Na2Tl crystallizes in the orthorhombic C222_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent Na(3), two equivalent Tl(1), and two equivalent Tl(2) atoms. In the second Na site, Na(2) is bonded in a 12-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), two equivalent Tl(1), and four equivalent Tl(2) atoms. In the third Na site, Na(3) is bonded in a 13-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), three equivalent Na(5), two equivalent Tl(2), and three equivalent Tl(1) atoms. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), two equivalent Tl(1), and two equivalent Tl(2) atoms. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one Na(2), three equivalent Na(3), one Tl(2), and two equivalent Tl(1) atoms. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 12-coordinate geometry to one Na(1), one Na(2), two equivalent Na(4), two equivalent Na(5), three equivalent Na(3), one Tl(1), and two equivalent Tl(2) atoms. In the second Tl site, Tl(2) is bonded in a 11-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), one Tl(2), and two equivalent Tl(1) atoms.
Na2Tl crystallizes in the orthorhombic C222_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent Na(3), two equivalent Tl(1), and two equivalent Tl(2) atoms. Both Na(1)-Na(3) bond lengths are 3.39 Å. Both Na(1)-Tl(1) bond lengths are 3.37 Å. Both Na(1)-Tl(2) bond lengths are 3.30 Å. In the second Na site, Na(2) is bonded in a 12-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), two equivalent Tl(1), and four equivalent Tl(2) atoms. Both Na(2)-Na(3) bond lengths are 3.58 Å. Both Na(2)-Na(4) bond lengths are 3.29 Å. Both Na(2)-Na(5) bond lengths are 3.51 Å. Both Na(2)-Tl(1) bond lengths are 3.31 Å. There are two shorter (3.35 Å) and two longer (3.59 Å) Na(2)-Tl(2) bond lengths. In the third Na site, Na(3) is bonded in a 13-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), three equivalent Na(5), two equivalent Tl(2), and three equivalent Tl(1) atoms. The Na(3)-Na(3) bond length is 3.95 Å. There is one shorter (3.50 Å) and one longer (3.52 Å) Na(3)-Na(4) bond length. There are a spread of Na(3)-Na(5) bond distances ranging from 3.55-3.76 Å. There is one shorter (3.66 Å) and one longer (3.71 Å) Na(3)-Tl(2) bond length. There are a spread of Na(3)-Tl(1) bond distances ranging from 3.37-3.58 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), two equivalent Tl(1), and two equivalent Tl(2) atoms. There is one shorter (3.15 Å) and one longer (3.26 Å) Na(4)-Tl(1) bond length. There is one shorter (3.19 Å) and one longer (3.24 Å) Na(4)-Tl(2) bond length. In the fifth Na site, Na(5) is bonded in a 3-coordinate geometry to one Na(2), three equivalent Na(3), one Tl(2), and two equivalent Tl(1) atoms. The Na(5)-Tl(2) bond length is 3.27 Å. There is one shorter (3.33 Å) and one longer (3.43 Å) Na(5)-Tl(1) bond length. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 12-coordinate geometry to one Na(1), one Na(2), two equivalent Na(4), two equivalent Na(5), three equivalent Na(3), one Tl(1), and two equivalent Tl(2) atoms. The Tl(1)-Tl(1) bond length is 3.21 Å. There is one shorter (3.19 Å) and one longer (3.32 Å) Tl(1)-Tl(2) bond length. In the second Tl site, Tl(2) is bonded in a 11-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(3), two equivalent Na(4), one Tl(2), and two equivalent Tl(1) atoms. The Tl(2)-Tl(2) bond length is 3.22 Å.