BaBBiS4 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), three equivalent S(3), and four equivalent S(2) atoms. B(1) is bonded in a trigonal planar geometry to one S(1) and two equivalent S(2) atoms. Bi(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1), one B(1), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to two equivalent Ba(1), one B(1), and one Bi(1) atom. In the third S site, S(3) is bonded to three equivalent Ba(1) and one Bi(1) atom to form a mixture of edge and corner-sharing SBa3Bi trigonal pyramids.
BaBBiS4 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), three equivalent S(3), and four equivalent S(2) atoms. There is one shorter (3.27 Å) and one longer (3.28 Å) Ba(1)-S(1) bond length. There is one shorter (3.31 Å) and two longer (3.32 Å) Ba(1)-S(3) bond lengths. There are two shorter (3.40 Å) and two longer (3.50 Å) Ba(1)-S(2) bond lengths. B(1) is bonded in a trigonal planar geometry to one S(1) and two equivalent S(2) atoms. The B(1)-S(1) bond length is 1.80 Å. Both B(1)-S(2) bond lengths are 1.81 Å. Bi(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. The Bi(1)-S(3) bond length is 2.54 Å. Both Bi(1)-S(1) bond lengths are 3.18 Å. Both Bi(1)-S(2) bond lengths are 2.72 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to two equivalent Ba(1), one B(1), and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to two equivalent Ba(1), one B(1), and one Bi(1) atom. In the third S site, S(3) is bonded to three equivalent Ba(1) and one Bi(1) atom to form a mixture of edge and corner-sharing SBa3Bi trigonal pyramids.