Structural and magnetic studies on three new mixed metal copper(II) selenites and tellurites
Xue-Li Cao1, Fang Kong, Zhang-Zhen He
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China. mjg@fjirsm.ac.cn.
Abstract:
Three new transition metal copper(II) selenites or tellurites, namely, CdCu(SeO3)2 (1), HgCu(SeO3)2 ()2, and Hg2Cu3(Te3O8)2 (3), have been obtained by conventional hydrothermal reactions of CdO (or Hg2Cl2), CuO and SeO2 (or TeO2). Compounds 1 and 2 are isostructural and crystallize in P2(1)/c. Their structures feature a 3D anionic framework of Cu(SeO3)2(2-) with 1D channels of eight-membered rings (MRs) along the c-axis and a-axis, respectively, which are filled by Cd(2+) or Hg(2+) cations. Compound 3 crystallizes in a tetragonal system of space group P42(1)2. Its structure is characterized by a [Cu3(Te3O8)2](2-) honeycomb layer composed of [Te3O8](4-) anions interconnected by Cu(2+) ions with 1D channels of 8-MRs along the c-axis. TOPOS analysis indicates that the copper(ii) tellurite layer exhibits a new topological structure with a Schläfli symbol of {4(6)·8(9)}(2){4(6)}(3). The above anionic copper(II) tellurite layers are further linked by dumbbell Hg2(2+) cations to form a novel 3D framework. Magnetic measurements based on magnetic susceptibility and heat capacity indicate that compounds 1 and 2 show a spin-singlet ground state with a spin gap based on the [Cu2O8](12-) dimeric model, whereas compound e3 xhibits a 2D spin-system with an antiferromagnetic ordering around 25 K correlated with its honeycomb [Cu3(Te3O8)2](2-) layer. Furthermore, crystalline structures, thermal stabilities, IR spectra and UV-Vis diffuse reflectance spectra have also been studied.
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