CsP7 crystallizes in the orthorhombic Pbcm space group. Cs(1) is bonded in a 12-coordinate geometry to two equivalent P(1), two equivalent P(3), two equivalent P(4), two equivalent P(5), and four equivalent P(2) atoms. There are five inequivalent P sites. In the first P site, P(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(1), one P(3), and two equivalent P(5) atoms. In the second P site, P(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(2), one P(4), and one P(5) atom. In the third P site, P(3) is bonded to two equivalent Cs(1), one P(1), and one P(4) atom to form corner-sharing PCs2P2 tetrahedra. In the fourth P site, P(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(3), and two equivalent P(2) atoms. In the fifth P site, P(5) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(1), one P(2), and one P(5) atom.
CsP7 crystallizes in the orthorhombic Pbcm space group. Cs(1) is bonded in a 12-coordinate geometry to two equivalent P(1), two equivalent P(3), two equivalent P(4), two equivalent P(5), and four equivalent P(2) atoms. Both Cs(1)-P(1) bond lengths are 4.16 Å. Both Cs(1)-P(3) bond lengths are 3.67 Å. Both Cs(1)-P(4) bond lengths are 3.76 Å. Both Cs(1)-P(5) bond lengths are 3.83 Å. All Cs(1)-P(2) bond lengths are 3.94 Å. There are five inequivalent P sites. In the first P site, P(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(1), one P(3), and two equivalent P(5) atoms. The P(1)-P(3) bond length is 2.14 Å. Both P(1)-P(5) bond lengths are 2.21 Å. In the second P site, P(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(2), one P(4), and one P(5) atom. The P(2)-P(2) bond length is 2.23 Å. The P(2)-P(4) bond length is 2.24 Å. The P(2)-P(5) bond length is 2.20 Å. In the third P site, P(3) is bonded to two equivalent Cs(1), one P(1), and one P(4) atom to form corner-sharing PCs2P2 tetrahedra. The P(3)-P(4) bond length is 2.13 Å. In the fourth P site, P(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(3), and two equivalent P(2) atoms. In the fifth P site, P(5) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(1), one P(2), and one P(5) atom. The P(5)-P(5) bond length is 2.22 Å.