3D [Ag–Mg] polyanionic frameworks in the La4Ag10Mg3 and La4Ag10.3Mg12 new ternary compounds

The crystal structures of two new ternary phases, La{sub 4}Ag{sub 10}Mg{sub 3} and La{sub 4}Ag{sub 10.3}Mg{sub 12}, were refined from X-ray single crystal diffraction data. La{sub 4}Ag{sub 10}Mg{sub 3} crystallizes in the Ca{sub 4}Au{sub 10}In{sub 3} structure type, an ordered variant of the binary Zr{sub 7}Ni{sub 10} compound: orthorhombic, Cmce, oS68, a=14.173(5), b=10.266(3), c=10.354(3) A, Z=4, wR{sub 2}=0.0826, 676 F{sup 2} values, 50 variables. La{sub 4}Ag{sub 10.3}Mg{sub 12} represents a new structure type: orthorhombic, Cmmm, oS116-10.32, a=9.6130(3), b=24.9663(8), c=9.6333(2) A, Z=4, wR{sub 2}=0.0403, 1185 F{sup 2} values, 101 variables. The structural analysis of both compounds, highlighting a significant contraction of the Ag-Mg distances, suggests the existence of three-dimensional [Ag-Mg] networks hosting La atoms. LMTO calculations applied to La{sub 4}Ag{sub 10}Mg{sub 3} indicate that the strongest bonds occur for Ag-Ag and Ag-Mg interactions, and confirm the presence of a 3D{sub {infinity}}[Ag{sub 10}Mg{sub 3}]{sup {delta}}{sup -} polyanionic framework balanced by positively charged La atoms. -- Graphical abstract: An independent fragment of the 3D [Ag-Mg] framework in La{sub 4}Ag{sub 10}Mg{sub 3} together with an ELF section (1/2 0 0 basal plane). Display Omitted