METALLIC COMPLEXATION BY INNER AND OUTER NITROGENS OF BIS(DIAZINE) HETEROCYCLES - THE CASES OF 4,4'-BIPYRIMIDINE AND 2,2'-BIPYRAZINE

The synthesis of [Cu(6,6'-dimethyl-2,2'-bipyrazine)(2)][BF4] (4), [Cu(2,2'-dimethyl-6,6'-diphenyl-4,4'-bipyrimidine)(2)]-[PF6] (3), and catena-poly-[(2,2'-dimethyl-4,4'-bipyrimidine-N,N',N')bis(acetonitrile)dicopper(I)] (5) was realized from the corresponding free heterocyclic ligands. X-ray structures of the two last products were determined, and their structural data are as follows. 3: chemical formula (CuN8C44H36PF6; lattice constants with esd's (a-c, Angstrom; alpha-gamma, deg) 12.089(1), 16.229(7), 21.196(3), 90, 98.46(1), 90; crystal system monoclinic; space group P2(1)/n; Z = 4. 4: chemical formula CuN8C20H20BF4. 5: chemical formula CuN5C12H13PF6; lattice constants with esd's (a-c, A; alpha-gamma, deg) 12.900(3), 8.773(3), 14.702(4); 90, 101.99(2), 90; crystal system monoclinic; space group P2(1)/n; Z = 4. The proton NMR and crystallographic results of the unsubstituted 4,4'-bipyrimidine show that both inner and outer nitrogens are involved in the coordination metal center process, giving a structure of an infinite-chain copper(I) polymer.