Rb3VS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. In the second Rb site, Rb(2) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. V(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Rb(2), four equivalent Rb(1), and one V(1) atom to form distorted edge-sharing SRb5V octahedra. In the second S site, S(2) is bonded in a distorted single-bond geometry to two equivalent Rb(2), four equivalent Rb(1), and one V(1) atom. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Rb(2), three equivalent Rb(1), and one V(1) atom.
Rb3VS4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. There is one shorter (3.30 Å) and one longer (3.33 Å) Rb(1)-S(1) bond length. There is one shorter (3.49 Å) and one longer (3.53 Å) Rb(1)-S(2) bond length. There are a spread of Rb(1)-S(3) bond distances ranging from 3.39-3.47 Å. In the second Rb site, Rb(2) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(3) atoms. The Rb(2)-S(1) bond length is 3.31 Å. There is one shorter (3.44 Å) and one longer (3.47 Å) Rb(2)-S(2) bond length. Both Rb(2)-S(3) bond lengths are 3.50 Å. V(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. The V(1)-S(1) bond length is 2.15 Å. The V(1)-S(2) bond length is 2.16 Å. Both V(1)-S(3) bond lengths are 2.15 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Rb(2), four equivalent Rb(1), and one V(1) atom to form distorted edge-sharing SRb5V octahedra. In the second S site, S(2) is bonded in a distorted single-bond geometry to two equivalent Rb(2), four equivalent Rb(1), and one V(1) atom. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Rb(2), three equivalent Rb(1), and one V(1) atom.