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

The crystal structures of two new ternary phases, La4Ag10Mg3 and La4Ag10.3Mg12, were refined from X-ray single crystal diffraction data. La4Ag10Mg3 crystallizes in the Ca4Au10In3 structure type, an ordered variant of the binary Zr7Ni10 compound: orthorhombic, Cmce, oS68, a=14.173(5), b=10.266(3), c=10.354(3) Å, Z=4, wR2=0.0826, 676 F2 values, 50 variables. La4Ag10.3Mg12 represents a new structure type: orthorhombic, Cmmm, oS116-10.32, a=9.6130(3), b=24.9663(8), c=9.6333(2) Å, Z=4, wR2=0.0403, 1185 F2 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 La4Ag10Mg3 indicate that the strongest bonds occur for Ag–Ag and Ag–Mg interactions, and confirm the presence of a 3D∞[Ag10Mg3]δ− polyanionic framework balanced by positively charged La atoms.

An independent fragment of the 3D [Ag–Mg] framework in La4Ag10Mg3 together with an ELF section (1/2 0 0 basal plane). Figure optionsDownload as PowerPoint slide