The structures and spectroscopic properties of azirine (C2H3N), a nitrogen-containing three-membered cyclic molecule, and its isomers were studied with state-of-the-art ab initio quantum chemical methods. Azirine is isomeric with methyl cyanide (CH3CN) and methyl isocyanide (CH3NC)-both observed in the star-forming regions of Sgr B2. In this study, we characterize the stationary points on the potential energy surface, relative energies, dipole moments, rotational constants, and harmonic vibrational frequencies of the 2 H-azirine ( a), 1 H-2,2 H-azirine ( b, carbene isomer), and 1 H-azirine ( c) cyclic isomers. The CCSD(T) method and density functional theory (DFT), using the ωB97-X functional, along with Dunning's cc-pVXZ (X = T and Q) basis sets were used to optimize molecular geometries and calculate vibrational frequencies. The 2 H-azirine, an imine isomer ( a), was found to be the lowest in energy among the cyclic isomers, followed by the carbene isomer ( b), and last the 1 H-azirine, an enamine isomer ( c). All three cyclic isomers have a C s symmetry equilibrium structure. Azirines, if identified (three linear C2H3N isomers are already identified in the same source toward the galactic center, Sgr B2), would be the first nitrogen-containing cyclic molecules identified in an astronomical observation.