Eight-coordinated arsenic in the Zintl phases RbCd4As3 and RbZn4As3: synthesis and structural characterization

Reported are two new series of Zintl phases, ACd(4)Pn(3) and AZn(4)Pn(3) (A = Na, K, Rb, Cs; Pn = As, P), whose structures feature complex atomic arrangements based on four- and eight-coordinated arsenic and phosphorus. A total of 12 compounds have been synthesized from the corresponding elements via high temperature reactions, and their structures have been established by X-ray diffraction. RbCd(4)As(3), KCd(4)As(3), NaCd(4)As(3), NaZn(4)As(3), KCd(4)P(3), and KZn(4)P(3) crystallize with a new rhombohedral structure (space group R3m, Z = 3, Pearson symbol hR24), while the isoelectronic RbZn(4)As(3), CsCd(4)As(3), CsZn(4)As(3), KZn(4)As(3), CsZn(4)P(3), and RbZn(4)P(3) adopt the tetragonal KCu(4)S(3)-type structure (space group P4/mmm, Z = 1, Pearson symbol tP8). Both structures are very closely related to the ubiquitous CaAl(2)Si(2) and ThCr(2)Si(2) structure types, and the corresponding relationships are discussed. The experimental results have been complemented by linear muffin-tin orbital (LMTO) tight-binding band structure calculations. Preliminary transport properties measurements on polycrystalline samples suggest that the compounds of these families could be promising thermoelectric materials.