Ba2BiInS5 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(2), one S(5), two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In(1) is bonded to one S(2), one S(3), and two equivalent S(5) atoms to form corner-sharing InS4 tetrahedra. Bi(1) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(2), and two equivalent S(4) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Bi(1) atom to form SBa4Bi square pyramids that share corners with two equivalent S(2)Ba3InBi2 octahedra, corners with four equivalent S(3)Ba4In square pyramids, corners with two equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with three equivalent S(2)Ba3InBi2 octahedra, edges with two equivalent S(1)Ba4Bi square pyramids, edges with two equivalent S(3)Ba4In square pyramids, and edges with three equivalent S(4)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the second S site, S(2) is bonded to one Ba(1), two equivalent Ba(2), one In(1), and two equivalent Bi(1) atoms to form distorted SBa3InBi2 octahedra that share corners with two equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(3)Ba4In square pyramids, corners with two equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with two equivalent S(2)Ba3InBi2 octahedra, edges with three equivalent S(1)Ba4Bi square pyramids, edges with three equivalent S(4)Ba3Bi2 trigonal bipyramids, and  a faceface with one S(3)Ba4In square pyramid. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one In(1) atom to form distorted SBa4In square pyramids that share corners with four equivalent S(2)Ba3InBi2 octahedra, corners with four equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with two equivalent S(1)Ba4Bi square pyramids, edges with two equivalent S(3)Ba4In square pyramids,  an edgeedge with one S(4)Ba3Bi2 trigonal bipyramid, and  a faceface with one S(2)Ba3InBi2 octahedra. The corner-sharing octahedral tilt angles range from 42-67°. In the fourth S site, S(4) is bonded to one Ba(2), two equivalent Ba(1), and two equivalent Bi(1) atoms to form SBa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)Ba3InBi2 octahedra, corners with two equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(3)Ba4In square pyramids, edges with three equivalent S(2)Ba3InBi2 octahedra,  an edgeedge with one S(3)Ba4In square pyramid, edges with three equivalent S(1)Ba4Bi square pyramids, and edges with two equivalent S(4)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 12°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent In(1), and one Bi(1) atom.
Ba2BiInS5 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(2), one S(5), two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms. The Ba(1)-S(2) bond length is 3.56 Å. The Ba(1)-S(5) bond length is 3.70 Å. Both Ba(1)-S(1) bond lengths are 3.25 Å. Both Ba(1)-S(3) bond lengths are 3.18 Å. Both Ba(1)-S(4) bond lengths are 3.25 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(4), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ba(2)-S(4) bond length is 3.20 Å. The Ba(2)-S(5) bond length is 3.41 Å. Both Ba(2)-S(1) bond lengths are 3.23 Å. Both Ba(2)-S(2) bond lengths are 3.46 Å. Both Ba(2)-S(3) bond lengths are 3.25 Å. In(1) is bonded to one S(2), one S(3), and two equivalent S(5) atoms to form corner-sharing InS4 tetrahedra. The In(1)-S(2) bond length is 2.57 Å. The In(1)-S(3) bond length is 2.45 Å. Both In(1)-S(5) bond lengths are 2.53 Å. Bi(1) is bonded in a 6-coordinate geometry to one S(1), one S(5), two equivalent S(2), and two equivalent S(4) atoms. The Bi(1)-S(1) bond length is 2.63 Å. The Bi(1)-S(5) bond length is 3.22 Å. Both Bi(1)-S(2) bond lengths are 2.95 Å. Both Bi(1)-S(4) bond lengths are 2.81 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Bi(1) atom to form SBa4Bi square pyramids that share corners with two equivalent S(2)Ba3InBi2 octahedra, corners with four equivalent S(3)Ba4In square pyramids, corners with two equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with three equivalent S(2)Ba3InBi2 octahedra, edges with two equivalent S(1)Ba4Bi square pyramids, edges with two equivalent S(3)Ba4In square pyramids, and edges with three equivalent S(4)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 33°. In the second S site, S(2) is bonded to one Ba(1), two equivalent Ba(2), one In(1), and two equivalent Bi(1) atoms to form distorted SBa3InBi2 octahedra that share corners with two equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(3)Ba4In square pyramids, corners with two equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with two equivalent S(2)Ba3InBi2 octahedra, edges with three equivalent S(1)Ba4Bi square pyramids, edges with three equivalent S(4)Ba3Bi2 trigonal bipyramids, and  a faceface with one S(3)Ba4In square pyramid. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one In(1) atom to form distorted SBa4In square pyramids that share corners with four equivalent S(2)Ba3InBi2 octahedra, corners with four equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(4)Ba3Bi2 trigonal bipyramids, edges with two equivalent S(1)Ba4Bi square pyramids, edges with two equivalent S(3)Ba4In square pyramids,  an edgeedge with one S(4)Ba3Bi2 trigonal bipyramid, and  a faceface with one S(2)Ba3InBi2 octahedra. The corner-sharing octahedral tilt angles range from 42-67°. In the fourth S site, S(4) is bonded to one Ba(2), two equivalent Ba(1), and two equivalent Bi(1) atoms to form SBa3Bi2 trigonal bipyramids that share corners with two equivalent S(2)Ba3InBi2 octahedra, corners with two equivalent S(1)Ba4Bi square pyramids, corners with four equivalent S(3)Ba4In square pyramids, edges with three equivalent S(2)Ba3InBi2 octahedra,  an edgeedge with one S(3)Ba4In square pyramid, edges with three equivalent S(1)Ba4Bi square pyramids, and edges with two equivalent S(4)Ba3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 12°. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent In(1), and one Bi(1) atom.