Ba(V5S8)2 crystallizes in the triclinic P-1 space group. Ba(1) is bonded in a distorted q6 geometry to two equivalent S(1), two equivalent S(2), two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(3), one S(4), one S(5), one S(7), and two equivalent S(6) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second V site, V(2) is bonded to one S(3), one S(4), one S(6), one S(8), and two equivalent S(5) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the third V site, V(3) is bonded to two equivalent S(1), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the fourth V site, V(4) is bonded to two equivalent S(2), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the fifth V site, V(5) is bonded to one S(1), one S(2), one S(4), one S(8), and two equivalent S(3) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. In the sixth V site, V(6) is bonded to one S(1), one S(2), one S(3), one S(7), and two equivalent S(4) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(3), one V(5), and one V(6) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(4), one V(5), and one V(6) atom. In the third S site, S(3) is bonded to one V(1), one V(2), one V(6), and two equivalent V(5) atoms to form distorted SV5 trigonal bipyramids that share  a cornercorner with one S(6)BaV3 trigonal pyramid,  an edgeedge with one S(3)V5 trigonal bipyramid, edges with three equivalent S(4)V5 trigonal bipyramids, and  an edgeedge with one S(6)BaV3 trigonal pyramid. In the fourth S site, S(4) is bonded to one V(1), one V(2), one V(5), and two equivalent V(6) atoms to form distorted SV5 trigonal bipyramids that share corners with three equivalent S(6)BaV3 trigonal pyramids,  an edgeedge with one S(4)V5 trigonal bipyramid, and edges with three equivalent S(3)V5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(1), and two equivalent V(2) atoms. In the sixth S site, S(6) is bonded to one Ba(1), one V(2), and two equivalent V(1) atoms to form distorted SBaV3 trigonal pyramids that share  a cornercorner with one S(3)V5 trigonal bipyramid, corners with three equivalent S(4)V5 trigonal bipyramids,  a cornercorner with one S(6)BaV3 trigonal pyramid,  an edgeedge with one S(3)V5 trigonal bipyramid, and  an edgeedge with one S(6)BaV3 trigonal pyramid. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(1), one V(3), one V(4), and one V(6) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one V(2), one V(3), one V(4), and one V(5) atom.
Ba(V5S8)2 crystallizes in the triclinic P-1 space group. Ba(1) is bonded in a distorted q6 geometry to two equivalent S(1), two equivalent S(2), two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms. Both Ba(1)-S(1) bond lengths are 3.21 Å. Both Ba(1)-S(2) bond lengths are 3.29 Å. Both Ba(1)-S(5) bond lengths are 3.39 Å. Both Ba(1)-S(6) bond lengths are 3.41 Å. Both Ba(1)-S(7) bond lengths are 3.44 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(3), one S(4), one S(5), one S(7), and two equivalent S(6) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(1)-S(3) bond length is 2.49 Å. The V(1)-S(4) bond length is 2.49 Å. The V(1)-S(5) bond length is 2.43 Å. The V(1)-S(7) bond length is 2.49 Å. There is one shorter (2.33 Å) and one longer (2.38 Å) V(1)-S(6) bond length. In the second V site, V(2) is bonded to one S(3), one S(4), one S(6), one S(8), and two equivalent S(5) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The V(2)-S(3) bond length is 2.55 Å. The V(2)-S(4) bond length is 2.53 Å. The V(2)-S(6) bond length is 2.40 Å. The V(2)-S(8) bond length is 2.49 Å. There is one shorter (2.32 Å) and one longer (2.34 Å) V(2)-S(5) bond length. In the third V site, V(3) is bonded to two equivalent S(1), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Both V(3)-S(1) bond lengths are 2.45 Å. Both V(3)-S(7) bond lengths are 2.40 Å. Both V(3)-S(8) bond lengths are 2.38 Å. In the fourth V site, V(4) is bonded to two equivalent S(2), two equivalent S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. Both V(4)-S(2) bond lengths are 2.43 Å. Both V(4)-S(7) bond lengths are 2.41 Å. Both V(4)-S(8) bond lengths are 2.40 Å. In the fifth V site, V(5) is bonded to one S(1), one S(2), one S(4), one S(8), and two equivalent S(3) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. The V(5)-S(1) bond length is 2.32 Å. The V(5)-S(2) bond length is 2.38 Å. The V(5)-S(4) bond length is 2.46 Å. The V(5)-S(8) bond length is 2.38 Å. There is one shorter (2.51 Å) and one longer (2.56 Å) V(5)-S(3) bond length. In the sixth V site, V(6) is bonded to one S(1), one S(2), one S(3), one S(7), and two equivalent S(4) atoms to form a mixture of edge, corner, and face-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The V(6)-S(1) bond length is 2.32 Å. The V(6)-S(2) bond length is 2.36 Å. The V(6)-S(3) bond length is 2.53 Å. The V(6)-S(7) bond length is 2.36 Å. There is one shorter (2.46 Å) and one longer (2.51 Å) V(6)-S(4) bond length. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(3), one V(5), and one V(6) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(4), one V(5), and one V(6) atom. In the third S site, S(3) is bonded to one V(1), one V(2), one V(6), and two equivalent V(5) atoms to form distorted SV5 trigonal bipyramids that share  a cornercorner with one S(6)BaV3 trigonal pyramid,  an edgeedge with one S(3)V5 trigonal bipyramid, edges with three equivalent S(4)V5 trigonal bipyramids, and  an edgeedge with one S(6)BaV3 trigonal pyramid. In the fourth S site, S(4) is bonded to one V(1), one V(2), one V(5), and two equivalent V(6) atoms to form distorted SV5 trigonal bipyramids that share corners with three equivalent S(6)BaV3 trigonal pyramids,  an edgeedge with one S(4)V5 trigonal bipyramid, and edges with three equivalent S(3)V5 trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(1), and two equivalent V(2) atoms. In the sixth S site, S(6) is bonded to one Ba(1), one V(2), and two equivalent V(1) atoms to form distorted SBaV3 trigonal pyramids that share  a cornercorner with one S(3)V5 trigonal bipyramid, corners with three equivalent S(4)V5 trigonal bipyramids,  a cornercorner with one S(6)BaV3 trigonal pyramid,  an edgeedge with one S(3)V5 trigonal bipyramid, and  an edgeedge with one S(6)BaV3 trigonal pyramid. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Ba(1), one V(1), one V(3), one V(4), and one V(6) atom. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one V(2), one V(3), one V(4), and one V(5) atom.