The preparation, characterization, crystal structure and biological activities of some copper(II) complexes of the 2-benzoylpyridine Schiff bases of S-methyl- and S-benzyldithiocarbazate

The complexes [Cu(NNS)X] (HNNS represents the 2-benzoylpyridine Schiff bases of S-methyl- or S-benzyldithiocarbazate; XCl, Br, NO3) have been prepared and characterized by a variety of physico-chemical techniques. Magnetic and spectral evidence support a square-planar structure for the [Cu(BpSR)X] (BpSR=the benzoylpyridine Schiff bases; RCH3, CH2C6H5; XCl, Br) and [Cu(BpSMe)NO3] complexes and a five-coordinate distorted square-pyramidal structure for the [Cu(BpSBz)NO3] complex. The crystal structures of [Cu(BpSMe)NO3] and [Cu(BpSBz)NO3] have been determined by X-ray diffraction studies. The complex [Cu(BpSMe)NO3] crystallizes in the triclinic space group P1 with a=7.600(3), b=10.5346(2), c=11.564(3) A, α=116.0033(14), β=103.91(3), γ=91.55(3)°, V=798.3(4) A and Z=2. The complex has a distorted square-planar geometry with the copper ion lying in an approximate plane of four coordinating atoms, three of which come from the 2-benzoylpyridine Scniff base of S-methyldithiocarbazate while the fourth coordination site is occupied by an oxygen from the nitrate ligand. The complex, [Co(BpSBz)NO3] crystallizes in the monoclinic space group P21/a with a=9.0124(19), b=18.501(5), c=13.0642(24) A, β=106.377(15)°, V=2089(9) A3 and Z=4. The coordination environment around the copper(II) ion is a distorted square-pyramid with three donor atoms (NNS) coming from the 2-benzoylpyridine Schiff base and the fourth and fifth atoms (oxygen) coming from the bidentade NO3− ion. The antifugal and antibacterial properties of the Schiff bases and their copper(II) complexes have been evaluated against three pathogenic fungi and two bacteria. The Schiff bases and copper(II) complexes display moderate antifungal activities but their activities are less than that of the commercially important antifungal agent nystatin.

[1]  J. Waters,et al.  Preparation and characterization of complexes of the antitumour copper(II) 2-formylpyridine thiosemicarbazone (HL) system and the single-crystal X-ray structures of [{Cu(HL)(CF3CO2)}2][CF3CO2]2 and [Cu(HL)(H2O)(CLO4)2]·2H2O , 1991 .

[2]  James A. Ibers,et al.  International tables for X-ray crystallography , 1962 .

[3]  C. Lambros,et al.  2-Acetylpyridine thiosemicarbazones. 9. Derivatives of 2-acetylpyridine 1-oxide as potential antimalarial agents. , 1984, Journal of medicinal chemistry.

[4]  F. Smith,et al.  Metal ion induced rearrangements of 1,3,4-thiadiazolidine-2-thiones—I. The rearrangements of 3-methyl-5-(2-pyridyl)- and 3-methyl-5-(6-methylpyrid-2-yl)-1,3,4-thiadiazolidine-2-thiones with nickel(II), zinc(II) and cadmium(II) ions , 1990 .

[5]  A. E. Liberta,et al.  Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 6. The chemical and antifungal properties of 2-acetylpyridine4N-diethyl- and4N-dipropylthiosemicarbazones and their copper(II) complexes , 1990 .

[6]  D. L. Klayman,et al.  2-Acetylpyridine thiosemicarbazones. 8. Derivatives of 1-acetylisoquinoline as potential antimalarial agents. , 1984, Journal of medicinal chemistry.

[7]  S. Bhattacharjee,et al.  Synthesis, characterization, electrochemistry and oxo-transfer kinetics of oxomolybdenum-(VI), -(V) and -(IV) complexes with ONS donors , 1992 .

[8]  E. Baker,et al.  The characterization of both the coordinated and non-coordinated saccharinate ion. The syntheses and crystal structures of aqua(2-formylpyridine thiosemicarbazonato)(saccharinato-N)copper(II) hemihydrate and 2,2′-bipyridyl-(2-formylpyridine thiosemicarbazonato)copper(II) saccharinate dihydrate , 1990 .

