Li2V2S5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. V(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of distorted corner and edge-sharing VS5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal pyramidal geometry to two equivalent Li(1) and two equivalent V(1) atoms.
Li2V2S5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(1), and two equivalent S(2) atoms. The Li(1)-S(3) bond length is 2.50 Å. There is one shorter (2.55 Å) and one longer (2.83 Å) Li(1)-S(1) bond length. There is one shorter (2.51 Å) and one longer (2.55 Å) Li(1)-S(2) bond length. V(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form a mixture of distorted corner and edge-sharing VS5 trigonal bipyramids. The V(1)-S(3) bond length is 2.39 Å. There is one shorter (2.18 Å) and one longer (2.46 Å) V(1)-S(1) bond length. There is one shorter (2.28 Å) and one longer (2.30 Å) V(1)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal pyramidal geometry to two equivalent Li(1) and two equivalent V(1) atoms.