We use steady-state and ultrafast nonlinear spectroscopies in combination with density functional theory calculations to explain light emission below the optical gap energy (Eo) of crystalline samples of 5,12-diphenyl tetracene (DPT). In particular, the properties of vibrational coherences imprinted on a probe pulse transmitted through a DPT single crystal indicate discrete electronic transitions below Eo of this organic semiconductor. Analysis of coherence spectra leads us to propose structural defect states give rise to these discrete transitions and subgap light emission. We use the polarization dependence of vibrational coherence spectra to tentatively assign these defects in our DPT samples. Our results provide fundamental insights into the properties of midgap states in organic materials important for their application in next-generation photonics and optoelectronics technologies.