DNA fragments containing the sequence d(GCGAAAGC) adopt a base-intercalated (zipper-like) duplex in crystalline state at high ionic strength. To investigate effects of point mutation at the 5th residue on the structure, two crystal structures of d(GCGAGAGC) and d(GCGATAGC) have been determined by X-ray crystallography. In both crystals, the two octamers related by a crystallographic two-fold symmetry are aligned in an anti-parallel fashion and associated to each other to form a duplex, suggesting that the base-intercalated duplex is stable even when the 5th residue is mutated with other bases. The sheared G3:A6 pair formation makes the two phosphate backbones closer and facilitates formation of the A-X*-X-A* base-intercalated motif. The three duplexes are assembled around the two hexamine cobalt chlorides. The central X and X* residues are bound to a different cation depending on the kinds of bases.