Die Lanthanoid(III)-Oxid-Oxoselenate(IV) Ln 2O[SeO3]2 (Ln=Sm–Tm)

Abstract

Abstract Single crystals of compounds with the composition Ln 2O[SeO3]2 (Ln=Sm–Tm) were synthesized by solid-state reactions of the lanthanoid sesquioxides (Ln 2O3) with the corresponding tribromides (LnBr3) and selenium dioxide (SeO2) in a molar ratio of 2:1:2 in evacuated torch-sealed silica ampoules. For the terbium case, Tb4O7 and SeO2 have been reacted with elemental Tb in a molar ratio of 3:14:2. These lanthanoid(III) oxide oxoselenates(IV) all crystallize tetragonally with the space group P42/ncm and decreasing lattice parameters from the lighter to the heavier Ln 3+ cations (from a=1077.03(8) pm and c=526.38(4) pm for Ln=Sm to a=1049.60(8) pm and c=516.04(4) pm for Ln=Tm) according to the lanthanide contraction. They show a three-dimensional network of condensed [LnO8]13− polyhedra with a channel structure, where all ψ 1-tetrahedral [SeO3]2− units are coordinating with their O2− anions to square antiprisms [LnO8]13− and pointing with their non-bonding electron pairs into the empty channels, which propagate along [001]. As another characteristic feature of the crystal structure, [OLn 4]10+ tetrahedra containing the non-selenium-bonded O2− anions are trans-edge-connected to form {[O L n 4 / 2 e ] 4 + } ∞ 1 ${}_\infty ^{\rm{1}}{\rm{\{ [O}}Ln_{4/2}^{\rm{e}}{{\rm{]}}^{{\rm{4}} + }}{\rm{\} }}$ chains, which run parallel to the lone-pair channels in [001] direction and build up a tetragonal rod-packing.