Hg3Bi2(SCl4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted linear geometry to two equivalent S(1) and two equivalent Cl(3) atoms. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(1) atoms. Bi(1) is bonded to one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted edge-sharing BiCl5 square pyramids. S(1) is bonded in a trigonal non-coplanar geometry to one Hg(2) and two equivalent Hg(1) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to two equivalent Bi(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Bi(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Hg(1) and one Bi(1) atom.
Hg3Bi2(SCl4)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted linear geometry to two equivalent S(1) and two equivalent Cl(3) atoms. Both Hg(1)-S(1) bond lengths are 2.45 Å. Both Hg(1)-Cl(3) bond lengths are 3.06 Å. In the second Hg site, Hg(2) is bonded in a linear geometry to two equivalent S(1) atoms. Both Hg(2)-S(1) bond lengths are 2.43 Å. Bi(1) is bonded to one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted edge-sharing BiCl5 square pyramids. The Bi(1)-Cl(3) bond length is 2.63 Å. Both Bi(1)-Cl(1) bond lengths are 2.77 Å. Both Bi(1)-Cl(2) bond lengths are 2.75 Å. S(1) is bonded in a trigonal non-coplanar geometry to one Hg(2) and two equivalent Hg(1) atoms. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to two equivalent Bi(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Bi(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Hg(1) and one Bi(1) atom.