Syntheses, crystal structure, and properties of the cage-like, hexaacidic P12S12N8(NH)(6) center dot 14H(2)O and its salts Li-6[P12S12N14] center dot 26 H2O, (NH4)(6)[P12S12N14] center dot 10 H2O, and K-6[P12S12N14] center dot 8 H2O [German]

摘要

The cage-like acid P12S12N8(NH)(6) . 14 H2O was obtained by the reaction of KSCN with P4S10 via the formation of K-6[P12S12N14] . 8 H2O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li-6[P12S12N14] . 26 H2O and (NH4)(6)[P12S12N14] . 10 H2O were synthesized. According to X-ray single-crystal structure analyses the compounds are built up by isosteric P-N cages [(P12S12N8N6[2])-N-[3]](6-). Each of them is made up of twelve P3N3 rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m (3) over bar; P12S12N8(NH)(6) . 14 H2O: P (1) over bar, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, alpha = 80,186(4), beta = 60,391(4), gamma = 60,605(4)degrees, Z = 1; Li-6[P12S12N14] . 26 H2O: Fm (3) over bar, a = 1797,4(1) pm, Z = 4; (NH4)(6)[P12S12N14] . 10 H2O: P6(3), a = 1153,2(1), c = 2035,6(2) pm, Z = 2; K-6[P12S12N14] . 8 H2O: R (3) over barc, a = 1142,37(5), c = 6009,6(3) 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. [References: 21]