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We present the magnetic properties of the metal-organic framework {[CoCxAPy]·2.15 H₂O}_n (Cx = bis(carboxypropyl)tetramethyldisiloxane; APy = 4,4`-azopyridine) (<b>1</b>) that builds up from the stacking of 2D coordination polymers. The 2D-coordination polymer in the <i>bc </i>plane is formed by the adjacent bonding of [CoCxAPy] 1D two-leg ladders with Co dimer rungs, running parallel to the <i>c</i>-axis. The crystal packing of 2D layers shows the presence of infinite channels running along the <i>c</i> crystallographic axis, which accommodate the disordered solvate molecules. The Co(II) is six-coordinated in a distorted octahedral geometry, where the equatorial plane is occupied by four carboxylate oxygen atoms. Two nitrogen atoms from APy ligands are coordinated in apical positions. The single-ion magnetic anisotropy has been determined by low temperature EPR and magnetization measurements on an isostructural compound {[Zn_0.8Co_0.2CxAPy]·1.5 CH₃OH}_n (<b>2</b>). The results show that the Co(II) ion has orthorhombic anisotropy with the hard-axis direction in the C_2V main axis, lying the easy axis in the distorted octahedron equatorial plane, as predicted by the <i>ab initio</i> calculations of the <b><i>g</i></b>-tensor. Magnetic and heat capacity properties at very low temperatures are rationalized within a <i>S</i>* = 1/2 magnetic dimer model with anisotropic antiferromagnetic interaction. The magnetic dimer exhibits slow relaxation of the magnetization (SMM) below 6 K in applied field, with a t_lf ≈ 2 s direct process at low frequencies, and an Orbach process at higher frequencies with <i>U</i>/k_B = 6.7 ± 0.5 K. This compound represents a singular SMM MOF built-up of Co-dimers with an anisotropic exchange interaction.