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By the oxidation of terbium metal with sulfur and tellurium in the presence of cesium bromide as flux at 850°C for 10 days, the first quaternary cesium terbium chalcogenides with ordered S 2−  and Te 2−  anions could be obtained as main products. The new compounds CsTb 3 STe 4  and CsTb 5 S 2 Te 6  occur as black needles. While CsTb 3 STe 4  crystallizes in the orthorhombic space group  Pnma  with  a =1924.08(16),  b =433.61(3) and  c =1493.47(13) pm for  Z =4, CsTb 5 S 2 Te 6  adopts the monoclinic space group  C 2/ m  with  a =2146.17(18),  b =431.42(3),  c =1049.68(9) pm and  β =102.064(3)° for  Z =2. Both crystal structures are characterized by parallel cationic and anionic strands ({    [    STb   3   ]    7  +    }∞  1${}_\infty ^1\{ {[{\rm{ST}}{{\rm{b}}_{\rm{3}}}]^{7 + }}\} $    and{    [    CsTe   4   ]    7  −    }∞  1${}_\infty ^1\{ {[{\rm{CsT}}{{\rm{e}}_4}]^{7 - }}\} $    for CsTb 3 STe 4  as well as{    [   S  2Tb   5   ]    11  +    }∞  1${}_\infty ^1\{ {[{{\rm{S}}_{\rm{2}}}{\rm{T}}{{\rm{b}}_{\rm{5}}}{\rm{]}}^{11 + }}\} $    and{    [    CsTe   6   ]    11  –    }∞  1${}_\infty ^1\{ {[{\rm{CsT}}{{\rm{e}}_6}]^{11-}}\} $    for CsTb 5 S 2 Te 6 ), all running along [010]. The cationic chains result from vertex-connected [STb 4 ] 10+  tetrahedra ( d (S 2− –Tb 3+ )=271–277 pm), whereas face-sharing bicapped trigonal or square prisms [CsTe 6+2 ] 15−  or [CsTe 8+2 ] 19− , respectively, form their anionic counterparts.

CsTb 3 STe 4 und CsTb 5 S 2 Te 6 : Zwei pseudo-ternäre Caesium-Terbium-Chalkogenide mit geordneten S 2− - und Te 2− -Anionen