Synthese, Kristallstruktur und Eigenschaften der käfigartigen, sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Abstract

pm, Z = 6. Im Kristall sind die Ka È fige der Sa È ure u È ber Hydratwasser durch Wasserstoffbru È cken miteinander verknu È pft. Die Kationen in den Salzen besitzen eine hohe Mobilita È t und befinden sich zwischen den Ka È figen.Abstract. The cage-like acid P 12 S 12 N 8 (NH) 6´1 4 H 2 O was obtained by the reaction of KSCN with P 4 S 10 via the formation of K 6 [P 12 S 12 N 14 ]´8 H 2 O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li 6 [P 12 S 12 N 14 ]´26 H 2 O and (NH 4 ) 6 [P 12 S 12 N 14 ]´10 H 2 O were synthesized. According to X-ray single-crystal structure analyses the compounds are built up by isosteric P±N cages [P 12 S 12 N [3] 8 N [2] 6 ] 6± . Each of them is made up of twelve P 3 N 3 rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P 12 S 12 N 8 (NH) 61 pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high-mobility and are located between the cages.