A theoretical study of the intermolecular magnetic interaction of [CrN(salpn)] is discussed based on DFT calculations. The close contact between the 2p orbitals on the axial nitrogen and other 3d orbitals besides the 3d(xy) orbital on the adjacent chromium is effective for ferromagnetic coupling. The magnetic interaction is rationally explained by the significantly large spin polarization of the axial nitrogen. (C) 2011 Elsevier B.V. All rights reserved.