Na5TlSn3 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 4-coordinate geometry to one Sn(1), one Sn(3), and two equivalent Sn(2) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one Tl(1), one Sn(2), one Sn(3), and two equivalent Sn(1) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to two equivalent Tl(1), one Sn(1), one Sn(2), and one Sn(3) atom. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Tl(1), one Sn(2), two equivalent Sn(1), and two equivalent Sn(3) atoms. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Tl(1), one Sn(1), two equivalent Sn(2), and two equivalent Sn(3) atoms. Tl(1) is bonded in a 8-coordinate geometry to one Na(2), one Na(4), one Na(5), two equivalent Na(3), one Sn(1), one Sn(2), and one Sn(3) atom. There are three inequivalent Sn sites. In the first Sn site, Sn(3) is bonded in a 10-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), two equivalent Na(5), one Tl(1), one Sn(1), and one Sn(2) atom. In the second Sn site, Sn(1) is bonded in a 10-coordinate geometry to one Na(1), one Na(3), one Na(5), two equivalent Na(2), two equivalent Na(4), one Tl(1), one Sn(2), and one Sn(3) atom. In the third Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Na(2), one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(5), one Tl(1), one Sn(1), and one Sn(3) atom.
Na5TlSn3 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 4-coordinate geometry to one Sn(1), one Sn(3), and two equivalent Sn(2) atoms. The Na(1)-Sn(1) bond length is 3.13 Å. The Na(1)-Sn(3) bond length is 3.22 Å. There is one shorter (3.15 Å) and one longer (3.53 Å) Na(1)-Sn(2) bond length. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one Tl(1), one Sn(2), one Sn(3), and two equivalent Sn(1) atoms. The Na(2)-Tl(1) bond length is 3.30 Å. The Na(2)-Sn(2) bond length is 3.71 Å. The Na(2)-Sn(3) bond length is 3.35 Å. There is one shorter (3.27 Å) and one longer (3.43 Å) Na(2)-Sn(1) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to two equivalent Tl(1), one Sn(1), one Sn(2), and one Sn(3) atom. There is one shorter (3.18 Å) and one longer (3.35 Å) Na(3)-Tl(1) bond length. The Na(3)-Sn(1) bond length is 3.34 Å. The Na(3)-Sn(2) bond length is 3.22 Å. The Na(3)-Sn(3) bond length is 3.17 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Tl(1), one Sn(2), two equivalent Sn(1), and two equivalent Sn(3) atoms. The Na(4)-Tl(1) bond length is 3.19 Å. The Na(4)-Sn(2) bond length is 3.41 Å. There is one shorter (3.49 Å) and one longer (3.59 Å) Na(4)-Sn(1) bond length. There is one shorter (3.17 Å) and one longer (3.44 Å) Na(4)-Sn(3) bond length. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Tl(1), one Sn(1), two equivalent Sn(2), and two equivalent Sn(3) atoms. The Na(5)-Tl(1) bond length is 3.20 Å. The Na(5)-Sn(1) bond length is 3.28 Å. There is one shorter (3.23 Å) and one longer (3.34 Å) Na(5)-Sn(2) bond length. There is one shorter (3.57 Å) and one longer (3.62 Å) Na(5)-Sn(3) bond length. Tl(1) is bonded in a 8-coordinate geometry to one Na(2), one Na(4), one Na(5), two equivalent Na(3), one Sn(1), one Sn(2), and one Sn(3) atom. The Tl(1)-Sn(1) bond length is 3.13 Å. The Tl(1)-Sn(2) bond length is 3.14 Å. The Tl(1)-Sn(3) bond length is 3.12 Å. There are three inequivalent Sn sites. In the first Sn site, Sn(3) is bonded in a 10-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), two equivalent Na(5), one Tl(1), one Sn(1), and one Sn(2) atom. The Sn(3)-Sn(1) bond length is 2.96 Å. The Sn(3)-Sn(2) bond length is 2.98 Å. In the second Sn site, Sn(1) is bonded in a 10-coordinate geometry to one Na(1), one Na(3), one Na(5), two equivalent Na(2), two equivalent Na(4), one Tl(1), one Sn(2), and one Sn(3) atom. The Sn(1)-Sn(2) bond length is 2.92 Å. In the third Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Na(2), one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(5), one Tl(1), one Sn(1), and one Sn(3) atom.