Interplay between size and electronic effects in determining the homogeneity range of the A9Zn4+xPn9 and A9Cd4+xPn9 phases (0 < or = x < or = 0.5), A = Ca, Sr, Yb, Eu; Pn = Sb, Bi.

Seven cadmium- and zinc-containing Zintl phases, A9Zn(4+x)Pn9 and A9Cd(4+x)Pn9 (0 < or = x < or = 0.5), A = Ca, Sr, Yb, Eu; Pn = Sb, Bi, have been synthesized, and their structures have been determined by single-crystal X-ray diffraction. All compounds are isostructural and crystallize in the centrosymmetric orthorhombic space group Pbam (no. 55, Z = 2), and their structures feature tetrahedra of the pnicogens, centered by the transition metal. The tetrahedra are not isolated but are connected through corner sharing to form ribbons, which are separated by the divalent cations. The occurrence of a small phase width and its variation across this family of compounds has been systematically studied by variable temperature crystallography, resistivity, and magnetic susceptibility measurements, and these results have been reconciled with electronic structure calculations performed using the tight-binding linear muffin-tin orbital (TB-LMTO-ASA) method. These analyses of the crystal and electronic structure indicate that the polyanionic subnetwork requires 19 additional electrons, whereas only 18 electrons are provided by the cations. Such apparent "electron deficiency" necessitates the presence of an interstitial atom in order for an optimal bonding to be achieved; however, an interplay between the sizes of the cations and anions and the total valence electron concentration (governed by the stoichiometry breadth) is suggested as a possible mechanism for achieving structure stability. The structural relationship between these and some known structures with two-dimensional layers are discussed as well.