Ba2HgS5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. Hg(1) is bonded in a linear geometry to one S(2) and one S(3) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent S(4) atoms. In the second S site, S(2) is bonded to four equivalent Ba(1) and one Hg(1) atom to form distorted SBa4Hg trigonal bipyramids that share corners with four equivalent S(2)Ba4Hg trigonal bipyramids, corners with eight equivalent S(4)Ba3S trigonal pyramids, and edges with two equivalent S(4)Ba3S trigonal pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Hg(1) atom. In the fourth S site, S(4) is bonded to three equivalent Ba(1) and one S(1) atom to form distorted SBa3S trigonal pyramids that share corners with four equivalent S(2)Ba4Hg trigonal bipyramids, corners with five equivalent S(4)Ba3S trigonal pyramids,  an edgeedge with one S(2)Ba4Hg trigonal bipyramid, and  an edgeedge with one S(4)Ba3S trigonal pyramid.
Ba2HgS5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. There is one shorter (3.47 Å) and one longer (3.50 Å) Ba(1)-S(1) bond length. There is one shorter (3.19 Å) and one longer (3.25 Å) Ba(1)-S(2) bond length. There is one shorter (3.26 Å) and one longer (3.32 Å) Ba(1)-S(3) bond length. There are a spread of Ba(1)-S(4) bond distances ranging from 3.20-3.32 Å. Hg(1) is bonded in a linear geometry to one S(2) and one S(3) atom. The Hg(1)-S(2) bond length is 2.36 Å. The Hg(1)-S(3) bond length is 2.35 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to four equivalent Ba(1) and two equivalent S(4) atoms. Both S(1)-S(4) bond lengths are 2.07 Å. In the second S site, S(2) is bonded to four equivalent Ba(1) and one Hg(1) atom to form distorted SBa4Hg trigonal bipyramids that share corners with four equivalent S(2)Ba4Hg trigonal bipyramids, corners with eight equivalent S(4)Ba3S trigonal pyramids, and edges with two equivalent S(4)Ba3S trigonal pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Hg(1) atom. In the fourth S site, S(4) is bonded to three equivalent Ba(1) and one S(1) atom to form distorted SBa3S trigonal pyramids that share corners with four equivalent S(2)Ba4Hg trigonal bipyramids, corners with five equivalent S(4)Ba3S trigonal pyramids,  an edgeedge with one S(2)Ba4Hg trigonal bipyramid, and  an edgeedge with one S(4)Ba3S trigonal pyramid.