Heteroatomic deltahedral clusters of main-group elements:: Synthesis and structure of the Zintl ions [In4Bi5]3-, [InBi3]2-, and [GaBi3]2-

Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, indium or gallium and bismuth. Nine-atom clusters [In4Bi5](3-) are characterized in two different compounds, (Na-crypt)(3)[In4Bi5] (4, P2(1)/n, a = 23.572(6) Angstrom, b = 15.042(4) Angstrom, c = 24.071(4) Angstrom, beta = 106.00(3)degrees, Z = 4) and (K-crypt)(6)[In4Bi5][In4Bi5](.)1.5en(.)0.5tol (5, P2(1)/c, a = 28.532(2) Angstrom, b = 23.707(2) Angstrom, c = 28.021(2) Angstrom, beta = 93.274(4)degrees, Z = 4). Tetrahedra of [InBi3](2-) or [GaBi3](2-) are found in (K-crypt)(2)[InBi3](.)en (1, P2(1), a = 12.347(4) Angstrom, b = 20.884(4) Angstrom, c = 12.619(7) Angstrom, beta = 119.02(4)degrees, Z = 2) and in the isostructural (Rb-crypt)(2)[InBi3](.)en (2, a = 12.403(8) Angstrom, b = 20.99(1) Angstrom, c = 12.617(9) Angstrom, beta = 118.83(4)degrees) and (K-crypt)(2)[GaBi3](.)en (3, a = 12.324(5) Angstrom, b = 20.890(8) Angstrom, c = 12.629(5) Angstrom, beta = 118.91(3)degrees). All compounds are crystallized from ethylenediamine/crypt solutions of precursors with nominal composition A(5)E(2)Bi(4) where A = Na, K, or Rb and E = Ga or In. The cluster in 4 is a well-ordered monocapped square antiprism with the four indium atoms occupying the five-bonded positions. Compound 5 contains two independent [In4Bi5](3-) clusters; one is the same as the cluster in 4, while the other is a tricapped trigonal prism with two elongated prismatic edges. All compounds are EPR-silent and therefore diamagnetic.