Li5GeP3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Ge(1), one P(2), and three equivalent P(1) atoms to form distorted LiGeP4 tetrahedra that share  a cornercorner with one Li(3)Ge2P4 tetrahedra, corners with six equivalent Li(1)GeP4 tetrahedra,  an edgeedge with one Li(1)GeP4 tetrahedra, and edges with three equivalent Li(3)Ge2P4 tetrahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Ge(1), one P(2), and three equivalent P(1) atoms. In the third Li site, Li(3) is bonded to two equivalent Ge(1), two equivalent P(1), and two equivalent P(2) atoms to form distorted LiGe2P4 tetrahedra that share corners with two equivalent Li(1)GeP4 tetrahedra, corners with four equivalent Li(3)Ge2P4 tetrahedra, and edges with six equivalent Li(1)GeP4 tetrahedra. Ge(1) is bonded in a 10-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), two equivalent P(1), and two equivalent P(2) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded in a body-centered cubic geometry to one Li(3), three equivalent Li(1), three equivalent Li(2), and one Ge(1) atom. In the second P site, P(2) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Ge(1) atoms.
Li5GeP3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Ge(1), one P(2), and three equivalent P(1) atoms to form distorted LiGeP4 tetrahedra that share  a cornercorner with one Li(3)Ge2P4 tetrahedra, corners with six equivalent Li(1)GeP4 tetrahedra,  an edgeedge with one Li(1)GeP4 tetrahedra, and edges with three equivalent Li(3)Ge2P4 tetrahedra. The Li(1)-Ge(1) bond length is 2.96 Å. The Li(1)-P(2) bond length is 2.54 Å. There are a spread of Li(1)-P(1) bond distances ranging from 2.52-2.57 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one Ge(1), one P(2), and three equivalent P(1) atoms. The Li(2)-Ge(1) bond length is 2.94 Å. The Li(2)-P(2) bond length is 2.51 Å. There are a spread of Li(2)-P(1) bond distances ranging from 2.49-2.70 Å. In the third Li site, Li(3) is bonded to two equivalent Ge(1), two equivalent P(1), and two equivalent P(2) atoms to form distorted LiGe2P4 tetrahedra that share corners with two equivalent Li(1)GeP4 tetrahedra, corners with four equivalent Li(3)Ge2P4 tetrahedra, and edges with six equivalent Li(1)GeP4 tetrahedra. There is one shorter (2.86 Å) and one longer (3.00 Å) Li(3)-Ge(1) bond length. Both Li(3)-P(1) bond lengths are 2.53 Å. Both Li(3)-P(2) bond lengths are 2.53 Å. Ge(1) is bonded in a 10-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), two equivalent P(1), and two equivalent P(2) atoms. Both Ge(1)-P(1) bond lengths are 2.32 Å. Both Ge(1)-P(2) bond lengths are 2.61 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a body-centered cubic geometry to one Li(3), three equivalent Li(1), three equivalent Li(2), and one Ge(1) atom. In the second P site, P(2) is bonded in a body-centered cubic geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and two equivalent Ge(1) atoms.