We investigate the role of interstitial electronic states in the metal-to-semiconductor transition and the origin of the volume collapse in Ca2N during the pressure-induced phase transitions accompanied by changes of electride subspace dimensionality. Our findings highlight the importance of correlation effects in the electride subsystem as an essential component of the complex phase transformation mechanism. By employing a simplified model that incorporates the distortion of the local environment surrounding the interstitial quasi-atom (ISQ) which emerges under pressure and solving this model by Dynamical Mean Field Theory (DMFT), we successfully reproduced the evolution between the metallic and semiconducting phases and captured the remarkable volume collapse. Central to this observation is a significant enhancement of the localization of excess electrons and the emergence of antiferromagnetic pairing among them, leading to a spin-state transition with a notable reduction in the magnetic moment on the interstitial states.