New tetragonal structure type for A2Ca10S(9 (A = Li, Mg). Electronic variability around a Zintl phase

The phases LiMgCa(10)Sb(9) (1), Mg(2)Ca(10)Sb(9) (2), and Li(1.38(2))Ca(10.62)Sb(9) (3) have been synthesized by high-temperature solid-state means and characterized by single-crystal means and property measurements. These occur in space group P4(2)/mnm, Z = 4, with a = 11.8658(5), 11.8438(6), 11.9053(7) Angstroms and c = 17.181(2), 17.297(2), 17.152(2) Angstroms, respectively. The two types of A atoms occupy characteristic sites in a Ca-Sb network that contains a 5:2 proportion of (formal) Sb(3-) and Sb(2)(4-) anions and can be described in terms of two slab types stacked along 001]. Bonding appears to be strong in these salts with generally normal distances and high coordination numbers except for the 4-bonded atoms in a C(2)(v) position for the second type of A that is occupied by Li, Mg or Ca(0.62(2))Li(0.38), respectively. The three compounds are, respectively, an ideal electron-precise Zintl phase, one e(-)-rich and 0.40(4) e(-)-short per formula unit. The LiMgCa(10)Sb(9) compound is correspondingly diamagnetic and presumably a semiconductor.