Abstract

The title compounds were synthesized by reacting the elements in sealed tantalum tubes in a high-frequency furnace. They were investigated by X-ray diffraction on both powders and single crystals. With the trivalent rare earth elements they adopt the ZrNiAl-type structure, space group P62m:a=782.5(3) pm, c=432.8(1) pm, wR2=0.0420, and 277 F2 values for CeAgMg and a=775.7(3) pm, c=426.1(1) pm, wR2=0.0387, and 271 F2 values for NdAgMg with 15 parameters for each refinement. Geometrical motifs in CeAgMg are two types of silver-centered tricapped trigonal prisms: [Ag1Mg3Ce6] and [Ag2Mg6Ce3]. The silver and magnesium atoms form a three-dimensional [AgMg] network in which the cerium atoms fill distorted hexagonal channels. With divalent europium and ytterbium the orthorhombic TiNiSi-type occurs, space group Pnma:a=777.4(2) pm, b=463.0(1) pm, c=898.8(2) pm, wR2=0.0430, and 401 F2 values for EuAgMg and a=753.66(7) pm, b=446.49(7) pm, c=887.2(1) pm, wR2=0.0742, and 485 F2 values for YbAgMg with 21 parameters for each refinement. The europium(ytterbium) and magnesium atoms form zigzag chains of edge- and face-sharing trigonal prisms which are centered by the silver atoms. Also in EuAgMg and YbAgMg a three-dimensional [AgMg] network occurs in which the europium(ytterbium) atoms are embedded. The magnesium positions of the cerium, neodymium, europium, and ytterbium compound show a small mixed magnesium/silver occupancy, leading to the refined compositions CeAg1.034(7)Mg0.966(7), NdAg1.035(6)Mg0.965(6), EuAg1.032(6)Mg0.968(6), and YbAg1.053(8)Mg0.947(8) for the crystals investigated. The crystal chemistry and chemical bonding in these intermetallics is briefly discussed.

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