A novel technetium (IV) complex of a tetradentate Schiff base ligand was synthesized from the reaction of H₂dmsalen [dmsalen; N, N'-ethylenebis (3, 5-dimethylsalicylideniminato) ] and trans-⁹⁹Tc^IVCl₄ (PPh₃) ₂ [PPh₃; triphenylphosphin]. The complex ⁹⁹Tc^IVCl₂ (dmsalen), the structure of which was determined by X-ray crystallography, has an octahedral coordination geometry. The dmsalen ligand coordinates to the technetium atom through two N and two O atoms of the tetradentate ligand in the equatorial plane. Two chloro ligands are in the trans apical position with an average Tc-Cl bond length of 2.35 Å.