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Single crystals of compounds with the composition  Ln  2 O[SeO 3 ] 2  ( Ln =Sm–Tm) were synthesized by solid-state reactions of the lanthanoid sesquioxides ( Ln  2 O 3 ) with the corresponding tribromides ( Ln Br 3 ) and selenium dioxide (SeO 2 ) in a molar ratio of 2:1:2 in evacuated torch-sealed silica ampoules. For the terbium case, Tb 4 O 7  and SeO 2  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  P 4 2 / 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 [ Ln O 8 ] 13−  polyhedra with a channel structure, where all  ψ  1 -tetrahedral [SeO 3 ] 2−  units are coordinating with their O 2−  anions to square antiprisms [ Ln O 8 ] 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, [O Ln  4 ] 10+  tetrahedra containing the  non- selenium-bonded O 2−  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.

Die Lanthanoid(III)-Oxid-Oxoselenate(IV) Ln 2 O[SeO 3 ] 2 ( Ln =Sm–Tm)