tetrahedra. In the second S site, S(3) is bonded to two equivalent K(1), one Hg(2), and one Sn(1) atom to form distorted SK2SnHg trigonal pyramids that share corners with three equivalent S(4)KSnHg2 tetrahedra, corners with three equivalent S(3)K2SnHg trigonal pyramids, and corners with five equivalent S(2)K2SnHg trigonal pyramids. In the third S site, S(4) is bonded to one K(1), two equivalent Hg(1), and one Sn(1) atom to form distorted SKSnHg2 tetrahedra that share corners with two equivalent S(4)KSnHg2 tetrahedra, corners with three equivalent S(2)K2SnHg trigonal pyramids, corners with three equivalent S(3)K2SnHg trigonal pyramids, and  an edgeedge with one S(2)K2SnHg trigonal pyramid. In the fourth S site, S(1) is bonded in a 4-coordinate geometry to two equivalent K(1), one Hg(1), and one Sn(1) atom.
K2Hg3Sn2S8 crystallizes in the orthorhombic Aea2 space group. K(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The K(1)-S(4) bond length is 3.26 Å. There is one shorter (3.28 Å) and one longer (3.67 Å) K(1)-S(1) bond length. There is one shorter (3.39 Å) and one longer (3.60 Å) K(1)-S(2) bond length. There is one shorter (3.34 Å) and one longer (3.63 Å) K(1)-S(3) bond length. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted see-saw-like geometry to one S(1), one S(2), and two equivalent S(4) atoms. The Hg(1)-S(1) bond length is 2.47 Å. The Hg(1)-S(2) bond length is 2.46 Å. There is one shorter (2.86 Å) and one longer (2.91 Å) Hg(1)-S(4) bond length. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(3) atoms. Both Hg(2)-S(3) bond lengths are 2.38 Å. Sn(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Sn(1)-S(1) bond length is 2.44 Å. The Sn(1)-S(2) bond length is 2.44 Å. The Sn(1)-S(3) bond length is 2.47 Å. The Sn(1)-S(4) bond length is 2.38 Å. There are four inequivalent S sites. In the first S site, S(2) is bonded to two equivalent K(1), one Hg(1), and one Sn(1) atom to form distorted SK2SnHg trigonal pyramids that share corners with three equivalent S(4)KSnHg2 tetrahedra, corners with two equivalent S(2)K2SnHg trigonal pyramids, corners with five equivalent S(3)K2SnHg trigonal pyramids, and  an edgeedge with one S(4)KSnHg2 tetrahedra. In the second S site, S(3) is bonded to two equivalent K(1), one Hg(2), and one Sn(1) atom to form distorted SK2SnHg trigonal pyramids that share corners with three equivalent S(4)KSnHg2 tetrahedra, corners with three equivalent S(3)K2SnHg trigonal pyramids, and corners with five equivalent S(2)K2SnHg trigonal pyramids. In the third S site, S(4) is bonded to one K(1), two equivalent Hg(1), and one Sn(1) atom to form distorted SKSnHg2 tetrahedra that share corners with two equivalent S(4)KSnHg2 tetrahedra, corners with three equivalent S(2)K2SnHg trigonal pyramids, corners with three equivalent S(3)K2SnHg trigonal pyramids, and  an edgeedge with one S(2)K2SnHg trigonal pyramid. In the fourth S site, S(1) is bonded in a 4-coordinate geometry to two equivalent K(1), one Hg(1), and one Sn(1) atom.