Na6TlSb4 crystallizes in the monoclinic C2/c space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent Tl(1), one Sb(1), one Sb(3), and two equivalent Sb(2) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(3), two equivalent Sb(1), and two equivalent Sb(4) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Tl(1), one Sb(4), two equivalent Sb(2), and two equivalent Sb(3) atoms. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Tl(1), one Sb(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Sb(1), one Sb(3), two equivalent Sb(2), and two equivalent Sb(4) atoms. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one Tl(1), one Sb(2), one Sb(3), one Sb(4), and two equivalent Sb(1) atoms. Tl(1) is bonded in a 9-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(1), one Tl(1), one Sb(1), one Sb(2), one Sb(3), and one Sb(4) atom. There are four inequivalent Sb sites. In the first Sb site, Sb(3) is bonded in a 10-coordinate geometry to one Na(1), one Na(2), one Na(5), one Na(6), two equivalent Na(3), two equivalent Na(4), one Tl(1), and one Sb(4) atom. In the second Sb site, Sb(4) is bonded in a 11-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(2), two equivalent Na(5), one Tl(1), one Sb(1), one Sb(2), and one Sb(3) atom. In the third Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(4), two equivalent Na(6), one Tl(1), and one Sb(4) atom. In the fourth Sb site, Sb(2) is bonded in a 10-coordinate geometry to one Na(2), one Na(6), two equivalent Na(1), two equivalent Na(3), two equivalent Na(5), one Tl(1), and one Sb(4) atom.
Na6TlSb4 crystallizes in the monoclinic C2/c space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent Tl(1), one Sb(1), one Sb(3), and two equivalent Sb(2) atoms. There is one shorter (3.62 Å) and one longer (3.65 Å) Na(1)-Tl(1) bond length. The Na(1)-Sb(1) bond length is 3.54 Å. The Na(1)-Sb(3) bond length is 3.58 Å. There is one shorter (3.16 Å) and one longer (3.23 Å) Na(1)-Sb(2) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(3), two equivalent Sb(1), and two equivalent Sb(4) atoms. The Na(2)-Sb(2) bond length is 3.34 Å. The Na(2)-Sb(3) bond length is 3.33 Å. There is one shorter (3.25 Å) and one longer (3.30 Å) Na(2)-Sb(1) bond length. There is one shorter (3.39 Å) and one longer (3.43 Å) Na(2)-Sb(4) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Tl(1), one Sb(4), two equivalent Sb(2), and two equivalent Sb(3) atoms. The Na(3)-Tl(1) bond length is 3.30 Å. The Na(3)-Sb(4) bond length is 3.49 Å. There is one shorter (3.36 Å) and one longer (3.57 Å) Na(3)-Sb(2) bond length. There is one shorter (3.21 Å) and one longer (3.43 Å) Na(3)-Sb(3) bond length. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Tl(1), one Sb(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. The Na(4)-Tl(1) bond length is 3.44 Å. The Na(4)-Sb(4) bond length is 3.31 Å. There is one shorter (3.34 Å) and one longer (3.49 Å) Na(4)-Sb(1) bond length. There is one shorter (3.26 Å) and one longer (3.49 Å) Na(4)-Sb(3) bond length. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Sb(1), one Sb(3), two equivalent Sb(2), and two equivalent Sb(4) atoms. The Na(5)-Sb(1) bond length is 3.39 Å. The Na(5)-Sb(3) bond length is 3.31 Å. There is one shorter (3.15 Å) and one longer (3.26 Å) Na(5)-Sb(2) bond length. There is one shorter (3.47 Å) and one longer (3.56 Å) Na(5)-Sb(4) bond length. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one Tl(1), one Sb(2), one Sb(3), one Sb(4), and two equivalent Sb(1) atoms. The Na(6)-Tl(1) bond length is 3.23 Å. The Na(6)-Sb(2) bond length is 3.48 Å. The Na(6)-Sb(3) bond length is 3.31 Å. The Na(6)-Sb(4) bond length is 3.79 Å. There is one shorter (3.23 Å) and one longer (3.65 Å) Na(6)-Sb(1) bond length. Tl(1) is bonded in a 9-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(1), one Tl(1), one Sb(1), one Sb(2), one Sb(3), and one Sb(4) atom. The Tl(1)-Tl(1) bond length is 3.07 Å. The Tl(1)-Sb(1) bond length is 3.18 Å. The Tl(1)-Sb(2) bond length is 3.11 Å. The Tl(1)-Sb(3) bond length is 3.13 Å. The Tl(1)-Sb(4) bond length is 3.60 Å. There are four inequivalent Sb sites. In the first Sb site, Sb(3) is bonded in a 10-coordinate geometry to one Na(1), one Na(2), one Na(5), one Na(6), two equivalent Na(3), two equivalent Na(4), one Tl(1), and one Sb(4) atom. The Sb(3)-Sb(4) bond length is 3.25 Å. In the second Sb site, Sb(4) is bonded in a 11-coordinate geometry to one Na(3), one Na(4), one Na(6), two equivalent Na(2), two equivalent Na(5), one Tl(1), one Sb(1), one Sb(2), and one Sb(3) atom. The Sb(4)-Sb(1) bond length is 3.01 Å. The Sb(4)-Sb(2) bond length is 3.20 Å. In the third Sb site, Sb(1) is bonded in a 10-coordinate geometry to one Na(1), one Na(5), two equivalent Na(2), two equivalent Na(4), two equivalent Na(6), one Tl(1), and one Sb(4) atom. In the fourth Sb site, Sb(2) is bonded in a 10-coordinate geometry to one Na(2), one Na(6), two equivalent Na(1), two equivalent Na(3), two equivalent Na(5), one Tl(1), and one Sb(4) atom.