Hexanuclear Copper(II) Cages Built on a Central {μ3–O···H···μ3–O} Moiety, 1,3-Bis(dimethylamino)-2-propanolato and Capping R-phosphonates: Crystal Structures, Magnetic Behavior, and DFT Studies

The syntheses, structural characterization, and magnetic behavior of two new hexanuclear copper­(II) complexes derived from R-phosphonic acids and 1,3-bis­(dimethylamino)-2-propanol (Hbdmap) with formulas [Cu6(μ-bdmap)3(μ3-Ph-PO3)2(μ3–O···H···μ3–O)­(ClO4)2(H2O)]·5H2O (1) and [Cu6(μ-bdmap)3(μ3-t-Bu-PO3)2(μ3–O···H···μ3–O)­(μ1,3-dca)­(dca)­(H2O)]·6H2O (2) (Ph-H2PO3 = phenylphosphonic acid, t-Bu-H2PO3 = tert-butylphosphonic acid, dca = dicyanamide) are reported. Compounds 1 and 2 are hexanuclear 3.111 R-phosphonate­(2-)/1,3-bis­(dimethylamino)-2-propanolato­(1-) cages including in the center the [μ3–O···H···μ3–O]3– unit. The temperature dependence of the magnetic properties of 1 and 2 clearly indicates an overall strong antiferromagnetic coupling confirmed by DFT calculations.