NdP5 crystallizes in the monoclinic P2_1/m space group. Nd(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Nd(1), one P(2), and one P(3) atom to form PNd2P2 tetrahedra that share corners with four equivalent P(3)Nd2P2 tetrahedra, corners with five equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(2)NdP3 tetrahedra, and  an edgeedge with one P(3)Nd2P2 tetrahedra. In the second P site, P(1) is bonded to two equivalent Nd(1) and two equivalent P(2) atoms to form distorted PNd2P2 tetrahedra that share corners with two equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(2)NdP3 tetrahedra, and corners with ten equivalent P(3)Nd2P2 tetrahedra. In the third P site, P(2) is bonded to one Nd(1), one P(1), one P(2), and one P(3) atom to form PNdP3 tetrahedra that share corners with three equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(3)Nd2P2 tetrahedra, and  an edgeedge with one P(2)NdP3 tetrahedra.
NdP5 crystallizes in the monoclinic P2_1/m space group. Nd(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There is one shorter (3.06 Å) and one longer (3.09 Å) Nd(1)-P(1) bond length. Both Nd(1)-P(2) bond lengths are 3.04 Å. There are two shorter (3.04 Å) and two longer (3.08 Å) Nd(1)-P(3) bond lengths. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Nd(1), one P(2), and one P(3) atom to form PNd2P2 tetrahedra that share corners with four equivalent P(3)Nd2P2 tetrahedra, corners with five equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(2)NdP3 tetrahedra, and  an edgeedge with one P(3)Nd2P2 tetrahedra. The P(3)-P(2) bond length is 2.15 Å. The P(3)-P(3) bond length is 2.20 Å. In the second P site, P(1) is bonded to two equivalent Nd(1) and two equivalent P(2) atoms to form distorted PNd2P2 tetrahedra that share corners with two equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(2)NdP3 tetrahedra, and corners with ten equivalent P(3)Nd2P2 tetrahedra. Both P(1)-P(2) bond lengths are 2.20 Å. In the third P site, P(2) is bonded to one Nd(1), one P(1), one P(2), and one P(3) atom to form PNdP3 tetrahedra that share corners with three equivalent P(1)Nd2P2 tetrahedra, corners with six equivalent P(3)Nd2P2 tetrahedra, and  an edgeedge with one P(2)NdP3 tetrahedra. The P(2)-P(2) bond length is 2.20 Å.