AbstractThe one‐bond13C13C coupling constants (1JCC) in all nine possible dithieno[b,d]pyridines were measured at natural isotope abundance by using the INADEQUATE pulse sequence technique. The unambiguous assignments of the13C NMR shifts of these compounds are also reported. Assignments are based on proton decoupled13C spectra, heteronuclear correlation spectra (HETCOR) and 1D‐INADEQUATE13C NMR spectroscopy. The effect of the fusion pattern and the influence of the heteroatoms in the ring skeleton on the NMR parameters are discussed. By a multivariate principal components data analysis, it was shown that the magnitude of1J(CC) of the pyridine subunit could be satisfactorily predicted from shift data, the azomethine CH coupling constant and MNDO bond orders. The last parameter gave only a minor contribution to the coupling vari