The synthesis, structural characterization, and magnetic behavior of a new 2D copper(II) compound with formula {[Cu-2(mu-O2CMe)(mu-MedapO)(mu(1,1)-N-3)(2)](n)(CH3OH)(n)} 1, in which MedapOH is N-methyl-1,3-diamino-2-propanol is reported herein. 1 crystallizes in the triclinic system, space group P (1) over bar, with unit cell parameters a = 6.688(5) angstrom, b = 10.591(6) angstrom, c = 12.100(7) angstrom, alpha = 113.01(3)degrees, beta = 105.08(4)degrees, gamma = 93.93(3)degrees, Z = 2. The structure of 1 consists of neutral alternate 1 D chains formed by the sequence of [Cu(1)-(mu(1,1)-N-3)(2)-Cu(1)-(MedapO/acetate)-Cu(2)-(mu(1,1)-N-3)(2)Cu-2)]. Each dinuclear [Cu(1)-Cu(2)] unit interacts with similar dinuclear units of neighbor chains in basis to large Cu-N(azido) distances to give a 2D arrangement. The magnetic behavior of 1 has been checked giving a net ferromagnetic coupling. The fit of the chi(M) versus T data as dinuclear compound affords a J value of 53.0 cm(-1) as a consequence of the orbital countercomplementarity phenomenon. The exchange pathways have been justified by density functional calculations.