Ternary CaCu{sub 4}P{sub 2}-type pnictides AAg{sub 4}Pn{sub 2} (A=Sr, Eu; Pn=As, Sb)

Four ternary pnictides AAg{sub 4}Pn{sub 2} (A=Sr, Eu; Pn=As, Sb) were prepared by reactions of the elements at 850 Degree-Sign C and their crystal structures were determined from single-crystal X-ray diffraction studies. These silver-containing pnictides AAg{sub 4}Pn{sub 2} adopt the trigonal CaCu{sub 4}P{sub 2}-type structure (Pearson symbol hR21, space group R3-bar m, Z=3; a=4.5555(6) A, c=24.041(3) A for SrAg{sub 4}As{sub 2}; a=4.5352(2) A, c=23.7221(11) A for EuAg{sub 4}As{sub 2}; a=4.7404(4) A, c=25.029(2) A for SrAg{sub 4}Sb{sub 2}; a=4.7239(3) A, c=24.689(2) A for EuAg{sub 4}Sb{sub 2}), which can be derived from the trigonal CaAl{sub 2}Si{sub 2}-type structure of the isoelectronic zinc-containing pnictides AZn{sub 2}Pn{sub 2} by insertion of additional Ag atoms into trigonal planar sites within [M{sub 2}Pn{sub 2}]{sup 2-} slabs built up of edge-sharing tetrahedra. Band structure calculations on SrAg{sub 4}As{sub 2} and SrAg{sub 4}Sb{sub 2} revealed that these charge-balanced Zintl phases actually exhibit no gap at the Fermi level and are predicted to be semimetals. - Graphical abstract: SrAg{sub 4}As{sub 2} and related pnictides adopt a CaCu{sub 4}P{sub 2}-type structure in which additional Ag atoms enter trigonal planar sites within slabs built from edge-sharing tetrahedra. Highlights: Black-Right-Pointing-Pointer AAg{sub 4}Pn{sub 2} are the first Ag-containing members of the CaCu{sub 4}P{sub 2}-type structure. Black-Right-Pointing-Pointer Ag atoms are stuffed in trigonal planar sites within CaAl{sub 2}Si{sub 2}-type slabs. Black-Right-Pointing-Pointer Ag-Ag bonding develops through attractive d{sup 10}-d{sup 10} interactions.