The complex salts (Bz2H)+Y−, Bz = benzimidazole, Y = PF6− or BF4− have been identified in solution, and the molecularity of the fluoroborate, which has been crystallised, confirmed gravimetrically. Infrared and Raman spectra, together with those of the deuterated systems, indicate a similar structure in solution and the crystal, viz., an asymmetric single minimum bridging proton potential, in conformity with the X-ray structure, proving that the pronounced doublet observed in the vs band of the H bridged system is not due to proton tunnelling. The origin of the asymmetric structure is discussed.