The crystalline isotypic solvates Rb4Sn4·2NH3, Cs4Sn4·2NH3, and Rb4Pb4·2NH3 have been synthesized using the direct reduction of elemental tin or tetraphenyltin, respectively, with heavier alkali metals or the dissolution of the binary phase RbPb in liquid ammonia. These compounds contain the cluster ions [Sn4]4– or [Pb4]4– respectively. This is the first time that[Tt4]4– ions (Tt = tetrels) are detected as result of a solution reaction. The accommodation of the ammonia molecules, which build up ion‐dipole interactions to alkali metal cations, requires some modifications of the crystal structures compared to the binary phases RbSn, CsSn, and RbPb. The tetrahedral [Tt4]4– anions have a slightly lower coordination by Rb+ or Cs+ cations and, furthermore, the intercluster distances show a remarkable increase.
Tin I 4800 Tetrahedral [Tt4] 4-Zintl Anions Through Solution Chemistry: Syntheses and Crystal Structures of the Ammoniates Rb 4 Sn 4 ·2NH 3 , Cs 4 Sn 4 ·2NH 3 , and Rb4Pb4·2NH3. -The title compounds are prepared by reaction of the elements in liq. NH3 or, in the case of Cs4Sn4·2NH3, by reaction of Ph4Sn with excess Cs in liq. NH3 (-38°C, several months). The three isotypic compounds crystallize in the monoclinic space group P21/a with Z = 4. The compounds are the first examples for the formation of [Sn 4 ] 4and [Pb 4 ] 4-Zintl ions in a solution reaction. Compared to the binary phases RbSn, CsSn, and RbPb, the tetrahedral [M4] 4-(M:Sn, Pb) compounds have a slightly lower coordination by Rb + or Cs + cations and the intercluster distances show a remarkable increase. -(WIESLER, K.; BRANDL, K.; FLEISCHMANN, A.; KORBER*, N.; Z. Anorg. Allg. Chem. 635 (2009) 3, 508-512; Inst. Anorg. Chem., Univ. Regensburg, D-93053 Regensburg, Germany; Eng.) -Schramke 21-016
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