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Eu5Ga2As6 and Ba5In2As6-xSbx: new As-containing members of the Sr5Al2Sb6 structure type
Md Rashed Alam1, Robert Lane2, Mojib Pourashouri Khajkini3
1Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA.
Abstract:
The ternary Zintl arsenide Eu5Ga2As6 and two members of the Ba5In2As6-xSbx [x = 0.49 (2) and 2.92 (2)] solid solution series were obtained from Pb-flux reactions and characterized by single-crystal X-ray diffraction methods. They adopt the uncommon Sr5Al2Sb6 structure type and represent the first As-bearing compounds adopting this structure type. The polyanionic substructure consists of 1D chains of edge- and corner-sharing [TrPn4] (Tr = Ga, In; Pn = As, Sb) tetrahedra extending along the [100] direction, with pendant [Pn2] dumbbells. Non-random As/Sb site preferences within the polyanionic substructure of Ba5In2As6-xSbx are also discussed. Formal electron counting supports valence-precise Zintl notation for all reported compositions. First-principles electronic structure calculations for Eu5Ga2As6 reveal a moderate indirect band gap of ∼0.8 eV. Comparative calculations for the chemically related Eu3GaAs3 phase, also isolated during the present study, predict a narrow direct band gap of ∼0.2 eV and provide additional context for the bonding and electronic structure of Eu5Ga2As6.
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