Ba2BiFeS5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. Fe(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. Bi(1) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(1) atoms. There are four inequivalent S sites. In the first S site, S(4) is bonded to four equivalent Ba(1) and one Fe(1) atom to form distorted SBa4Fe square pyramids that share corners with four equivalent S(2)Ba4Bi square pyramids, corners with six equivalent S(1)Ba2FeBi2 trigonal bipyramids, edges with two equivalent S(2)Ba4Bi square pyramids, edges with two equivalent S(4)Ba4Fe square pyramids, and edges with two equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the second S site, S(1) is bonded to two equivalent Ba(1), one Fe(1), and two equivalent Bi(1) atoms to form distorted SBa2FeBi2 trigonal bipyramids that share corners with two equivalent S(2)Ba4Bi square pyramids, corners with three equivalent S(4)Ba4Fe square pyramids, corners with five equivalent S(1)Ba2FeBi2 trigonal bipyramids,  an edgeedge with one S(4)Ba4Fe square pyramid, edges with two equivalent S(2)Ba4Bi square pyramids, and edges with two equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the third S site, S(2) is bonded to four equivalent Ba(1) and one Bi(1) atom to form SBa4Bi square pyramids that share corners with four equivalent S(2)Ba4Bi square pyramids, corners with four equivalent S(4)Ba4Fe square pyramids, corners with four equivalent S(1)Ba2FeBi2 trigonal bipyramids, edges with two equivalent S(4)Ba4Fe square pyramids, and edges with four equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the fourth S site, S(3) is bonded in a 1-coordinate geometry to four equivalent Ba(1) and one Fe(1) atom.
Ba2BiFeS5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There is one shorter (3.35 Å) and one longer (3.39 Å) Ba(1)-S(1) bond length. There is one shorter (3.30 Å) and one longer (3.35 Å) Ba(1)-S(2) bond length. There is one shorter (3.28 Å) and one longer (3.34 Å) Ba(1)-S(3) bond length. There is one shorter (3.30 Å) and one longer (3.32 Å) Ba(1)-S(4) bond length. Fe(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. The Fe(1)-S(3) bond length is 2.25 Å. The Fe(1)-S(4) bond length is 2.21 Å. Both Fe(1)-S(1) bond lengths are 2.29 Å. Bi(1) is bonded in a 5-coordinate geometry to one S(2) and four equivalent S(1) atoms. The Bi(1)-S(2) bond length is 2.57 Å. There are two shorter (2.68 Å) and two longer (3.12 Å) Bi(1)-S(1) bond lengths. There are four inequivalent S sites. In the first S site, S(4) is bonded to four equivalent Ba(1) and one Fe(1) atom to form distorted SBa4Fe square pyramids that share corners with four equivalent S(2)Ba4Bi square pyramids, corners with six equivalent S(1)Ba2FeBi2 trigonal bipyramids, edges with two equivalent S(2)Ba4Bi square pyramids, edges with two equivalent S(4)Ba4Fe square pyramids, and edges with two equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the second S site, S(1) is bonded to two equivalent Ba(1), one Fe(1), and two equivalent Bi(1) atoms to form distorted SBa2FeBi2 trigonal bipyramids that share corners with two equivalent S(2)Ba4Bi square pyramids, corners with three equivalent S(4)Ba4Fe square pyramids, corners with five equivalent S(1)Ba2FeBi2 trigonal bipyramids,  an edgeedge with one S(4)Ba4Fe square pyramid, edges with two equivalent S(2)Ba4Bi square pyramids, and edges with two equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the third S site, S(2) is bonded to four equivalent Ba(1) and one Bi(1) atom to form SBa4Bi square pyramids that share corners with four equivalent S(2)Ba4Bi square pyramids, corners with four equivalent S(4)Ba4Fe square pyramids, corners with four equivalent S(1)Ba2FeBi2 trigonal bipyramids, edges with two equivalent S(4)Ba4Fe square pyramids, and edges with four equivalent S(1)Ba2FeBi2 trigonal bipyramids. In the fourth S site, S(3) is bonded in a 1-coordinate geometry to four equivalent Ba(1) and one Fe(1) atom.