CaV2S5 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. V(1) is bonded to one S(1), one S(3), and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing VS5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1) and two equivalent V(1) atoms to form distorted corner-sharing SCa2V2 tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ca(1) and three equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one V(1) atom.
CaV2S5 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. Both Ca(1)-S(1) bond lengths are 2.91 Å. Both Ca(1)-S(2) bond lengths are 3.19 Å. All Ca(1)-S(3) bond lengths are 2.97 Å. V(1) is bonded to one S(1), one S(3), and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing VS5 trigonal bipyramids. The V(1)-S(1) bond length is 2.34 Å. The V(1)-S(3) bond length is 2.13 Å. There are two shorter (2.36 Å) and one longer (2.40 Å) V(1)-S(2) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1) and two equivalent V(1) atoms to form distorted corner-sharing SCa2V2 tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ca(1) and three equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one V(1) atom.