NaLi5Sn4 crystallizes in the trigonal R3m space group. Na(1) is bonded in a 10-coordinate geometry to one Li(3), three equivalent Li(1), three equivalent Li(4), and three equivalent Sn(1) atoms. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), one Li(2), one Sn(1), and three equivalent Sn(4) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one Li(1) and three equivalent Sn(3) atoms. In the third Li site, Li(3) is bonded to one Na(1), one Sn(2), and three equivalent Sn(4) atoms to form distorted corner-sharing LiNaSn4 tetrahedra. In the fourth Li site, Li(4) is bonded in a distorted body-centered cubic geometry to three equivalent Na(1), one Li(5), one Sn(4), and three equivalent Sn(1) atoms. In the fifth Li site, Li(5) is bonded in a 7-coordinate geometry to one Li(4), three equivalent Sn(1), and three equivalent Sn(2) atoms. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 11-coordinate geometry to three equivalent Na(1), one Li(1), three equivalent Li(4), three equivalent Li(5), and one Sn(2) atom. In the second Sn site, Sn(2) is bonded in a distorted body-centered cubic geometry to one Li(3), three equivalent Li(5), one Sn(1), and three equivalent Sn(3) atoms. In the third Sn site, Sn(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Li(2), one Sn(4), and three equivalent Sn(2) atoms. In the fourth Sn site, Sn(4) is bonded in a 7-coordinate geometry to one Li(4), three equivalent Li(1), three equivalent Li(3), and one Sn(3) atom.
NaLi5Sn4 crystallizes in the trigonal R3m space group. Na(1) is bonded in a 10-coordinate geometry to one Li(3), three equivalent Li(1), three equivalent Li(4), and three equivalent Sn(1) atoms. The Na(1)-Li(3) bond length is 3.17 Å. All Na(1)-Li(1) bond lengths are 3.19 Å. All Na(1)-Li(4) bond lengths are 2.90 Å. All Na(1)-Sn(1) bond lengths are 3.22 Å. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 8-coordinate geometry to three equivalent Na(1), one Li(2), one Sn(1), and three equivalent Sn(4) atoms. The Li(1)-Li(2) bond length is 2.72 Å. The Li(1)-Sn(1) bond length is 2.85 Å. All Li(1)-Sn(4) bond lengths are 3.02 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one Li(1) and three equivalent Sn(3) atoms. All Li(2)-Sn(3) bond lengths are 3.10 Å. In the third Li site, Li(3) is bonded to one Na(1), one Sn(2), and three equivalent Sn(4) atoms to form distorted corner-sharing LiNaSn4 tetrahedra. The Li(3)-Sn(2) bond length is 3.09 Å. All Li(3)-Sn(4) bond lengths are 2.98 Å. In the fourth Li site, Li(4) is bonded in a distorted body-centered cubic geometry to three equivalent Na(1), one Li(5), one Sn(4), and three equivalent Sn(1) atoms. The Li(4)-Li(5) bond length is 2.63 Å. The Li(4)-Sn(4) bond length is 2.79 Å. All Li(4)-Sn(1) bond lengths are 3.04 Å. In the fifth Li site, Li(5) is bonded in a 7-coordinate geometry to one Li(4), three equivalent Sn(1), and three equivalent Sn(2) atoms. All Li(5)-Sn(1) bond lengths are 3.29 Å. All Li(5)-Sn(2) bond lengths are 3.12 Å. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 11-coordinate geometry to three equivalent Na(1), one Li(1), three equivalent Li(4), three equivalent Li(5), and one Sn(2) atom. The Sn(1)-Sn(2) bond length is 2.84 Å. In the second Sn site, Sn(2) is bonded in a distorted body-centered cubic geometry to one Li(3), three equivalent Li(5), one Sn(1), and three equivalent Sn(3) atoms. All Sn(2)-Sn(3) bond lengths are 3.03 Å. In the third Sn site, Sn(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Li(2), one Sn(4), and three equivalent Sn(2) atoms. The Sn(3)-Sn(4) bond length is 2.93 Å. In the fourth Sn site, Sn(4) is bonded in a 7-coordinate geometry to one Li(4), three equivalent Li(1), three equivalent Li(3), and one Sn(3) atom.