Structures of the Phosphazenes [ClC(NPCl3)2]+PCl6 − and [CH3C(NPCl3)2]+SbCl6 − at 90 K

Abstract

The asymmetric units of both ionic compounds [N-(chloroformimidoyl)phosphorimidic trichloridato]trichlorophosphorus hexachlorophosphate, [ClC(NPCl3)2]+PCl^{-}_{6} (1), and [N-(acetimidoyl)phosphorimidic trichloridato]trichlorophosphorus hexachloroantimonate, [CH3C(NPCl3)2]+SbCl^{-}_{6} (2), contain two formula units with the atoms located on general positions. All the cations show cis–trans conformations with respect to their X—C—N—P torsion angles [X = Cl for (1), C for (2)], but quite different conformations with respect to their C—N—P—Cl torsion angles. Therefore, the two NPCl3 groups of a cation are inequivalent, even though they are equivalent in solution. The very flexible C—N—P angles ranging from 120.6 (3) to 140.9 (3)° can be attributed to the intramolecular Cl...Cl and Cl...N contacts. A widening of the C—N—P angles correlates with a shortening of the P—N distances. The rigid-body motion analysis shows that the non-rigid intramolecular motions in the cations cannot be explained by allowance for intramolecular torsion of the three rigid subunits about specific bonds.