Interconversion of a monomer and two coordination polymers of a copper(II)-reduced Schiff base ligand-1,10-phenanthroline complex based on hydrogen- and coordinative-bonding.

Two compounds, [Cu(3)(Sbal)(2)(phen)(H(2)O)(2)](ClO(4))(2)-3H(2)O (1) and [Cu(H(2)Sbal)(2)(phen)](ClO(4))(2) (2), were isolated in successive steps from the reaction mixture containing Cu(ClO(4))(2)-6H(2)O, 1,10-phenanthroline, N-(2-hydroxybenzyl)-beta-alanine (H(2)Sbal), and LiOH in the ratio of 1:1:1:1. When the ratio of the base was doubled, the neutral monomer [Cu(Sbal)(phen)]-2H(2)O (3) was obtained. The cation in 1 exists as a one-dimensional polymer in the solid state, while weak O--H...O hydrogen bonds in the cation of 2 generate Delta Lambda Delta Lambda. type one-dimensional spiral chains. Addition of HClO(4) to 3 furnished 1 and 2, and this mixture can be converted back to 3 by the addition of a base. This conversion of a monomer to two 1-D polymers was found to be reversible. Crystal data for 1: triclinic space group P one macro, a = 12.0353(5) A, b = 12.2848(5) A, c = 15.3185(6) A, alpha = 84.993(1) degrees, beta = 89.411(1) degrees, gamma = 67.414(1) degrees, V = 2082.5(2) A(3), Z = 2, rho(calcd) = 1.668 g cm(-3). Crystal data for 2: tetragonal space group P4(1)/a, a = 10.8095(1) A, c = 59.0159(4) A, V = 6895.7(1) A(3), Z = 8, rho(calcd) = 1.605 g cm(-3). Crystal data for 3: monoclinic space group Pn, a = 10.6344(3) A, b = 5.3953(1) A, c = 18.1983(1) A, V = 1029.26(4) A(3), Z = 2, rho(calcd) = 1.526 g cm(-3). When Cu(NO(3))(2) was used in the place of Cu(ClO(4))(2), [Cu(2)(Sbal)(phen)(3)](NO(3))(2)-2.5H(2)O (4) was the only isolable product for the 1:1:1:1 ratio, and 3 was the only isolable product for the 1:1:1:2 ratio. Crystal data for 4: triclinic space group P one macro, a = 10.8063(8) A, b = 13.919(1) A, c = 16.564(1) A, alpha = 88.957(2) degrees, beta = 71.008(1) degrees, gamma = 69.829(2) degrees, V = 2198.9(3) A(3), Z = 2, rho(calcd) = 1.556 g cm(-3). Variable temperature magnetic measurements showed that the polymeric structure in 1 behaves, magnetically, as a strongly coupled micro-phenoxo dimer (2J = -390 cm(-1)) plus an isolated monomer.

Cytotoxicity of salicylaldehyde benzoylhydrazone analogs and their transition metal complexes: quantitative structure-activity relationships.

A series of salicylaldehyde benzoylhydrazone derivatives, their copper(II) complexes and a range of transition metal complexes of the unsubstituted ligand has been synthesized and evaluated for cytotoxicity against a human adenocarcinoma cell line. A QSAR analysis revealed ligand cytotoxicity is strongly correlated with electronic and transport factors and can be modeled by treating each 'half' of the molecule as an isolated unit. Activity increases when substituents in the benzoyl ring were electron withdrawing whereas, for the salicylaldehyde ring, electron donation was required. The cytotoxicity of the Cu(II) complexes was greater than, and paralleled the ligands. Activity for the transition metal complexes of the unsubstituted ligand mirrored charge density on the metal.

Nitrogen, sulfur and oxygen donor adducts with copper(II) complexes of antitumor 2-formylpyridinethiosemicarbazone analogs: physicochemical and cytotoxic studies.

The preparation of N-, S- and O-donor ligand adducts with CuX+ (HX = 6-methyl-2-formylpyridinethiosemicarbazone (6HL); 2-formylpyridine-2'-methylthiosemicarbazone (2'L); 2-formylpyridine-4'-methylthiosemicarbazone (4'HL) is described. The N-donors, 2,2'-bipyridyl (bipy), 4-dimethylaminopyridine (dmap) give the complexes [Cu(6L)(bipy)]PF6, [Cu(6L)(bipy)]Cl.5H2O, [Cu(4'L)(bipy)]PF6, [Cu(6L)(dmap)2]PF6.2.5 H2O and [Cu(4'L)(dmap)2]PF6.H2O which have been characterized by physical and spectroscopic techniques. Pentafluorothiophenolate (pftp) gives S-donor complexes [CuX(pftp)] (X = 6L and 4'L) and thiolato co-ordination is proposed on the basis of spectroscopic evidence. Paratritylphenolate (ptp) and HPO4(2-) give O-donor complexes [Cu(6L)(ptp)], [Cu(4'L)(ptp)], [¿Cu(6L)¿2HPO4].4H2O, and [¿Cu(4'L)¿2HPO4].5H2O which have been characterized by physical and spectroscopic techniques, as have the precursor complexes [Cu(6L)(CH3COO)].H2O, [Cu(4'L)(CH3COO)], Cu(6HL)(CF3COO)](CF3COO).0.5H2O, [Cu(4'HL)(CF3COO)](CF3COO), [Cu(2'L)Cl2) and [Cu(2'L)(NO3)2]. Protonation constants for the ligands and some of their complexes have been determined. 2-Formylpyridinethiosemicarbazone (HL) complexes of silver, gold, zinc, mercury, cadmium and lead are also discussed. Cytotoxicity against the human tumor cell line HCT-8 and antiviral data for selected compounds are presented.

Complexes of salicylaldehyde acylhydrazones: cytotoxicity, QSAR and crystal structure of the sterically hindered t-butyl dimer.

A series of acylhydrazones of salicylaldehyde and their transition metal complexes, predominantly copper(II), have been prepared and characterized. The crystal structure of the Cu(II) complex of the sterically hindered t-butyl derivative contains a phenolato bridged dimer with the ligand coordinated as a tridentate moiety. QSAR analyses of the cytotoxicity of the chelators and their Cu(II) complexes reveals that solubility is the dominant factor for activity. Compounds display a maximum with respect to lipophilicity, allowing optimization of the bioactivity for both the ligands and their complexes. Copper complexes are significantly more cytotoxic than the metal-free ligands and complexes of other metals: Cu > Ni > Zn = Mn > Fe = Cr > Cr > Co.