The Ni(II) complex of N-(2,4-dimethoxy benzylidene)-2-mercaptoaniline, [Ni(C15H14NO2S)(2)] was prepared and investigated. The structure derived from the two dimensional (2-D) NMR techniques, the infrared spectra, elemental analysis and mass spectra is consistent with that of the single crystal X-ray diffraction. Crystal system is monoclinic, space group Cc(no:9), number of formulae per unit cell Z = 4. Cell parameters are a = 14.283(4), b = 13.828(4), c = 14.345(5) Angstrom, beta = 102.84(3), V = 2762(2) Angstrom(3). Two singly deprotonated ligands coordinate the metal atom in a distorted square planar geometry. The molecular geometry was also effected by C-H...N and C-H...O intramolecular hydrogen bonds.