Na5GeAs3 crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one As(2), two equivalent As(1), and two equivalent As(3) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one As(1), two equivalent As(2), and two equivalent As(3) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one As(3), two equivalent As(1), and two equivalent As(2) atoms. In the fourth Na site, Na(4) is bonded to one As(2), one As(3), and two equivalent As(1) atoms to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. In the fifth Na site, Na(5) is bonded to one As(1), one As(3), and two equivalent As(2) atoms to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. Ge(1) is bonded in a 4-coordinate geometry to one As(1), one As(2), and two equivalent As(3) atoms. There are three inequivalent As sites. In the first As site, As(3) is bonded in a 9-coordinate geometry to one Na(3), one Na(4), one Na(5), two equivalent Na(1), two equivalent Na(2), and two equivalent Ge(1) atoms. In the second As site, As(1) is bonded in a 9-coordinate geometry to one Na(2), one Na(5), two equivalent Na(1), two equivalent Na(3), two equivalent Na(4), and one Ge(1) atom. In the third As site, As(2) is bonded in a 9-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), two equivalent Na(3), two equivalent Na(5), and one Ge(1) atom.
Na5GeAs3 crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one As(2), two equivalent As(1), and two equivalent As(3) atoms. The Na(1)-As(2) bond length is 2.93 Å. There is one shorter (3.10 Å) and one longer (3.11 Å) Na(1)-As(1) bond length. There is one shorter (3.41 Å) and one longer (3.49 Å) Na(1)-As(3) bond length. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one As(1), two equivalent As(2), and two equivalent As(3) atoms. The Na(2)-As(1) bond length is 3.07 Å. There is one shorter (3.03 Å) and one longer (3.50 Å) Na(2)-As(2) bond length. There is one shorter (3.00 Å) and one longer (3.37 Å) Na(2)-As(3) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one As(3), two equivalent As(1), and two equivalent As(2) atoms. The Na(3)-As(3) bond length is 3.10 Å. There is one shorter (3.11 Å) and one longer (3.28 Å) Na(3)-As(1) bond length. There is one shorter (3.21 Å) and one longer (3.30 Å) Na(3)-As(2) bond length. In the fourth Na site, Na(4) is bonded to one As(2), one As(3), and two equivalent As(1) atoms to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. The Na(4)-As(2) bond length is 2.94 Å. The Na(4)-As(3) bond length is 2.97 Å. There is one shorter (2.95 Å) and one longer (3.05 Å) Na(4)-As(1) bond length. In the fifth Na site, Na(5) is bonded to one As(1), one As(3), and two equivalent As(2) atoms to form a mixture of distorted corner and edge-sharing NaAs4 tetrahedra. The Na(5)-As(1) bond length is 2.94 Å. The Na(5)-As(3) bond length is 2.90 Å. Both Na(5)-As(2) bond lengths are 2.92 Å. Ge(1) is bonded in a 4-coordinate geometry to one As(1), one As(2), and two equivalent As(3) atoms. The Ge(1)-As(1) bond length is 2.46 Å. The Ge(1)-As(2) bond length is 2.44 Å. There is one shorter (2.50 Å) and one longer (2.54 Å) Ge(1)-As(3) bond length. There are three inequivalent As sites. In the first As site, As(3) is bonded in a 9-coordinate geometry to one Na(3), one Na(4), one Na(5), two equivalent Na(1), two equivalent Na(2), and two equivalent Ge(1) atoms. In the second As site, As(1) is bonded in a 9-coordinate geometry to one Na(2), one Na(5), two equivalent Na(1), two equivalent Na(3), two equivalent Na(4), and one Ge(1) atom. In the third As site, As(2) is bonded in a 9-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), two equivalent Na(3), two equivalent Na(5), and one Ge(1) atom.