The complex of the hexanucleotide duplex d(CGTACG) and the antitumor drug 3'-(2-methoxy-4-morpholinyl)-doxorubicin was investigated by two-dimensional 1H nuclear magnetic resonance spectroscopy. After complete assignment of the non-exchanging DNA protons and nearly all drug protons, eight nuclear Overhauser enhancement interactions between drug and DNA were measured at short mixing times. A model was built which shows that the overall structure is very similar to the related daunomycin complex, with the new morpholinyl-substituent extending further into the minor groove of the DNA double helix. The structural information is used for the discussion of the possible formation of DNA-adducts by the new anticancer drug.