Na2Ba3Sb4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(3), one Sb(4), 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. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one Sb(1), two equivalent Sb(2), two equivalent Sb(3), and two equivalent Sb(4) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one Sb(1), two equivalent Sb(2), two equivalent Sb(3), and two equivalent Sb(4) atoms. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), one Ba(1), one Ba(2), two equivalent Ba(3), and one Sb(2) atom. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to one Na(2), two equivalent Na(1), one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Sb(1) atom. In the third Sb site, Sb(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(2), two equivalent Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one Sb(3) atom. In the fourth Sb site, Sb(4) is bonded in a 9-coordinate geometry to one Na(1), two equivalent Na(2), one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Sb(4) atom.
Na2Ba3Sb4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(3), one Sb(4), and two equivalent Sb(2) atoms. The Na(1)-Sb(1) bond length is 3.19 Å. The Na(1)-Sb(3) bond length is 3.76 Å. The Na(1)-Sb(4) bond length is 3.66 Å. There is one shorter (3.29 Å) and one longer (3.33 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 3.53 Å. The Na(2)-Sb(3) bond length is 3.46 Å. There is one shorter (3.37 Å) and one longer (3.66 Å) Na(2)-Sb(1) bond length. There is one shorter (3.33 Å) and one longer (3.36 Å) Na(2)-Sb(4) bond length. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one Sb(1), two equivalent Sb(2), two equivalent Sb(3), and two equivalent Sb(4) atoms. The Ba(1)-Sb(1) bond length is 3.68 Å. There is one shorter (3.59 Å) and one longer (3.60 Å) Ba(1)-Sb(2) bond length. There is one shorter (3.61 Å) and one longer (4.00 Å) Ba(1)-Sb(3) bond length. There is one shorter (3.59 Å) and one longer (3.64 Å) Ba(1)-Sb(4) bond length. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one Sb(1), two equivalent Sb(2), two equivalent Sb(3), and two equivalent Sb(4) atoms. The Ba(2)-Sb(1) bond length is 3.61 Å. There is one shorter (3.58 Å) and one longer (3.61 Å) Ba(2)-Sb(2) bond length. There is one shorter (3.65 Å) and one longer (3.67 Å) Ba(2)-Sb(3) bond length. There is one shorter (3.60 Å) and one longer (4.05 Å) Ba(2)-Sb(4) bond length. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one Sb(2), one Sb(4), two equivalent Sb(1), and two equivalent Sb(3) atoms. The Ba(3)-Sb(2) bond length is 3.59 Å. The Ba(3)-Sb(4) bond length is 3.44 Å. There is one shorter (3.40 Å) and one longer (3.41 Å) Ba(3)-Sb(1) bond length. There is one shorter (3.47 Å) and one longer (3.53 Å) Ba(3)-Sb(3) bond length. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), one Ba(1), one Ba(2), two equivalent Ba(3), and one Sb(2) atom. The Sb(1)-Sb(2) bond length is 2.88 Å. In the second Sb site, Sb(2) is bonded in a 9-coordinate geometry to one Na(2), two equivalent Na(1), one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Sb(1) atom. In the third Sb site, Sb(3) is bonded in a 9-coordinate geometry to one Na(1), one Na(2), two equivalent Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one Sb(3) atom. The Sb(3)-Sb(3) bond length is 2.96 Å. In the fourth Sb site, Sb(4) is bonded in a 9-coordinate geometry to one Na(1), two equivalent Na(2), one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Sb(4) atom. The Sb(4)-Sb(4) bond length is 2.90 Å.