Abstract

Abstract The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) with the composition Na2 RE 3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu) has been synthesized via solid-state reactions. For these conversions mixtures of the respective rare-earth metal(III) oxides, tellurium dioxide and sodium chloride as flux and reactant were prepared, intimately ground and heated for 5 days at 1225 K. The almost colorless single crystals were characterized via single-crystal X-ray diffractometry. In the monoclinic crystal structure of these compounds two crystallographically different rare-earth metal(III), but only one sodium cation sites occur. [REO8]13− polyhedra around both RE 3+ positions as well as sodium-centered polyhedra [NaO4Cl4]8− form layers via different connectivity modes. These layers spread out parallel to the (001) plane and arrange alternatingly resulting in the three-dimensional network of the Na2 RE 3Cl3[TeO3]4 structure, where the Te4+ lone-pair cations at two different sites work as linkers by forming isolated ψ 1-tetrahedra [TeO3]2−. Some of these compounds were represented before in different settings of space group C2/c. Now the complete series of the Na2 RE 3Cl3[TeO3]4 representatives with RE = Y, La–Nd, Sm–Lu is described consistently for a better comparison and understanding. Additionally, a single crystal of Na2Pr3Cl3[TeO3]4 was measured via energy dispersive X-ray analysis to verify the included elements, powder samples of Na2Nd3Cl3[TeO3]4 were characterized by X-ray diffractometer data for a phase-purity check and a single-crystal Raman spectrum of Na2Yb3Cl3[TeO3]4 served for proving the signature of discrete [TeO3]2− anions.

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