CsP7 crystallizes in the orthorhombic Pca2_1 space group. Cs(1) is bonded in a 12-coordinate geometry to one P(2), one P(6), two equivalent P(1), two equivalent P(3), two equivalent P(4), two equivalent P(5), and two equivalent P(7) atoms. There are seven inequivalent P sites. In the first P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(4), one P(6), and one P(7) atom. In the second P site, P(2) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(3), one P(6), and one P(7) atom. In the third P site, P(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one P(2), one P(5), and one P(6) atom. In the fourth P site, P(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(1), one P(5), and one P(7) atom. In the fifth P site, P(5) is bonded to two equivalent Cs(1), one P(3), and one P(4) atom to form corner-sharing PCs2P2 tetrahedra. In the sixth P site, P(6) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(1), one P(2), and one P(3) atom. In the seventh P site, P(7) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(1), one P(2), and one P(4) atom.
CsP7 crystallizes in the orthorhombic Pca2_1 space group. Cs(1) is bonded in a 12-coordinate geometry to one P(2), one P(6), two equivalent P(1), two equivalent P(3), two equivalent P(4), two equivalent P(5), and two equivalent P(7) atoms. The Cs(1)-P(2) bond length is 3.82 Å. The Cs(1)-P(6) bond length is 3.81 Å. There is one shorter (3.89 Å) and one longer (3.91 Å) Cs(1)-P(1) bond length. There is one shorter (4.12 Å) and one longer (4.16 Å) Cs(1)-P(3) bond length. There is one shorter (3.73 Å) and one longer (3.77 Å) Cs(1)-P(4) bond length. Both Cs(1)-P(5) bond lengths are 3.64 Å. There is one shorter (3.92 Å) and one longer (3.96 Å) Cs(1)-P(7) bond length. There are seven inequivalent P sites. In the first P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(4), one P(6), and one P(7) atom. The P(1)-P(4) bond length is 2.24 Å. The P(1)-P(6) bond length is 2.20 Å. The P(1)-P(7) bond length is 2.22 Å. In the second P site, P(2) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(3), one P(6), and one P(7) atom. The P(2)-P(3) bond length is 2.20 Å. The P(2)-P(6) bond length is 2.21 Å. The P(2)-P(7) bond length is 2.20 Å. In the third P site, P(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one P(2), one P(5), and one P(6) atom. The P(3)-P(5) bond length is 2.14 Å. The P(3)-P(6) bond length is 2.20 Å. In the fourth P site, P(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(1), one P(5), and one P(7) atom. The P(4)-P(5) bond length is 2.13 Å. The P(4)-P(7) bond length is 2.24 Å. In the fifth P site, P(5) is bonded to two equivalent Cs(1), one P(3), and one P(4) atom to form corner-sharing PCs2P2 tetrahedra. In the sixth P site, P(6) is bonded in a distorted see-saw-like geometry to one Cs(1), one P(1), one P(2), and one P(3) atom. In the seventh P site, P(7) is bonded in a 5-coordinate geometry to two equivalent Cs(1), one P(1), one P(2), and one P(4) atom.