The title compound, (E)-5-methoxy-2-((4-methoxyphenylimino)methyl)phenol (C(15)H(15)NO(3)), crystallizes in monoclinic, space group P2(1)/(c) with a = 9.4361(6), b = 10.6212(5), c = 12.9338(9) angstrom,beta = 93.064(5)degrees, V= 1294.41(14) angstrom(3), Z = 4, D(c) = 1.320 g/cm(3), F(000) = 544, R(int) = 0.116, T= 296 K, mu = 0.09 mm(-1), the final R = 0.051 and wR = 0.148 for 1836 observed reflections with I > 2 sigma(I). An extensive two-dimensional network of C-H center dot center dot center dot O hydrogen bonds and pi-ring interactions are responsible for the crystal stabilization. Intermolecular hydrogen bonds and C-H center dot center dot center dot pi interactions produce R(2)(2)(14), R(4)(4)(30) and R(4)(4)(31) rings. In addition to the molecular geometry from X-ray experiment, the molecular geometry of the title compound in the ground state has been calculated using the semi-empirical (AM1 and PM3) and density functional theory method (DFT) (B3LYP) with 6-31G(d) basis set. To determine the conformational flexibility, molecular energy profile of the title compound was obtained by semi-empirical (PM3 and AM1) and DFT/B3LYP calculations with respect to the selected degree of torsional freedom, which varied from 180 to +180 degrees in a step of 10 degrees.