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A novel hybrid cobalt phosphite, (H2DAB)[Co(H2PO3)4] 2H2O, was synthesized by using a slow evaporation method in the presence of cobalt nitrate, phosphorous acid, and 1,4-diaminobutane (DAB = 1,4-diaminobutane) as a structure-directing agent. Single-crystal X-ray diffraction analysis showed that the compound crystallizes in the triclinic system (space group P-1(n.2)) with the following unit cell parameters (Å, °) a = 5.4814 (3), b = 7.5515 (4), c = 10.8548 (6), α = 88.001 (4), β = 88.707 (5), γ = 85.126 (5), and V = 447.33 (4) Å3. The crystal structure is built up from corner-sharing [CoO6] octahedra, forming chains parallel to [001], which are interconnected by H2PO3− pseudo-tetrahedral units. The diprotonated cations, residing between the parallel chains, interact with the inorganic moiety via hydrogen bonds, thus leading to the formation of the 3D crystal structure. The Fourier transform infrared spectrum showed characteristic bands corresponding to the phosphite group and the organic amine. The thermal behavior of the compound mainly consisted of the loss of its organic moiety and the water molecules. The biological tests exhibited significant activity against Candida albicans and Escherichia coli strains at different concentrations, while less inhibitory activity was pronounced against Staphylococcus epidermidis and Saccharomyces cerevisiae, and in the case of multi-cellular organisms, no activity against the nematode model Steinernema feltiae was detected. [ABSTRACT FROM AUTHOR]