A centro-symmetric binuclear compound of formula [Dy(L)·(CH3COO)2·(H2O)2]2 (1) was isolated from the reaction between the 2,4-dinitrobenzoate anion (L) and the tris(acetate) of Dy(III). Single crystal diffraction studies reveal a μ1–κ2,η1:η1 chelating binding mode of L while the binuclear compound is formed by the two bridging (μ2–κ3,η1:η2) acetate anions. The nona-coordinated sphere of each Dy(III) ion is filled with a chelating (κ2,η1:η1) acetate anion and two terminal water molecules. Static magnetic measurements combined with ab initio SA-CASSCF/RASSI-SO calculations lead to two intramolecular competitive interactions i.e. ferromagnetic exchange interactions (0.04 cm−1) and antiferromagnetic dipolar interactions (−0.5 cm−1). Finally, dynamic magnetic measurements revealed a Single-Molecule Magnet behaviour in a zero-applied magnetic field with an effective energy barrier Δ = 21.5(2) cm−1 and τ0 = 7(3) × 10−6 s through Orbach and Quantum Tunnelling of the Magnetization relaxation mechanisms.