ANTITUMOR COPPER(II) SALICYLALDEHYDE BENZOYLHYDRAZONE (H(2)SB) COMPLEXES - PHYSICOCHEMICAL PROPERTIES AND THE SINGLE-CRYSTAL X-RAY STRUCTURES OF [(CU(H(2)SB)(CCL3CO2)(2))(2)] AND [(CU(HSB)(CLO4)(C2H5OH))(2)] AND THE RELATED SALICYLALDEHYDE ACETYLHYDRAZONE (H(2)SA) COMPLEX, [CU(HSA)CL(H2O)]CENTER-DOT-H2O

Copper(II) complexes of the antitumour ligand salicylaldehyde benzoylh ydrazone (H(2)sb) have been prepared. In the presence of strong acids, complexes of the neutral ligand were isolated: [{Cu(H(2)sb)X-2}(2)].n H(2)O (X=Br, n=1; X=CCl3CO2, n=0) and [Cu(H(2)sb)Cl-2(H2O)]. In weakly acid or neutral media, monoanionic compounds separated: [{Cu(Hsb)X}(2 ).nH(2)O] (X=Cl, Br, NO3, 0.5SO(4), n=0; X=ClO4, n=1). With base, only the highly insoluble dianionic complex [{Cu(sb)}(2)] was isolated. Al so prepared was the related anionic ligand complex [Cu(Hsa)Cl(H2O)].H2 O (H(2)sa=salicylaldehyde acetylhydrazone). The complexes have been ch aracterised by a range of physicochemical techniques and the crystal a nd molecular structures of [{Cu(H(2)sb)(CCl3CO2)(2)}(2)], [{Cu(Hsb)ClO 4(C2H5OH)}(2)] and [Cu(Hsa)Cl(H2O)].H2O, determined by single-crystal X-ray diffraction studies. Crystals of [{Cu(H(2)sb)(CCl3CO2)(2)}(2)] a re triclinic, space group P (1) over bar, with a=10.130(2),b=11.660(2) ,c=11.876(2) Angstrom,alpha=67.07(2),beta=109.09(2), gamma=107.84(2)de grees and Z=2. The complex is a centrosymmetric dimer, the monomeric u nits being bridged through the phenol oxygen. The copper coordination is tetragonal with the equatorial donor atoms coming from the tridenta te 'ONO' donor ligand and the symmetry related phenol oxygen. The more weakly bound axial donor oxygens are from the coordinated trichloroac etates. Crystals of [{Cu(Hsb)ClO4(C2H5OH)}(2)] are monoclinic, space g roup P2(1)/c, with a=11.2281(8),b=7.9129(4), c=21.043(1) Angstrom,beta =98.560(6)degrees and Z=4. This complex is also a centrosymmetric dime r, the monomeric units being bridged through the phenoxy oxygen. The c opper coordination is tetragonal with the equatorial donor atoms comin g from the tridentate 'ONO' iigand and the symmetry related phenoxy ox ygen. The more weakly bound axial donor oxygens are supplied by the et hanol and perchlorato moieties. Crystals of [Cu(Hsa)Cl(H2O)].H2O are m onoclinic, space group P2(1)/c, with a=7.4877(4),b=15.5806(7),c=10.520 8(3) Angstrom, beta=103.56(4)degrees and Z=4. The complex is monomeric with the copper(II) adopting a square-pyramidal coordination. The fou r in-plane donors are provided by the tridentate 'ONO' donor Hsa and a n oxygen from a coordinated water molecule; the axial site is occupied by the chloride ion. Most of the complexes have low magnetic moments and are assigned dimeric side-by-side structures. Powder ESR spectra h ave g(parallel to) and g(perpendicular to) resolved often with Delta M -s=2 transitions present. (C) 1998 Elsevier Science S.A.