含2-胺基-4,6-二甲基嘧啶之配位基與過渡金屬鹵化物之合成及結構鑑定

Abstract

The reactions of the polydentate ligand 2-amino-4,6-dimethyl- pyrimidine (L) with CuX ( X = Cl , Br ) and ZnCl2 afforded the following complexes: Cu4Cl6(HL)2, 1, [Cu4Br6][HL]2, 2, [Cu Cl3][H2L] , 3, and [ZnCl4][HL] 2．H2O , 4. All the complexes have been structurally characterized by X-ray crystallography. In the new tetranuclear complex Cu4Cl6(HL)2 , 1, with uncommon square Cu(I) tetramers of mixed Td-Tp-Td-Tp geometries, the Cu(I) atoms are bridged and bonded by six chloride atoms and two mono-protonated, HL+, ligands. The molecules in 1 are interlinked through N-H---Cl hydrogen bonds to form 3-D supramolecular structures. In complex [Cu4Br6][HL]2 , 2, the μ4- and μ2- bromide atoms of the mono-protonated, HL+, ligands interact with the 1-D Cu4Br6 inorganic chains through C-H---Br and N-H---Br hydrogen bonds. The cations and anions in 2 are interlinked through C-H---Br, N-H---Br and N-H---N hydrogen bonds to form a 3-D hydrogen-bounded structure. Complex [CuCl3][H2L], 3 shows 2-D layer formed by bis-protonated H2L2+ ligands and CuCl32- anions which are interlinked through N-H---Cl and C-H---Cl hydrogen bonds. The structure of [ZnCl4][HL]2．H2O, 4, consists a tetrahedral ZnCl42- anion, two mono-protonated HL+ ligands and one water molecule. Their molecules are interlinked through N-H---Cl, C-H---Cl, O-H---Cl hydrogen bonds and π – π stackings.