Complexation of N-allyl derivatives of morpholinium with copper(I) halides: Synthesis and crystal structure of [C4H8ON(C3H5)(2)](+)[Cu4Cl5](-), [C4H8ONH(C3H5)](+)[CuBr2](-), and [C4H8ONH(C3H5)](+)[CuBr1.41Cl0.59](-)

Abstract

The compounds [C4H8ON(C3H5)(2)(+)[Cu4Cl5](-) (I), [C4H8ONH(C3H5)](+)[CuBr2](-) (II), and [C4H8ONH(C3H5)](+)[CuBr1.41]Cl-0.59](-) (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I pi-complex, the centrosymmetric Cu8Cl10 fragments are associated into layers perpendicular to the b axis. The N,N'-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III sigma-complexes, the edge-shared CuX4 tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N-H (...) X and C-H (...) X (X = Cl, Br) hydrogen bonds.