36-Nuclear Coordination Compounds of Nickel(II) with Malonate Anions and Internal Aquated Magnesium and Sodium Cations

The new anionic dimethylmalonate complex {Ni36(H2O)12(OH)20(HMe2Mal)(Me2Mal)29@ [Mg(H2O)6]}5– (Me2Mal2– is the dimethylmalonate anion) containing the internal aquated [Mg(H2O)6]2+ ion and the external [Mg3(OH)(H2O)10(C2H5OH)3]5+ cation was prepared by hydrothermal synthesis. The crystalline compound isolated from the reaction mixture and characterized by X-ray diffraction had the formula [Mg3(OH)(H2O)10(C2H5OH)3]{Ni36(H2O)12(OH)20(HMe2Mal)(Me2Mal)29@[Mg(H2O)6]}·25H2O (I) (CIF file CCDC no. 2038910). The new anionic complex {Ni36(H2O)12(OH)19(O)(Cbdc)30@[Na(H2O)6]}8– (Cbdc2– is the cyclobutane-1,1-dicarboxylate anion) containing the internal aquated [Na(H2O)6]+ ion and outer-sphere tetrabutylammonium cations was prepared from an ethanol–acetonitrile solution. The crystals isolated from the reaction mixture were characterized by X-ray diffraction and were described the formula (NBu4)8{Ni36(H2O)12(OH)19(O)(Cbdc)30@[Na(H2O)6]} (CIF file CCDC no. 2038909) (II). It was found that the magnetic behavior of complex I is due to competing ferro- and antifferromagnetic exchange interactions between paramagnetic nickel(II) ions.