The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi-2(dpmdH)(2)(O2CCF3)(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO2CCF3 in tetrahydrofuran (THF). The reaction of Cu(OCH3)(2) with di-2-pyridyl ketone, H2O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO2CCH3)(2), 2, while the reaction of Cu(OAC)(2)(H2O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu-4[(2-Py)(2)CO(OH)](2)(O2CCH3)(6)(H2O)(2), 3 The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO2CCH3 molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data : 1, C38H34N4O14F12Bi2, triclinic P (1) over bar, a = 11.764(3) Angstrom, b = 11.949(3) Angstrom, c = 9.737(1) Angstrom, alpha = 101.36(2)degrees, beta = 105.64(2)degrees, gamma = 63.79(2)degrees, Z = 1; 2, C26H26N4O8Cu/CH2Cl2, monoclinic C2/c, a = 25.51(3) Angstrom, b = 7.861(7) Angstrom, c = 16.24(2) Angstrom, beta = 113.08(9)degrees, Z = 4; 3, C34H40N4O18Cu4/CH2Cl2, triclinic P (1) over bar, 10.494(2) Angstrom, b = 13.885(2) Angstrom, c = 7.900(4) Angstrom, Angstrom = 106.52(2)degrees, beta = 90.85(3)degrees, gamma = 94.12(1)degrees, Z = 1.