Using a new, low-temperature, fluoride-based process, thorium nitride imide of the chemical formula Th2N2(NH) was synthesized from thorium dioxide via an ammonium thorium fluoride intermediate. The resulting product phase was characterized by powder X-ray diffraction (XRD) analysis and was found to be crystallographically similar to Th2N3. Its unit cell was hexagonal with a space group of P3 (m) over bar1 and lattice parameters of a = b = 3.886(1) and c = 6.185(2) angstrom. The presence of NH in the nitride phase was verified by Fourier transform infrared spectroscopy (FTIR). Total energy calculations performed using all-electron scalar relativistic density functional theory (DFT) showed that the hydrogen atom in the Th2N2(NH) prefers to bond with nitrogen atoms occupying la Wyckoff positions of the unit cell. Lattice fringe disruptions observed in nanoparticle areas of the nitride species by high-resolution transmission electron microscopic (HRTEM) images also displayed some evidence for the presence of -NH group. As ThO2 was identified as an impurity, possible reaction mechanisms involving its formation are discussed.