Polymorphism of Li2Zn3

Abstract

Crystal structures of low- and high-temperature modifications of the binary phase Li(2)Zn(3) were determined by single-crystal X-ray diffraction techniques. The low-temperature modification is a disordered variant of Li(5)Sn(2), space group R\bar 3m (No. 166). The high-temperature modification crystallizes as an anti-type to Li(5)Ga(4), space group P\bar 3m1 (No. 164). Two polymorphs can be described as derivative structures to binary Li(5)Ga(4), Li(5)Sn(2), Li(13)Sn(5), Li(8)Pb(3), CeCd(2) and CdI(2) phases which belong to class 2 with the parent W-type in Krypyakevich's classification. All atoms in both polymorphs are coordinated by rhombic dodecahedra (coordination number CN = 14) like atoms in related structures. The Li(2)Zn(2.76) (for the low-temperature phase) and Li(2)Zn(2.82) (for the high-temperature phase) compositions were obtained after structure refinements. According to electronic structure calculations using the tight-binding-linear muffin-tin orbital-atomic spheres approximations (TB-LMTO-ASA) method, strong covalent Sn-Sn and Ga-Ga interactions were established in Li(5)Sn(2) and Li(5)Ga(4), but no similar Zn-Zn interactions were observed in Li(2)Zn(3).