K3Na2SnBi3 crystallizes in the orthorhombic Ibca space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one Sn(1), one Bi(1), and four equivalent Bi(2) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent Sn(1), two equivalent Bi(2), and three equivalent Bi(1) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Sn(1) and four equivalent Bi(2) atoms to form distorted NaSnBi4 tetrahedra that share corners with two equivalent Sn(1)K4Na4Bi4 cuboctahedra,  a cornercorner with one Na(2)Sn3Bi4 tetrahedra,  an edgeedge with one Sn(1)K4Na4Bi4 cuboctahedra, edges with two equivalent Na(1)SnBi4 tetrahedra, and edges with three equivalent Na(2)Sn3Bi4 tetrahedra. In the second Na site, Na(2) is bonded to three equivalent Sn(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted NaSn3Bi4 tetrahedra that share  a cornercorner with one Na(1)SnBi4 tetrahedra, corners with two equivalent Na(2)Sn3Bi4 tetrahedra, edges with three equivalent Sn(1)K4Na4Bi4 cuboctahedra, edges with three equivalent Na(1)SnBi4 tetrahedra, and faces with two equivalent Na(2)Sn3Bi4 tetrahedra. Sn(1) is bonded to two equivalent K(1), two equivalent K(2), one Na(1), three equivalent Na(2), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted SnK4Na4Bi4 cuboctahedra that share corners with two equivalent Sn(1)K4Na4Bi4 cuboctahedra, corners with two equivalent Na(1)SnBi4 tetrahedra,  an edgeedge with one Na(1)SnBi4 tetrahedra, edges with three equivalent Na(2)Sn3Bi4 tetrahedra, and faces with two equivalent Sn(1)K4Na4Bi4 cuboctahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), two equivalent Na(2), and two equivalent Sn(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to one K(2), four equivalent K(1), one Na(2), two equivalent Na(1), and one Sn(1) atom.
K3Na2SnBi3 crystallizes in the orthorhombic Ibca space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 5-coordinate geometry to one Sn(1), one Bi(1), and four equivalent Bi(2) atoms. The K(1)-Sn(1) bond length is 4.03 Å. The K(1)-Bi(1) bond length is 3.81 Å. There are a spread of K(1)-Bi(2) bond distances ranging from 3.72-3.96 Å. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent Sn(1), two equivalent Bi(2), and three equivalent Bi(1) atoms. Both K(2)-Sn(1) bond lengths are 3.94 Å. Both K(2)-Bi(2) bond lengths are 3.66 Å. There are two shorter (3.84 Å) and one longer (3.88 Å) K(2)-Bi(1) bond length. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Sn(1) and four equivalent Bi(2) atoms to form distorted NaSnBi4 tetrahedra that share corners with two equivalent Sn(1)K4Na4Bi4 cuboctahedra,  a cornercorner with one Na(2)Sn3Bi4 tetrahedra,  an edgeedge with one Sn(1)K4Na4Bi4 cuboctahedra, edges with two equivalent Na(1)SnBi4 tetrahedra, and edges with three equivalent Na(2)Sn3Bi4 tetrahedra. The Na(1)-Sn(1) bond length is 3.72 Å. There are two shorter (3.20 Å) and two longer (3.42 Å) Na(1)-Bi(2) bond lengths. In the second Na site, Na(2) is bonded to three equivalent Sn(1), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted NaSn3Bi4 tetrahedra that share  a cornercorner with one Na(1)SnBi4 tetrahedra, corners with two equivalent Na(2)Sn3Bi4 tetrahedra, edges with three equivalent Sn(1)K4Na4Bi4 cuboctahedra, edges with three equivalent Na(1)SnBi4 tetrahedra, and faces with two equivalent Na(2)Sn3Bi4 tetrahedra. There are two shorter (3.64 Å) and one longer (3.72 Å) Na(2)-Sn(1) bond length. Both Na(2)-Bi(1) bond lengths are 3.17 Å. Both Na(2)-Bi(2) bond lengths are 3.25 Å. Sn(1) is bonded to two equivalent K(1), two equivalent K(2), one Na(1), three equivalent Na(2), two equivalent Bi(1), and two equivalent Bi(2) atoms to form distorted SnK4Na4Bi4 cuboctahedra that share corners with two equivalent Sn(1)K4Na4Bi4 cuboctahedra, corners with two equivalent Na(1)SnBi4 tetrahedra,  an edgeedge with one Na(1)SnBi4 tetrahedra, edges with three equivalent Na(2)Sn3Bi4 tetrahedra, and faces with two equivalent Sn(1)K4Na4Bi4 cuboctahedra. Both Sn(1)-Bi(1) bond lengths are 3.10 Å. Both Sn(1)-Bi(2) bond lengths are 3.00 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 9-coordinate geometry to two equivalent K(1), three equivalent K(2), two equivalent Na(2), and two equivalent Sn(1) atoms. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to one K(2), four equivalent K(1), one Na(2), two equivalent Na(1), and one Sn(1) atom.