Organo-Functionalized Lacunary Double Cubane-Type Oxometallates: Synthesis, Structure, and Properties of [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (M=Co, Zn)

Organofunctionalized tetranuclear clusters [((MCl)-Cl-II)(2)((VO)-O-IV)(2){((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)(2))}(2)] (<bold>1</bold>, M=Co, <bold>2</bold>: M=Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo-alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single-crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of <bold>1</bold> and <bold>2</bold> in an unusual two-mode fashion, unobserved previously. In the crystalline state, the clusters of <bold>1</bold> and <bold>2</bold> are joined by hydrogen bonds to form a three-dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [J(iso)(V-IV-V-IV)=-5.4(<bold>1</bold>); -3.9(<bold>2</bold>) cm(-1)], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [J(iso) (V-IV-Co-II)=-12.6 and -7.5 cm(-1)] contained in <bold>1</bold>.