Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate

Abstract

The linear quadridentate N₂S₂ donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH₂)][ClO₄]₂, in the monoclinic space group P2₁/n, with Z= 4, a= 18.459(3), b= 10.362(2), c= 16.365(3)Å, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to R= 0.047 and R′= 0.075 for 3 343 independent reflections with l > 2σ(l). The compound consists of [Cu(bmdhp)(OH₂)]²⁺ ions and ClO₄^– counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu–N distances of 1.950(4) and 1.997(4)Å, Cu–O(water) 2.225(4)Å, and Cu–S 2.328(1) and 2.337(1)Å. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH₂)]²⁺ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO₄). E.s.r. and ligand-field spectra show that the copper(II) compounds adopt a tetragonal structure in donor solvents.