Cs5Nb2S4Cl9 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), one Cl(3), three equivalent Cl(2), and four equivalent Cl(1) atoms. In the second Cs site, Cs(2) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form corner-sharing CsCl6 octahedra. The corner-sharing octahedra are not tilted. Nb(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Nb(1), and one S(1) atom. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Nb(1) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Cs(2), three equivalent Cs(1), and one Nb(1) atom. In the third Cl site, Cl(3) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form corner-sharing ClCs6 octahedra. The corner-sharing octahedra are not tilted.
Cs5Nb2S4Cl9 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), one Cl(3), three equivalent Cl(2), and four equivalent Cl(1) atoms. Both Cs(1)-S(1) bond lengths are 3.81 Å. The Cs(1)-Cl(3) bond length is 3.56 Å. There is one shorter (3.43 Å) and two longer (3.72 Å) Cs(1)-Cl(2) bond lengths. There are two shorter (3.55 Å) and two longer (3.64 Å) Cs(1)-Cl(1) bond lengths. In the second Cs site, Cs(2) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form corner-sharing CsCl6 octahedra. The corner-sharing octahedra are not tilted. Both Cs(2)-Cl(3) bond lengths are 3.66 Å. All Cs(2)-Cl(2) bond lengths are 3.42 Å. Nb(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. All Nb(1)-S(1) bond lengths are 2.51 Å. Both Nb(1)-Cl(1) bond lengths are 2.55 Å. Both Nb(1)-Cl(2) bond lengths are 2.64 Å. S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Nb(1), and one S(1) atom. The S(1)-S(1) bond length is 2.00 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Nb(1) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Cs(2), three equivalent Cs(1), and one Nb(1) atom. In the third Cl site, Cl(3) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form corner-sharing ClCs6 octahedra. The corner-sharing octahedra are not tilted.