Ba2ZnS3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted BaS7 pentagonal bipyramids that share corners with two equivalent Ba(1)S7 pentagonal bipyramids,  a cornercorner with one Zn(1)S4 tetrahedra, edges with four equivalent Ba(1)S7 pentagonal bipyramids, and edges with four equivalent Zn(1)S4 tetrahedra. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(3), and three equivalent S(1) atoms. Zn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form ZnS4 tetrahedra that share  a cornercorner with one Ba(1)S7 pentagonal bipyramid, corners with two equivalent Zn(1)S4 tetrahedra, and edges with four equivalent Ba(1)S7 pentagonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), three equivalent Ba(2), and one Zn(1) atom to form distorted SBa5Zn octahedra that share corners with two equivalent S(2)Ba4Zn2 octahedra, corners with eight equivalent S(3)Ba5Zn octahedra,  an edgeedge with one S(3)Ba5Zn octahedra, edges with four equivalent S(1)Ba5Zn octahedra, edges with five equivalent S(2)Ba4Zn2 octahedra, and  a faceface with one S(3)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 15-57°. In the second S site, S(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zn(1) atoms to form distorted SBa4Zn2 octahedra that share corners with two equivalent S(2)Ba4Zn2 octahedra, corners with two equivalent S(1)Ba5Zn octahedra, corners with five equivalent S(3)Ba5Zn octahedra, edges with two equivalent S(2)Ba4Zn2 octahedra, edges with two equivalent S(3)Ba5Zn octahedra, edges with five equivalent S(1)Ba5Zn octahedra, and  a faceface with one S(3)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 15-61°. In the third S site, S(3) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one Zn(1) atom to form distorted SBa5Zn octahedra that share corners with five equivalent S(2)Ba4Zn2 octahedra, corners with eight equivalent S(1)Ba5Zn octahedra,  an edgeedge with one S(1)Ba5Zn octahedra, edges with two equivalent S(2)Ba4Zn2 octahedra, edges with four equivalent S(3)Ba5Zn octahedra,  a faceface with one S(2)Ba4Zn2 octahedra, and  a faceface with one S(1)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 26-61°.
Ba2ZnS3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted BaS7 pentagonal bipyramids that share corners with two equivalent Ba(1)S7 pentagonal bipyramids,  a cornercorner with one Zn(1)S4 tetrahedra, edges with four equivalent Ba(1)S7 pentagonal bipyramids, and edges with four equivalent Zn(1)S4 tetrahedra. Both Ba(1)-S(1) bond lengths are 3.23 Å. There is one shorter (3.22 Å) and one longer (3.24 Å) Ba(1)-S(2) bond length. There are two shorter (3.16 Å) and one longer (3.28 Å) Ba(1)-S(3) bond length. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to two equivalent S(2), two equivalent S(3), and three equivalent S(1) atoms. Both Ba(2)-S(2) bond lengths are 3.28 Å. Both Ba(2)-S(3) bond lengths are 3.27 Å. There are two shorter (3.22 Å) and one longer (3.24 Å) Ba(2)-S(1) bond length. Zn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form ZnS4 tetrahedra that share  a cornercorner with one Ba(1)S7 pentagonal bipyramid, corners with two equivalent Zn(1)S4 tetrahedra, and edges with four equivalent Ba(1)S7 pentagonal bipyramids. The Zn(1)-S(1) bond length is 2.34 Å. The Zn(1)-S(3) bond length is 2.31 Å. Both Zn(1)-S(2) bond lengths are 2.46 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), three equivalent Ba(2), and one Zn(1) atom to form distorted SBa5Zn octahedra that share corners with two equivalent S(2)Ba4Zn2 octahedra, corners with eight equivalent S(3)Ba5Zn octahedra,  an edgeedge with one S(3)Ba5Zn octahedra, edges with four equivalent S(1)Ba5Zn octahedra, edges with five equivalent S(2)Ba4Zn2 octahedra, and  a faceface with one S(3)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 15-57°. In the second S site, S(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zn(1) atoms to form distorted SBa4Zn2 octahedra that share corners with two equivalent S(2)Ba4Zn2 octahedra, corners with two equivalent S(1)Ba5Zn octahedra, corners with five equivalent S(3)Ba5Zn octahedra, edges with two equivalent S(2)Ba4Zn2 octahedra, edges with two equivalent S(3)Ba5Zn octahedra, edges with five equivalent S(1)Ba5Zn octahedra, and  a faceface with one S(3)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 15-61°. In the third S site, S(3) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one Zn(1) atom to form distorted SBa5Zn octahedra that share corners with five equivalent S(2)Ba4Zn2 octahedra, corners with eight equivalent S(1)Ba5Zn octahedra,  an edgeedge with one S(1)Ba5Zn octahedra, edges with two equivalent S(2)Ba4Zn2 octahedra, edges with four equivalent S(3)Ba5Zn octahedra,  a faceface with one S(2)Ba4Zn2 octahedra, and  a faceface with one S(1)Ba5Zn octahedra. The corner-sharing octahedral tilt angles range from 26-61°.