LiP5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded in a 3-coordinate geometry to one P(1), one P(3), one P(4), and two equivalent P(5) atoms. There are five inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to one Li(1), one P(2), one P(3), and one P(4) atom. In the second P site, P(2) is bonded in a 3-coordinate geometry to one P(1), one P(3), and one P(4) atom. In the third P site, P(3) is bonded to one Li(1), one P(1), one P(2), and one P(5) atom to form distorted PLiP3 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids and corners with four equivalent P(4)LiP3 trigonal pyramids. In the fourth P site, P(4) is bonded to one Li(1), one P(1), one P(2), and one P(5) atom to form distorted PLiP3 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids and corners with four equivalent P(3)LiP3 trigonal pyramids. In the fifth P site, P(5) is bonded to two equivalent Li(1), one P(3), and one P(4) atom to form distorted PLi2P2 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids, corners with two equivalent P(3)LiP3 trigonal pyramids, and corners with two equivalent P(4)LiP3 trigonal pyramids.
LiP5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded in a 3-coordinate geometry to one P(1), one P(3), one P(4), and two equivalent P(5) atoms. The Li(1)-P(1) bond length is 3.13 Å. The Li(1)-P(3) bond length is 2.65 Å. The Li(1)-P(4) bond length is 3.03 Å. There is one shorter (2.55 Å) and one longer (2.56 Å) Li(1)-P(5) bond length. There are five inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to one Li(1), one P(2), one P(3), and one P(4) atom. The P(1)-P(2) bond length is 2.22 Å. The P(1)-P(3) bond length is 2.22 Å. The P(1)-P(4) bond length is 2.23 Å. In the second P site, P(2) is bonded in a 3-coordinate geometry to one P(1), one P(3), and one P(4) atom. The P(2)-P(3) bond length is 2.23 Å. The P(2)-P(4) bond length is 2.22 Å. In the third P site, P(3) is bonded to one Li(1), one P(1), one P(2), and one P(5) atom to form distorted PLiP3 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids and corners with four equivalent P(4)LiP3 trigonal pyramids. The P(3)-P(5) bond length is 2.17 Å. In the fourth P site, P(4) is bonded to one Li(1), one P(1), one P(2), and one P(5) atom to form distorted PLiP3 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids and corners with four equivalent P(3)LiP3 trigonal pyramids. The P(4)-P(5) bond length is 2.17 Å. In the fifth P site, P(5) is bonded to two equivalent Li(1), one P(3), and one P(4) atom to form distorted PLi2P2 trigonal pyramids that share corners with two equivalent P(5)Li2P2 trigonal pyramids, corners with two equivalent P(3)LiP3 trigonal pyramids, and corners with two equivalent P(4)LiP3 trigonal pyramids.