CsNb4Cl11 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(5), and four equivalent Cl(2) atoms. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one Cl(4), one Cl(5), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of distorted edge and face-sharing NbCl6 octahedra. In the second Nb site, Nb(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms to form distorted edge-sharing NbCl6 octahedra. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted water-like geometry to one Cs(1) and two equivalent Nb(2) atoms. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Cs(1), one Nb(1), and one Nb(2) atom. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Nb(1) atoms. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the fifth Cl site, Cl(5) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Nb(1) atoms.
CsNb4Cl11 crystallizes in the orthorhombic Pmma space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(5), and four equivalent Cl(2) atoms. Both Cs(1)-Cl(1) bond lengths are 3.62 Å. Both Cs(1)-Cl(3) bond lengths are 3.73 Å. Both Cs(1)-Cl(5) bond lengths are 3.60 Å. All Cs(1)-Cl(2) bond lengths are 3.61 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one Cl(4), one Cl(5), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of distorted edge and face-sharing NbCl6 octahedra. The Nb(1)-Cl(4) bond length is 2.45 Å. The Nb(1)-Cl(5) bond length is 2.64 Å. Both Nb(1)-Cl(2) bond lengths are 2.43 Å. Both Nb(1)-Cl(3) bond lengths are 2.59 Å. In the second Nb site, Nb(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms to form distorted edge-sharing NbCl6 octahedra. Both Nb(2)-Cl(1) bond lengths are 2.60 Å. Both Nb(2)-Cl(2) bond lengths are 2.52 Å. Both Nb(2)-Cl(4) bond lengths are 2.52 Å. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted water-like geometry to one Cs(1) and two equivalent Nb(2) atoms. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Cs(1), one Nb(1), and one Nb(2) atom. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Nb(1) atoms. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the fifth Cl site, Cl(5) is bonded in a 4-coordinate geometry to two equivalent Cs(1) and two equivalent Nb(1) atoms.