Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O

Abstract

Abstract Coarsely crystalline [C(NH2)3]3(PO2NH)3 · H2O (1) and [C(NH2)3]4(PO2NH)4 · 4 H2O (2) have been obtained by addition of [C(NH2)3]2CO3 to a freshly prepared solution of H3(PO2NH)3 or to a suspension of H4(PO2NH)4 · 2 H2O , respectively, followed by diffusion controlled addition of acetone. The crystal structures of 1 and 2 have been determined by single crystal X-ray methods ([C(NH,)3]3(PO,NH)3 · H2O: Pbca; a = 1565.6(2), b = 1068.31(6), c = 2091.8(2) pm, Z = 8; [C(NH2)3]4(PO2NH)4 · 4 H2O: Pbcn; a = 1739.64(10), b = 1084.19(6), c = 1334.96(11) pm, Z = 4). The P3N3 and P4N4 rings of the anions exhibit the chair conformation. In 1 two cyclic anions are interconnected into pairs via hydrogen bonds. In 2 columns along [001] are formed by hydrogen bonds between the anions. Hydrogen bonding through water molecules and C(NH2)3 + ions results in a three-dimensional network in 2. Complete dehydration is achieved below 160 or 180 °C for 1 or 2, respectively. Heating to 700 °C causes condensation reactions with evolution of NH3 and H2O yielding X-ray amorphous products