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DOI: 10.1039/A607476F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1251-1256

Reaction of anionic oxygen donors with the antitumour copper(II)–pyridine-2-carbaldehyde thiosemicarbazone (HL) system and the crystal structure of [{Cu(HL)(H2PO4)}2][H2 PO4]2·2H3PO4 ·2H2O

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Eric W. Ainscough, Andrew M. Brodie, John D. Ranford and Joyce M. Waters

Abstract

The complexes [(CuL)2(XO4)]·nH2O (HL = pyridine-2-carbaldehyde thiosemicarbazone, X = HP, n = 6; X = Mo, n = 1), [{CuL(ptp)}2]·4H2O (Hptp = p-tritylphenol) and [{CuL(tip)}2] (Htip = 2,4,6-triiodophenol) have been prepared from the reaction of aqueous solutions of [{CuL(CH3CO2)}2] with salts of the appropriate oxygen donor. Also prepared were [{Cu(HL)(H2PO4)}2][H2 PO4]2·xH3PO 4·nH2O (x = 0, n = 3; x = 2, n = 2) from the reaction of [{CuL(CH3CO2)}2] with 2 mol dm-3 H3PO4 and phosphate species (arising from the hydrolysis of 2 mol dm-3 HPF6) respectively. The complexes have been characterized by a range of physicochemical techniques and the crystal and molecular structure of [{Cu(HL)(H2PO4)}2][H2 PO4]2·2H3PO4 ·2H2O determined by single-crystal X-ray diffraction. The complex cation is a centrosymmetric dimer, the monomeric units having one-atom bridges from two H2PO4- anions. The copper atom has a distorted square-pyramidal geometry with three donor atoms (NNS) from the neutral, tridentate HL ligand and the fourth in-plane donor (an oxygen) from the bridging anion. The fifth position is occupied by a less strongly bound oxygen from the second bridging anion. An extensive hydrogen-bonding scheme involving the bridging H2PO4- anions, non-co-ordinated H2PO4- anions, H3PO4 moieties, water molecules and ligand exists with one very strong contact of 2.436 Å. These complexes may serve as simple models for the interaction of this antitumour system with oxygen donors.

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