[9]  D. L. Klayman,et al.  Antiviral Activity of 2-Acetylpyridine Thiosemicarbazones Against Herpes Simplex Virus , 1981, Antimicrobial Agents and Chemotherapy.

[10]  C. Bell,et al.  Structure of the antitumour agent di‐μ‐acetato‐(O)‐bis[(2‐pyridinecarbaldehyde thiosemicarbazonato)copper(II)] , 1987 .

[11]  A. Müller,et al.  Synthetic, spectroscopic, and X-ray crystallographic studies on binuclear copper(II) complexes with a tridentate NNS-bonding 2-formylpyridine thiosemicarbazone ligand. The characterization of both neutral and deprotonated co-ordinated ligand structures , 1987 .

[12]  D. X. West,et al.  Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 2. The4N-dimethyl derivative , 1988 .

[13]  A. Castiñeiras,et al.  Cobalt(III) complexes with 2-acetyl- and 2-formylpyridine 4N-methylthiosemicarbazones , 1994 .

[14]  S. Livingstone,et al.  Cytotoxic action of some transition metal chelates of Schiff bases derived from S-methyldithiocarbazate. , 1978, British Journal of Cancer.

[15]  X. You,et al.  Transition metal complexes of the Schiff bases derived from S-alkyldithiocarbazate with 2-pyridinecarboxaldehyde N-oxide—I. Synthesis, properties and structure of four-coordinate copper(II) complexes , 1990 .

[16]  G. J. Palenik,et al.  The crystal structure of dichloro-(acetonethiosemicarbazone)zinc(II) , 1971 .

[17]  D. L. Klayman,et al.  2-Acetylpyridine thiosemicarbazones. 4. Complexes with transition metals as antimalarial and antileukemic agents. , 1982, Journal of medicinal chemistry.

[18]  M. Ali,et al.  Preparation, characterization and antifungal properties of transition metal ion complexes of quadridentate N3S ligands , 1993 .

[19]  S. Livingstone,et al.  Metal complexes of sulphur-nitrogen chelating agents , 1974 .

[20]  D. X. West,et al.  Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridine. Part 1. The4N-methyl derivative , 1987 .

[21]  R. Pasqualini,et al.  Complexes of Tcv and TcIII with tridentate Schiff bases derived from S-methyl dithiocarbazate. Crystal structures of chloro[S-methyl 3-(2′-hydroxy-1-naphthylmethylene)dithiocarbazato(2-)]oxotechnetium(V) and dichloro[S-methyl 3-(2-hydroxybenzylidene)dithiocarbazato(1-)]bis(triphenylphosphine)-techne , 1990 .

[22]  J. Begum,et al.  Synthesis, characterization and biological activities of some nickel(II) complexes of tridentate NNS ligands formed by condensation of 2-acetyl-and 2-benzoylpyridines with S-alkyldithiocarbazates , 1993 .

[23]  J. Zubieta,et al.  Transmetalation of tetranuclear copper complexes with tin transmetalators. Molecular structure of cis-dichloro-bis(trans-S-methyl isopropylidenehydrazinecarbodithioato)tin(IV) and consideration of transmetalation mechanisms , 1992 .

[24]  S. Bhattacharjee,et al.  Ligand-controlled synthesis, reactivity and oxo-transfer kinetics of oxomolybdenum-(VI) and -(IV) complexes , 1993 .

[25]  M. Ali,et al.  The preparation and characterization of some new nickel(II), copper(II), zinc(II) and cadmium(II) complexes of the pyrrole-2-carboxaldehyde Schiff bases ofS-alkyl esters of dithiocarbazic acid , 1995 .

[26]  H. Beraldo,et al.  Spectroscopic studies of metal complexes containing π-delocalized sulfur ligands. Mössbauer and kinetic studies of iron(II) and iron(III) complexes of the antitumor agent 2-formylpyridine thiosemicarbazone , 1990 .

[27]  M. Nardelli,et al.  The crystal and molecular structure of bisthiosemicarbazidato nickel(II) (red crystals) , 1962 .

[28]  Peter S. White,et al.  NRCVAX ― an interactive-program system for structure analysis , 1989 .