Twinned low-temperature structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate

Abstract

Tris(ethylenediamine)zinc(II) sulfate, [Zn(C2H8N2)3]SO4, (I), undergoes a reversible solid–solid phase transition during cooling, accompanied by a lowering of the symmetry from high-trigonal P31c to low-trigonal P3 and by merohedral twinning. The molecular symmetries of the cation and anion change from 32 (D3) to 3 (C3). This lower symmetry allows an ordered sulfate anion and generates in the complex cation two independent N atoms with significantly different geometries. The twinning is the same as in the corresponding Ni complex [Jameson et al. (1982). Acta Cryst. B38, 3016–3020]. The lowtemperature phase of tris(ethylenediamine)copper(II) sulfate, [Cu(C2H8N2)3]SO4, (II), has only triclinic symmetry and the unit-cell volume is doubled with respect to the roomtemperature structure in P31c. (II) was refined as a nonmerohedral twin with five twin domains. The asymmetric unit contains two independent formula units, and all cations and anions are located on general positions with 1 (C1) symmetry. Both molecules of the Cu complex are in elongated octahedral geometries because of the Jahn–Teller effect. This is in contrast to an earlier publication, which describes the complex as a compressed octahedron [Bertini et al. (1979). J. Chem. Soc. Dalton Trans. pp. 1409–1414].