title: New ternary germanides La4Mg5Ge6 and La4Mg7Ge6: crystal structure and chemical bonding.
abstract: The synthesis, structural characterization, and chemical-bonding peculiarities of the two new polar lanthanum-magnesium germanides La(4)Mg(5)Ge(6) and La(4)Mg(7)Ge(6) are reported. The crystal structures of these intermetallics were determined by single-crystal X-ray diffraction analysis. The La(4)Mg(5)Ge(6) phase crystallizes in the orthorhombic Gd(4)Zn(5)Ge(6) structure type [Cmc2(1), oS60, Z = 4, a = 4.5030(7) Å, b = 20.085(3) Å, c = 16.207(3) Å, wR2 = 0.0451, 1470 F(2) values, 93 variables]. The La(4)Mg(7)Ge(6) phase represents a new structure type with a monoclinic unit cell [C2/m, mS34, Z = 2, a = 16.878(3) Å, b = 4.4702(9) Å, c = 12.660(3) Å, β = 122.25(3)°, wR2 = 0.0375, 1466 F(2) values, 54 variables]. Crystallographic analysis together with linear muffin-tin orbital band structure calculations reveals the presence of strongly bonded 3D polyanionic [Mg-Ge] networks balanced by positively charged La atoms in both stoichiometric compounds. The La(4)Mg(5)Ge(6) compound is related to Zintl phases, showing a prominent density of states pseudogap at the Fermi level. A distinctive feature of the La(4)Mg(5)Ge(6) structure is the presence of Ge-Ge covalent dumbbells; in La(4)Mg(7)Ge(6), the higher Mg content generates a polyanionic network consisting exclusively of Mg-Ge heterocontacts. Nevertheless, the frameworks of the two phases are structurally similar, as is highlighted in this work.
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via Dodecaneso 31, I-16146 Genova, Italy. pavlo.solokha@unige.it
authors.forename: Pavlo
authors.initials: P
authors.lastname: Solokha
authors.forename: Serena
authors.initials: S
authors.lastname: De Negri
authors.forename: Monika
authors.initials: M
authors.lastname: Skrobanska
authors.forename: Adriana
authors.initials: A
authors.lastname: Saccone
authors.forename: Volodymyr
authors.initials: V
authors.lastname: Pavlyuk
authors.forename: Davide M
authors.initials: DM
authors.lastname: Proserpio