Four stable hydrogen- and lithium-bonded heterodimers containing the HF molecule and an electride-like Li₄C₄H₂N₂ molecule were predicted by ab initio calculations. Equilibrium geometries, binding energies, and dipole moments were determined. The interaction-induced contributions to dipole moments and natural bond orbital charges were analyzed. Infrared transition frequencies and intensities of two stronger heterodimers were calculated in the harmonic approximation. Variational 1D anharmonic calculations performed for all stable heterodimers predicted negative frequency shifts up to −1000 cm⁻¹ and an order of magnitude increase in intensity of the H–F stretching band upon formation of these systems.