Synthis And Characterization Of Benzaldehyde Schiff Base Derivatives And Their Complexes

Schiff base is a kind of very important ligands which contains nitrogen atom. The nitrogen atom in Schiff base can form coordination bond with transition metal. Benzaldehyde derivatives are the most important and widely studied Schiff base compounds. In recent years, the synthesis and study of benzaldehyde Schiff base derivatives are very active. Benzaldehyde Schiff base derivatives and its complexes are not only have important application value in the field of medicine and pesticide but also have good application prospect in catalysis, corrosion, and optical materials. As a result, the preparation of novel benzaldehyde Schiff base derivatives and their complexes and the study of their properties are very important to the development of coordination chemistry.In this paper, two new compounds4-aminoacetophenone O-benzyloxime and3-aminoacetophenone O-benzyloxime has been synthesized. Ten Schiff base ligands have been synthesized by the reactions of4-aminoacetophenone O-benzyloxime and3-aminoacetophenone O-benzyloxime with salicylic aldehyde,5-cholorosalicylidene,5-bromosalicylaldehyde,3,5-dicholorosalicylidene and3,5-dibromosalicylaldehyde. The products are characterized by solubility experiments, elemental analyses and IR spectra.The single crystals of three ligands and one complexe have been obtained by the method of naturally solvent evaporation.The ligand is:1-(4-{[-(3,5-dibromo-2-hydroxyphenyl)methylene]amino}phenyl)ethanone O-benzyloxime (HL5)The complexes are:Copper(Ⅱ) Complex with1-(4-{[(5-bromo-2-hydroxyphenyl)methylene]amino} phenyl)ethanone O-benzyloxime Cu(L3)2Copper(Ⅱ) Complex with1-(4-{[(3,5-dichlor-2-hydroxyphenyl)methylene] amino}phenyl)ethanone O-benzyloxime Cu(L4)2Copper(Ⅱ) Complex with1-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene] amino}phenyl)ethanone O-benzyloxime Cu(L5)2The chemical composition and structure of these ligands and complexes have been determined by X-ray single crystal diffraction. The main crystal data are as following: 1-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene]amino}phenyl)ethanone O-benzyloxime (HL5):empirical formula C22H18Br2N2O2; Mr:502.02; monoclinic; space group:P2(1)/c; cell parameters:a=27.1877(13)A, b=13.2199(6)A c=22.2556(12)A, a=90°, β=92.0690(10)°,γ=90°, Z=8, V=7993.9(7)A3, R1=0.0540, wR2=0.1009;Copper(Ⅱ) Complex with1-(4-{[(5-bromo-2-hydroxyphenyl)methylene]amino} phenyl)ethanone O-benzyloxime Cu(L3)2:empirical formula C44H36Br2CuN4O4; Mr:908.13; monoclinic; space group:P-1; cell parameters:a=11.5642(9)A b=13.7219(13)A, c=14.0440(12)A, a=63.683(1)°, β=87.227(2)°, γ=84.883(1)°, Z=2, V=1987.5(3)A3, Ri=0.0580, wR2=0.1380。Copper(Ⅱ) Complex with1-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene] amino}phenyl)ethanone O-benzyloxime Cu(L4)2:empirical formula C44H34Cl4CuN4O4; Mr:888.09; monoclinic; space group:C2/c; cell parameters:a=27.1877(13)A b=13.2199(6)A, c=22.2556(12)A, a=90°, β=92.0690(10)°, γ=90°, Z=8V=7993.9(7)A3, Ri=0.0540, wR2=0.1009。Copper(Ⅱ) Complex withl-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene] amino}phenyl)ethanone O-benzyloxime Cu(L5)2:empirical formula C44H34Br4CuN4O4; Mr:1065.93; monoclinic; space group:C2/c; cell parameters:a=27.4484(7)A b=13.3116(3)A, c=22.3609(5)A, α=90°,β=91.165(2)°, γ=90°, Z=8, V=8168.6(3)A3, Ri=0.0410, wR2=0.0647。Copper(Ⅱ) Complex with1-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene] amino}phenyl)ethanone O-benzyloxime Cu(L5)2has a novel structure. The supramolecular interaction and structure are complicated compared with the ligand,1-(4-{[(3,5-dibromo-2-hydroxyphenyl)methylene]amino}phenyl)ethanone O-benzyl oxime. Supramolecular interaction has changed greatly. In the crystal structure of the complex, intermolecular hydrogen bonds and π…π interaction assembl these monomeric units into a supramolecular structure. The Cu(Ⅱ) complex is a mononuclear complex. The Cu(Ⅱ) atom is four-coordinated by the phenolate O atoms and imine N atoms from two oxime-type ligands, in a distorted square plane geometry in which the dihedral angle two coordination plane (CulNlOl(or CulN2O2) and CulN3O3(or CulN4O4)) is13.00°.The research work in this thesis is meaningful for the deepening and expanding of Schiff base and complexes.