Electron capture by the sigma* LUMO of isoxazole triggers the dissociation of the O-N bond and the opening of the ring. Photodetachment of the resulting anion accesses a neutral structure, in which the O center dot and center dot N bond fragments interact through the intact remainder of the molecular ring and via a 3 angstrom gap created by the bond dissociation. These through-bond and through-space interactions result in a dense manifold of diradical states, including (in the order of increasing energy) a triplet, an open-shell singlet, a closed-shell singlet, and another triplet state. We report photoelectron spectra that reflect partially resolved signatures of these states. Remarkably, the structure of the isoxazole diradical manifold is qualitatively different from that of the analogous system in oxazole. The distinct properties of the two manifolds are explained by using a coupled-fragments molecular-orbital model. Consistent with the past conclusions [Culberson et al. Phys. Chem. Chem. Phys. 2014, 16, 3964-3972], the lingering through-space interactions between the O center dot and center dot C bond fragments in ring-open oxazole are responsible for the relative stabilization of the closed-shell singlet state, which correlates with the groundstate cyclic structure. In contrast, the placement of the N atom in the terminal position within the ring-open structure of isoxazole is the key factor leading to the near degeneracy of the pi and sigma* orbitals, favoring a triplet-state configuration.