LiP5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one P(1), one P(2), one P(4), one P(5), and two equivalent P(3) atoms to form distorted LiP6 pentagonal pyramids that share corners with two equivalent Li(1)P6 pentagonal pyramids, corners with two equivalent P(3)Li2P2 tetrahedra, corners with three equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(2)LiP3 tetrahedra, and corners with four equivalent P(5)LiP3 tetrahedra. There are five inequivalent P sites. In the first P site, P(1) is bonded to one Li(1), one P(4), and two equivalent P(2) atoms to form distorted PLiP3 tetrahedra that share corners with three equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(2)LiP3 tetrahedra, corners with two equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(3)Li2P2 tetrahedra, and corners with four equivalent P(5)LiP3 tetrahedra. In the second P site, P(2) is bonded to one Li(1), one P(5), and two equivalent P(1) atoms to form distorted PLiP3 tetrahedra that share corners with three equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(1)LiP3 tetrahedra,  a cornercorner with one P(5)LiP3 tetrahedra, corners with two equivalent P(2)LiP3 tetrahedra, and corners with three equivalent P(3)Li2P2 tetrahedra. In the third P site, P(3) is bonded to two equivalent Li(1), one P(4), and one P(5) atom to form distorted PLi2P2 tetrahedra that share corners with two equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(5)LiP3 tetrahedra, corners with two equivalent P(3)Li2P2 tetrahedra, corners with three equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(2)LiP3 tetrahedra, and  an edgeedge with one P(5)LiP3 tetrahedra. In the fourth P site, P(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one P(1), one P(3), and one P(5) atom. In the fifth P site, P(5) is bonded to one Li(1), one P(2), one P(3), and one P(4) atom to form PLiP3 tetrahedra that share corners with four equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(3)Li2P2 tetrahedra,  a cornercorner with one P(2)LiP3 tetrahedra, corners with four equivalent P(1)LiP3 tetrahedra, and  an edgeedge with one P(3)Li2P2 tetrahedra.
LiP5 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one P(1), one P(2), one P(4), one P(5), and two equivalent P(3) atoms to form distorted LiP6 pentagonal pyramids that share corners with two equivalent Li(1)P6 pentagonal pyramids, corners with two equivalent P(3)Li2P2 tetrahedra, corners with three equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(2)LiP3 tetrahedra, and corners with four equivalent P(5)LiP3 tetrahedra. The Li(1)-P(1) bond length is 2.64 Å. The Li(1)-P(2) bond length is 2.57 Å. The Li(1)-P(4) bond length is 2.90 Å. The Li(1)-P(5) bond length is 2.73 Å. There is one shorter (2.58 Å) and one longer (2.68 Å) Li(1)-P(3) bond length. There are five inequivalent P sites. In the first P site, P(1) is bonded to one Li(1), one P(4), and two equivalent P(2) atoms to form distorted PLiP3 tetrahedra that share corners with three equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(2)LiP3 tetrahedra, corners with two equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(3)Li2P2 tetrahedra, and corners with four equivalent P(5)LiP3 tetrahedra. The P(1)-P(4) bond length is 2.27 Å. There is one shorter (2.26 Å) and one longer (2.27 Å) P(1)-P(2) bond length. In the second P site, P(2) is bonded to one Li(1), one P(5), and two equivalent P(1) atoms to form distorted PLiP3 tetrahedra that share corners with three equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(1)LiP3 tetrahedra,  a cornercorner with one P(5)LiP3 tetrahedra, corners with two equivalent P(2)LiP3 tetrahedra, and corners with three equivalent P(3)Li2P2 tetrahedra. The P(2)-P(5) bond length is 2.25 Å. In the third P site, P(3) is bonded to two equivalent Li(1), one P(4), and one P(5) atom to form distorted PLi2P2 tetrahedra that share corners with two equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(5)LiP3 tetrahedra, corners with two equivalent P(3)Li2P2 tetrahedra, corners with three equivalent P(1)LiP3 tetrahedra, corners with three equivalent P(2)LiP3 tetrahedra, and  an edgeedge with one P(5)LiP3 tetrahedra. The P(3)-P(4) bond length is 2.21 Å. The P(3)-P(5) bond length is 2.20 Å. In the fourth P site, P(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one P(1), one P(3), and one P(5) atom. The P(4)-P(5) bond length is 2.25 Å. In the fifth P site, P(5) is bonded to one Li(1), one P(2), one P(3), and one P(4) atom to form PLiP3 tetrahedra that share corners with four equivalent Li(1)P6 pentagonal pyramids,  a cornercorner with one P(3)Li2P2 tetrahedra,  a cornercorner with one P(2)LiP3 tetrahedra, corners with four equivalent P(1)LiP3 tetrahedra, and  an edgeedge with one P(3)Li2P2 tetrahedra.