The availability of accurate crystal structures of CT co-crystal complexes is essential for developing chemical databases used by high-throughput screening methods for materials discovery. To this aim we report details of the syntheses and crystal structures of Npe:TCNB and Npe:TCNQ co-crystals. Our reinvestigation of the crystal structure of Npe:TCNB reveals a monoclinic structure, previously assigned as triclinic. High-resolution crystal structures are necessary for benchmarking theoretical models and identifying structural effects of component molecules on crystal packing. Experimental UV-Vis diffuse reflectance spectra were measured to assess the peak positions and intensities of bright states of the co-crystals. Comparing relative intensities of these states to those calculated for theoretical molecular model systems plays an integral role in assessing the quality of our D-A dimer models. Furthermore, experimental UV-Vis diffuse reflectance spectra of Npe:TCNQ reveal vibronic structure in the 600-900 nm region, indicating strong photon-induced CT. NBO analysis of the ground state of our model clusters reveals that the degree of S0 CT is slightly greater in Npe:TCNQ than in Npe:TCNB, as predicted from tests of the recently developed orbital similarity metric. We find that differences in the S0 and S1 degree of CT in each system are quite small, with each system exhibiting dominantly neutral character in the S0 state and ionic character in the S1 state. The integrated experimental-theoretical methodology presented here for quantifying ground and excited state CT in CT co-crystals enables high-accuracy benchmarking of models for future discovery of novel co-crystals with desired optoelectronic properties.