Ternary complexes of copper(II) with mixed acetylacetonate and nitrogen-containing ligands

Abstract

Ternary complexes of the type Cu(β-diketonate)′(β-diketonate)″(L) have been prepared where L =o-phenanthroline (phen), 2,2′-bipyridyl (bipy), and NNN′N′-tetramethylethane-l,2-diamine (tmen), and the β-diketonates present are selected from acetylacetone (Hacac), trifluoroacetylacetone (Htfac), and hexafluoroacetylacetone (Hhfac). Three dimensional X-ray crystal-structure analyses (heavy atom method) of the complexes Cu(acac)-(hfac)(phen), (1), and Cu(acac)(hfac)(phen)·2H₂O, (2), have been carried out. Both have Z= 2 in a triclinic unit cell with space group P(C_i, no. 2). Complex (1) has dimensions a= 12.623, b= 11.470, c= 8.111 Å, α= 81.17, β= 92.484, and γ= 97.691°, R= 0.064 6, for 2 470 reflections; (2) has a= 12.284, b= 14.437, c= 8.020 Å, α= 78.417, β= 109.315, and γ= 113.073°, R= 0.054 6 for 3 583 reflections. The two molecules contain a five-co-ordinated copper atom attached to a bidentate phen molecule and a chelating acac anion. In (1) the fifth site is occupied by a unidentate hfac anion whereas in (2) it is filled by a water molecule. The non-co-ordinated hfac in (2) is hydrogen bonded both to this water molecule and to a further unco-ordinated water molecule.