V7S8 crystallizes in the trigonal P3_121 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the second V site, V(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the third V site, V(3) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the fourth V site, V(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the fifth V site, V(5) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one V(1), one V(2), one V(4), one V(5), and two equivalent V(3) atoms to form distorted SV6 pentagonal pyramids that share corners with three equivalent S(1)V6 pentagonal pyramids, corners with three equivalent S(2)V5 trigonal bipyramids,  an edgeedge with one S(1)V6 pentagonal pyramid, edges with three equivalent S(2)V5 trigonal bipyramids, edges with four equivalent S(3)V5 trigonal bipyramids, and edges with four equivalent S(4)V5 trigonal bipyramids. In the second S site, S(2) is bonded to one V(1), one V(2), one V(3), one V(4), and one V(5) atom to form distorted SV5 trigonal bipyramids that share corners with three equivalent S(1)V6 pentagonal pyramids,  a cornercorner with one S(2)V5 trigonal bipyramid, corners with two equivalent S(4)V5 trigonal bipyramids, corners with three equivalent S(3)V5 trigonal bipyramids, edges with three equivalent S(1)V6 pentagonal pyramids,  an edgeedge with one S(2)V5 trigonal bipyramid, edges with two equivalent S(3)V5 trigonal bipyramids, and edges with two equivalent S(4)V5 trigonal bipyramids. In the third S site, S(3) is bonded to one V(2), one V(3), one V(4), and two equivalent V(1) atoms to form distorted SV5 trigonal bipyramids that share corners with two equivalent S(4)V5 trigonal bipyramids, corners with three equivalent S(2)V5 trigonal bipyramids, corners with four equivalent S(3)V5 trigonal bipyramids, edges with four equivalent S(1)V6 pentagonal pyramids, edges with two equivalent S(2)V5 trigonal bipyramids, and edges with two equivalent S(4)V5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one V(5), two equivalent V(1), and two equivalent V(3) atoms to form distorted SV5 trigonal bipyramids that share corners with two equivalent S(2)V5 trigonal bipyramids, corners with two equivalent S(3)V5 trigonal bipyramids, corners with five equivalent S(4)V5 trigonal bipyramids, edges with four equivalent S(1)V6 pentagonal pyramids, edges with two equivalent S(2)V5 trigonal bipyramids, and edges with two equivalent S(3)V5 trigonal bipyramids.
V7S8 crystallizes in the trigonal P3_121 space group. There are five inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The V(1)-S(1) bond length is 2.40 Å. The V(1)-S(2) bond length is 2.35 Å. There is one shorter (2.35 Å) and one longer (2.43 Å) V(1)-S(3) bond length. There is one shorter (2.35 Å) and one longer (2.43 Å) V(1)-S(4) bond length. In the second V site, V(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. Both V(2)-S(1) bond lengths are 2.36 Å. Both V(2)-S(2) bond lengths are 2.41 Å. Both V(2)-S(3) bond lengths are 2.40 Å. In the third V site, V(3) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The V(3)-S(2) bond length is 2.38 Å. The V(3)-S(3) bond length is 2.37 Å. There is one shorter (2.37 Å) and one longer (2.41 Å) V(3)-S(1) bond length. There is one shorter (2.37 Å) and one longer (2.38 Å) V(3)-S(4) bond length. In the fourth V site, V(4) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. Both V(4)-S(1) bond lengths are 2.38 Å. Both V(4)-S(2) bond lengths are 2.37 Å. Both V(4)-S(3) bond lengths are 2.37 Å. In the fifth V site, V(5) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. Both V(5)-S(1) bond lengths are 2.36 Å. Both V(5)-S(2) bond lengths are 2.41 Å. Both V(5)-S(4) bond lengths are 2.40 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one V(1), one V(2), one V(4), one V(5), and two equivalent V(3) atoms to form distorted SV6 pentagonal pyramids that share corners with three equivalent S(1)V6 pentagonal pyramids, corners with three equivalent S(2)V5 trigonal bipyramids,  an edgeedge with one S(1)V6 pentagonal pyramid, edges with three equivalent S(2)V5 trigonal bipyramids, edges with four equivalent S(3)V5 trigonal bipyramids, and edges with four equivalent S(4)V5 trigonal bipyramids. In the second S site, S(2) is bonded to one V(1), one V(2), one V(3), one V(4), and one V(5) atom to form distorted SV5 trigonal bipyramids that share corners with three equivalent S(1)V6 pentagonal pyramids,  a cornercorner with one S(2)V5 trigonal bipyramid, corners with two equivalent S(4)V5 trigonal bipyramids, corners with three equivalent S(3)V5 trigonal bipyramids, edges with three equivalent S(1)V6 pentagonal pyramids,  an edgeedge with one S(2)V5 trigonal bipyramid, edges with two equivalent S(3)V5 trigonal bipyramids, and edges with two equivalent S(4)V5 trigonal bipyramids. In the third S site, S(3) is bonded to one V(2), one V(3), one V(4), and two equivalent V(1) atoms to form distorted SV5 trigonal bipyramids that share corners with two equivalent S(4)V5 trigonal bipyramids, corners with three equivalent S(2)V5 trigonal bipyramids, corners with four equivalent S(3)V5 trigonal bipyramids, edges with four equivalent S(1)V6 pentagonal pyramids, edges with two equivalent S(2)V5 trigonal bipyramids, and edges with two equivalent S(4)V5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one V(5), two equivalent V(1), and two equivalent V(3) atoms to form distorted SV5 trigonal bipyramids that share corners with two equivalent S(2)V5 trigonal bipyramids, corners with two equivalent S(3)V5 trigonal bipyramids, corners with five equivalent S(4)V5 trigonal bipyramids, edges with four equivalent S(1)V6 pentagonal pyramids, edges with two equivalent S(2)V5 trigonal bipyramids, and edges with two equivalent S(3)V5 trigonal bipyramids.