Crystal structure, magnetic, thermal behavior, and spectroscopic studies of two new bimetallic hydrogenselenites: [Cu2−xNix (HSeO3)2Cl2.4H2O], (x = 0.62; 0.91)

Abstract

Two new iso-structural bimetallic hydrogenselenites [Cu2−xNix(HSeO3)2Cl2.4H2O] (x = 0.62; 0.91) have been synthesized from solution and characterized by single-crystal and powder X-ray diffraction. They crystallized in the orthorhombic Pnma space group with the following lattice parameters: for Cu1.09Ni0.91(HSeO3)2Cl2.4H2O: a = 9.0931 (2) Å, b = 17.7717 (4) Å, c = 7.1620 (2) Å, Z = 4, and for Cu1.38Ni0.62(HSeO3)2Cl2.4H2O: a = 9.0931 (4) Å, b = 17.7467 (7) Å, c = 7.1717 (3) Å; Z = 4. The crystal structure of this compound consists by a three-dimensional framework, but it may be described as a bi-dimensional structure consisting of layers, parallel to the (010) plane formed by two types of (Cu/Ni) octahedral and (HSeO3)− trigonal pyramids. The magnetic measurement, thermal and spectroscopic studies were performed for these compounds. The magnetic results reveal the appearance of a weak ferromagnetic behavior at low temperature (Tc = 16 K for x = 0.91 and 18.8 K for x = 0.62). The DSC analysis enabled us to locate two endothermic peaks. The first peak can be attributed to a completely dehydration of the material, in this transformation, the compounds undergo a structural phase transition which can favor a non-centrosymmetric phase at high temperature confirmed by the thermodiffractograms measurement. The second peak for these samples is due to the ferro-paraelectric phase transition which can be explained by an order– disorder transition.