Ba2GaSbS5 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. Ga(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. Sb(1) is bonded in a 3-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 Ga(1) atom to form distorted SBa4Ga square pyramids that share corners with four equivalent S(3)Ba4Ga square pyramids, corners with four equivalent S(2)Ba4Sb square pyramids,  an edgeedge with one S(3)Ba4Ga square pyramid, edges with two equivalent S(4)Ba4Ga square pyramids, edges with two equivalent S(2)Ba4Sb square pyramids, and  a faceface with one S(3)Ba4Ga square pyramid. In the second S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one Ga(1), and two equivalent Sb(1) atoms. In the third S site, S(2) is bonded to four equivalent Ba(1) and one Sb(1) atom to form distorted SBa4Sb square pyramids that share corners with four equivalent S(4)Ba4Ga square pyramids, corners with four equivalent S(2)Ba4Sb square pyramids, edges with two equivalent S(4)Ba4Ga square pyramids, and edges with four equivalent S(3)Ba4Ga square pyramids. In the fourth S site, S(3) is bonded to four equivalent Ba(1) and one Ga(1) atom to form distorted SBa4Ga square pyramids that share corners with four equivalent S(3)Ba4Ga square pyramids, corners with four equivalent S(4)Ba4Ga square pyramids,  an edgeedge with one S(4)Ba4Ga square pyramid, edges with four equivalent S(2)Ba4Sb square pyramids, and  a faceface with one S(4)Ba4Ga square pyramid.
Ba2GaSbS5 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 (3.37 Å) and one longer (3.44 Å) Ba(1)-S(1) bond length. There is one shorter (3.34 Å) and one longer (3.39 Å) Ba(1)-S(2) bond length. There is one shorter (3.29 Å) and one longer (3.39 Å) Ba(1)-S(3) bond length. There is one shorter (3.33 Å) and one longer (3.35 Å) Ba(1)-S(4) bond length. Ga(1) is bonded in a tetrahedral geometry to one S(3), one S(4), and two equivalent S(1) atoms. The Ga(1)-S(3) bond length is 2.26 Å. The Ga(1)-S(4) bond length is 2.23 Å. Both Ga(1)-S(1) bond lengths are 2.33 Å. Sb(1) is bonded in a 3-coordinate geometry to one S(2) and four equivalent S(1) atoms. The Sb(1)-S(2) bond length is 2.47 Å. There are two shorter (2.55 Å) and two longer (3.18 Å) Sb(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 Ga(1) atom to form distorted SBa4Ga square pyramids that share corners with four equivalent S(3)Ba4Ga square pyramids, corners with four equivalent S(2)Ba4Sb square pyramids,  an edgeedge with one S(3)Ba4Ga square pyramid, edges with two equivalent S(4)Ba4Ga square pyramids, edges with two equivalent S(2)Ba4Sb square pyramids, and  a faceface with one S(3)Ba4Ga square pyramid. In the second S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Ba(1), one Ga(1), and two equivalent Sb(1) atoms. In the third S site, S(2) is bonded to four equivalent Ba(1) and one Sb(1) atom to form distorted SBa4Sb square pyramids that share corners with four equivalent S(4)Ba4Ga square pyramids, corners with four equivalent S(2)Ba4Sb square pyramids, edges with two equivalent S(4)Ba4Ga square pyramids, and edges with four equivalent S(3)Ba4Ga square pyramids. In the fourth S site, S(3) is bonded to four equivalent Ba(1) and one Ga(1) atom to form distorted SBa4Ga square pyramids that share corners with four equivalent S(3)Ba4Ga square pyramids, corners with four equivalent S(4)Ba4Ga square pyramids,  an edgeedge with one S(4)Ba4Ga square pyramid, edges with four equivalent S(2)Ba4Sb square pyramids, and  a faceface with one S(4)Ba4Ga square pyramid.