Na15Ge8SnP crystallizes in the orthorhombic Cmcm space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one Ge(1), one Ge(2), two equivalent Ge(3), and one P(1) atom. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to two equivalent Sn(1), one Ge(1), one Ge(2), and one P(1) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent Sn(1), one Ge(1), one Ge(2), and two equivalent Ge(3) atoms. In the fourth Na site, Na(4) is bonded to one Sn(1), two equivalent Ge(3), and one P(1) atom to form corner-sharing NaSnGe2P tetrahedra. In the fifth Na site, Na(5) is bonded in a 5-coordinate geometry to one Sn(1), one Ge(2), two equivalent Ge(1), and two equivalent Ge(3) atoms. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to four equivalent Ge(3) and one P(1) atom. Sn(1) is bonded in a 14-coordinate geometry to two equivalent Na(4), four equivalent Na(2), four equivalent Na(3), and four equivalent Na(5) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted q6 geometry to one Na(2), one Na(3), two equivalent Na(1), four equivalent Na(5), one Ge(2), and two equivalent Ge(3) atoms. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), two equivalent Na(5), one Ge(1), and two equivalent Ge(3) atoms. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(1), two equivalent Na(5), one Ge(1), one Ge(2), and one Ge(3) atom. P(1) is bonded in a 9-coordinate geometry to one Na(6), two equivalent Na(2), two equivalent Na(4), and four equivalent Na(1) atoms.
Na15Ge8SnP crystallizes in the orthorhombic Cmcm space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one Ge(1), one Ge(2), two equivalent Ge(3), and one P(1) atom. The Na(1)-Ge(1) bond length is 3.19 Å. The Na(1)-Ge(2) bond length is 3.14 Å. There is one shorter (2.99 Å) and one longer (3.24 Å) Na(1)-Ge(3) bond length. The Na(1)-P(1) bond length is 2.85 Å. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to two equivalent Sn(1), one Ge(1), one Ge(2), and one P(1) atom. Both Na(2)-Sn(1) bond lengths are 3.65 Å. The Na(2)-Ge(1) bond length is 3.17 Å. The Na(2)-Ge(2) bond length is 3.12 Å. The Na(2)-P(1) bond length is 2.92 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent Sn(1), one Ge(1), one Ge(2), and two equivalent Ge(3) atoms. Both Na(3)-Sn(1) bond lengths are 3.49 Å. The Na(3)-Ge(1) bond length is 3.31 Å. The Na(3)-Ge(2) bond length is 3.38 Å. Both Na(3)-Ge(3) bond lengths are 3.36 Å. In the fourth Na site, Na(4) is bonded to one Sn(1), two equivalent Ge(3), and one P(1) atom to form corner-sharing NaSnGe2P tetrahedra. The Na(4)-Sn(1) bond length is 3.20 Å. Both Na(4)-Ge(3) bond lengths are 3.19 Å. The Na(4)-P(1) bond length is 3.00 Å. In the fifth Na site, Na(5) is bonded in a 5-coordinate geometry to one Sn(1), one Ge(2), two equivalent Ge(1), and two equivalent Ge(3) atoms. The Na(5)-Sn(1) bond length is 3.71 Å. The Na(5)-Ge(2) bond length is 3.11 Å. There is one shorter (3.33 Å) and one longer (3.34 Å) Na(5)-Ge(1) bond length. There is one shorter (3.13 Å) and one longer (3.24 Å) Na(5)-Ge(3) bond length. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to four equivalent Ge(3) and one P(1) atom. All Na(6)-Ge(3) bond lengths are 3.10 Å. The Na(6)-P(1) bond length is 2.87 Å. Sn(1) is bonded in a 14-coordinate geometry to two equivalent Na(4), four equivalent Na(2), four equivalent Na(3), and four equivalent Na(5) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted q6 geometry to one Na(2), one Na(3), two equivalent Na(1), four equivalent Na(5), one Ge(2), and two equivalent Ge(3) atoms. The Ge(1)-Ge(2) bond length is 2.59 Å. Both Ge(1)-Ge(3) bond lengths are 2.55 Å. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), two equivalent Na(5), one Ge(1), and two equivalent Ge(3) atoms. Both Ge(2)-Ge(3) bond lengths are 2.60 Å. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(1), two equivalent Na(5), one Ge(1), one Ge(2), and one Ge(3) atom. The Ge(3)-Ge(3) bond length is 2.52 Å. P(1) is bonded in a 9-coordinate geometry to one Na(6), two equivalent Na(2), two equivalent Na(4), and four equivalent Na(1) atoms.