Na5GeP3 crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one P(1), one P(3), and two equivalent P(2) atoms to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. In the second Na site, Na(2) is bonded to one P(2), one P(3), and two equivalent P(1) atoms to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(3) atoms. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one P(3), two equivalent P(1), and two equivalent P(2) atoms. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one P(1), one P(2), and two equivalent P(3) atoms. Ge(1) is bonded in a 4-coordinate geometry to one P(1), one P(2), and two equivalent P(3) atoms. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), and one Ge(1) atom. In the second P site, P(2) is bonded in a 8-coordinate geometry to one Na(2), one Na(3), one Na(5), two equivalent Na(1), two equivalent Na(4), and one Ge(1) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), two equivalent Na(5), and two equivalent Ge(1) atoms.
Na5GeP3 crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one P(1), one P(3), and two equivalent P(2) atoms to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. The Na(1)-P(1) bond length is 2.88 Å. The Na(1)-P(3) bond length is 2.84 Å. There is one shorter (2.85 Å) and one longer (2.86 Å) Na(1)-P(2) bond length. In the second Na site, Na(2) is bonded to one P(2), one P(3), and two equivalent P(1) atoms to form a mixture of distorted corner and edge-sharing NaP4 tetrahedra. The Na(2)-P(2) bond length is 2.88 Å. The Na(2)-P(3) bond length is 2.91 Å. There is one shorter (2.89 Å) and one longer (3.00 Å) Na(2)-P(1) bond length. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(3) atoms. The Na(3)-P(2) bond length is 2.85 Å. There is one shorter (3.00 Å) and one longer (3.05 Å) Na(3)-P(1) bond length. There is one shorter (3.36 Å) and one longer (3.39 Å) Na(3)-P(3) bond length. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one P(3), two equivalent P(1), and two equivalent P(2) atoms. The Na(4)-P(3) bond length is 3.05 Å. There is one shorter (3.01 Å) and one longer (3.20 Å) Na(4)-P(1) bond length. There is one shorter (3.10 Å) and one longer (3.26 Å) Na(4)-P(2) bond length. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one P(1), one P(2), and two equivalent P(3) atoms. The Na(5)-P(1) bond length is 2.99 Å. The Na(5)-P(2) bond length is 2.94 Å. There is one shorter (2.91 Å) and one longer (3.28 Å) Na(5)-P(3) bond length. Ge(1) is bonded in a 4-coordinate geometry to one P(1), one P(2), and two equivalent P(3) atoms. The Ge(1)-P(1) bond length is 2.35 Å. The Ge(1)-P(2) bond length is 2.33 Å. There is one shorter (2.40 Å) and one longer (2.43 Å) Ge(1)-P(3) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), and one Ge(1) atom. In the second P site, P(2) is bonded in a 8-coordinate geometry to one Na(2), one Na(3), one Na(5), two equivalent Na(1), two equivalent Na(4), and one Ge(1) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), two equivalent Na(5), and two equivalent Ge(1) atoms.