Rb3NbS4 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 7-coordinate geometry to one S(1), two equivalent S(2), and four equivalent S(3) atoms. Nb(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 Nb(1) atom to form edge-sharing SRb5Nb octahedra. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Rb(2), four equivalent Rb(1), and one Nb(1) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Rb(2), three equivalent Rb(1), and one Nb(1) atom.
Rb3NbS4 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 (3.35 Å) and one longer (3.36 Å) Rb(1)-S(1) bond length. There is one shorter (3.54 Å) and one longer (3.71 Å) Rb(1)-S(2) bond length. There are a spread of Rb(1)-S(3) bond distances ranging from 3.41-3.52 Å. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), and four equivalent S(3) atoms. The Rb(2)-S(1) bond length is 3.30 Å. There is one shorter (3.48 Å) and one longer (3.58 Å) Rb(2)-S(2) bond length. There are two shorter (3.52 Å) and two longer (3.90 Å) Rb(2)-S(3) bond lengths. Nb(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. The Nb(1)-S(1) bond length is 2.29 Å. The Nb(1)-S(2) bond length is 2.30 Å. Both Nb(1)-S(3) bond lengths are 2.28 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 Nb(1) atom to form edge-sharing SRb5Nb octahedra. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Rb(2), four equivalent Rb(1), and one Nb(1) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Rb(2), three equivalent Rb(1), and one Nb(1) atom.