Single Crystal X-Ray Structure Determination and Vibrational Spectroscopy of 2-Aminopyrimidinium Hydrogen Trioxofluorophosphate and bis(2-Aminopyrimidinium) Trioxofluorophosphate

Two single-crystal X-ray structure determinations of 2-aminopyrimidinium hydrogen tri oxofluorophosphate, (C4H6N3)+·(HFO3P)−, (I), and bis(2-aminopyrimidinium) trioxofluorophosphate, 2(C4H6N3)+·(FO3P)2−, (II), as well as their vibration spectra (FTIR on powder samples and the Raman spectra on unoriented single crystals) with a detailed assignment of vibrational modes are reported. The structure (I) consists of one independent 2-aminopyrimidinium cation and one hydrogen trioxofluorophosphate anion, while (II) consists of two symmetry independent 2-aminopyrimidinium cations and one trioxofluorophosphate anion. In (I), there is an O-H···O hydrogen bond of a moderate strength. A pair of these hydrogen bonds is situated about the symmetry centre and involved in the graph set motif R22(8). There are also N-H···O hydrogen bonds of a moderate strength, which are present in both structures while being involved in the graph set motifs R22(8), too. In addition, the N-H···O hydrogen bonds form R34(10) graph set motifs in (II). The latter motifs form ribbons which propagate parallel to the unit-cell axis a. In both structures, there are present π···π-electron ring interactions into which the primary amine groups are involved. In both structures, there are also present weak C-H···N hydrogen bonds with participation of the non-protonated ring N-atoms. The fluorine participates in the C-H···F hydrogen bonds in both title structures. The P-F distances are normal in both anions. The structure (I) differs from the known structure of 2-aminopyrimidinium hydrogen phosphite, the compositional isomer, though the main hydrogen bonds show similar geometry in both structures. The crystal of (I) was twinned.