The preparation and X-ray structures of two dinuclear complexes 4 and 5, derived from [(dien)Pt(GH-TV7)]2+ (1), containing the 9-methylguanine anion G (4, 5) and deprotonated 1-methyluracil U (5) are reported. ¡[(dien)Pt]2(G-/V7,/Vl)j(C104)3-2H20 (4) and c/j-[(NH3)2Pt(U-A3)(G-TV1,A7)Pt(dien)](C104)2<2.5H20 (5) crystallize in the monoclinic (4) and triclinic (5) systems, space groups C2/c (4) and PT (5). Cell dimensions are a = 32.494 (5) A (4), 8.504 (3) Á ( 5), b = 17.052 (3) Á (4), 13.466 (3) A ( 5), c = 11.507 (2) A (4), 15.736 (3) A ( 5), a = 104.34 (2)°( 5), ß = 104.65 (3)°(4), 108.66 (2)°(5), = 102.48 (2)°( 5), V = 6168.5 A3 (4), 1566.1 A3 (5), and Z = 8 (4), 2 (5). In both cations, a (dien)Pt11 entity is coordinated to the guanine via N7, whereas the N1 position is either occupied by a (dien)Pt11 (4) or a cw-(NH3)2Pt(U) (5) residue. Coordination of the Pt at N1 takes place from 1 under virtually physiological pH conditions. Compound 5 represents the first example of a hypothetical DNA cross-link of cisplatin with N1 of a purine and N3 of a pyrimidine, two sites normally in the interior of a DNA double helix.Both nucleobases adopt a head-head orientation, thus making 5 a realistic model of a guanine, thymine cross-link. The large dihedral angle of 102°between the two bases and the long separation of 9.5 A between the alkyl groups of both bases point toward a DNA distortion, which, if realized, should exceed that of the well-known G,G adduct at the DNA periphery by far. In slightly acidic medium, 1 interacts with Ag+ without deprotonation at N1 but rather Ag+ binding to N3.