Binuclear and polymeric copper(II) dicarboxylate complexes: syntheses and crystal structures of [Cu-2(pda)(Phen)(4)](ClO4)(2) center dot 5H(2)O center dot C2H5OH, [Cu-2(oda)(Phen)(4)](ClO4)(2) center dot 2.67H(2)O center dotC2H5OH and {[Cu-2(pda)(2)(NH3)(4)(H2O)(2)] center dot 4H(2)O}(n) (odaH(2)=octanedioic acid; pdaH(2)=pentanedioic acid; Phen=1,10-phenanthroline)

Reaction of [Cu(pda)(Phen)(2)]. 6H(2)O and [Cu(oda)(Phen)(2)] 8H(2)O {pdaH( 2)=pentanedioic acid; odaH(2)=octanedioic acid; Phen=1,10-phenanthroline) w ith ethanolic solutions of sodium perchlorate gives the two binuclear coppe r(II) perchlorate salts [Cu-2(pda)(Phen)(4)](ClO4)(2) . 5H(2)O C2H5OH (1) a nd [Cu-2(oda)(Phen)(4)](ClO4)(2) . 2.76H(2)O . C2H5OH (2), respectively. Th e X-ray crystal structures of 1 and 2 are quite similar with each comprisin g a discrete [Cu-2(dicarboxylate)(Phen)(4)](2+) dication, two uncoordinated perchlorate anions, an uncoordinated ethanol and several uncoordinated wat er molecules. The copper centres have N4O ligation with each metal having a pproximately square pyramidal geometry. {[Cu(pda)]}(n) reacts with ammonium hydroxide to form the polymeric copper(II) amine species {[Cu-2(pda)(2)(NH 3)(4)(H2O)(2)] . 4H(2)O}(n) (3). The structure of 3, as determined by X-ray crystallography, consists of polymeric chains in which the bridging pda(2- ) anions link two crystallographically similar copper atoms. The copper ato ms are also ligated by two transoidal ammonia nitrogens and an oxygen atom from an apical water molecule, giving the metals an overall N2O3, slightly distorted, square pyramidal geometry. Spectroscopic and magnetic data for t he three complexes are also reported. (C) 1999 Elsevier Science Ltd. All ri ghts reserved.