Interguanine hydrogen-bonding patterns in adducts with water and Zn-purine complexes (purine is 9-methyladenine and 9-methylguanine). Unexpected preference of Zn(II) for adenine-N7 over guanine-N7.

Guanine-guanine hydrogen bonding involving the Watson-Crick edge [N(1)H, N(2)H2] of one base and the Hoogsteen edge (N7, O6) of the other is the dominant association pattern in the solid-state structures of two hydrates of 9-ethylguanine (9-EtGH), and in adducts of 9-methylguanine (9-MeGH) with the Zn compounds [ZnCl2(H2O)(9-MeGH-N7)]*(9-MeGH) as well as [ZnCl2(H2O)(9-MeA-N7)]*2(9-MeGH) (9-MeA is 9-methyladenine). The structures of 9-EtGH*2H2O and 9-EtGH*3.5H2O are dominated by polymeric tape structures of the guanine and extended water clusters. In [ZnCl2(H2O)(9-MeGH-N7)]*(9-MeGH) the metalated guanine is involved in hydrogen bonding (GG3 motif) with a free 9-MeGH, which in turn is centrosymmetrically related to itself via hydrogen bonds involving N2H2 and N3 (GG4 motif). In [ZnCl2(H2O)(9-MeA-N7)]*2(9-MeGH) the metalated adenine base interacts via its Watson-Crick edge [N1, N(6)H2] with the sugar edge [N(2)H2, N3] of one of the guanine nucleobases of the GG pair. Crystallization of [ZnCl2(H2O)(9-MeA-N7)]*2(9-MeGH) from an aqueous solution containing 9-MeGH, 9-MeA, and ZnCl2 is fully unexpected in that the anticipated preference of Zn(II) for guanine-N7 is not realized and instead coordination to adenine-N7 is observed. The relevance of [ZnCl2(H2O)(9-MeGH-N7)]*(9-MeGH) and [ZnCl2(H2O)(9-MeA-N7)]*2(9-MeGH) for metal-containing nucleic acid triplex structures is discussed.