SYNTHESIS, CRYSTAL-STRUCTURE, AND PROPERTIES OF TRIGUANIDINIUM TRI-MU-IMIDOCYCLOTRIPHOSPHATE MONOHYDRATE AND TETRAGUANIDINIUM TETRA-MU-IMIDOCYCLOTETRAPHOSPHATE TETRAHYDRATE, [C(NH2)(3)](3)(PO2NH)(3).H2O AND [C(NH2)(3)](4)(PO2NH)(4).4H(2)O

Coarsely crystalline [C(NH2)(3)](3)(PO2NH)(3).H2O (1) and [C(NH2)(3)]( 4)(PO2NH)(4).4H(2)O (2) have been obtained by addition of [C(NH2)(3)]( 2)CO3 to a freshly prepared solution of H-3(PO2NH)(3) or to a suspensi on of H-4(PO2NH)(4).2H(2)O, respectively, followed by diffusion contro lled addition of acetone. The crystal structures of 1 and 2 have been determined by single crystal x-ray methods ([C(NH2)(3)](3)(PO2NH)(3).H 2O; Pbca; a = 1565.6(2), b = 1068.31(6), c = 2091.8(2) pm, Z = 8; [C(N H2)(3)](4)(PO2NH)(4).4H(2)O; Pbcn; a = 1739.64(10), b = 1084.19(6), c = 1334.96(11) pm, Z = 4). The P3N3 and P4N4 rings of the anions exhibi t the chair conformation. In 1 two cyclic anions are interconnected in to pairs via hydrogen bonds. In 2 columns along [001] are formed by hy drogen bonds between the anions. Hydrogen bonding through water molecu les and C(NH2)(3)(+) ions results in a three-dimensional network in 2. Complete dehydration is achieved below 160 or 180 degrees C for 1 or 2, respectively. Heating to 700 degrees C causes condensation reaction s with evolution of NH3 and H2O yielding x-ray amorphous products.