Dibutyltin(IV) complex [SnBu2(NCS)2] (1) has been prepared from the reaction of SnBu2Cl2 and potassium thiocyanate in a molar ratio of Sn:KNCS/1:2 in ethanol. The reaction of [SnBu2(NCS)2] (1) with 4,4ꞌ-di-tert-butyl-2,2ꞌ-bipyridine (bu2bpy) in a molar ratio of Sn:bu2bpy/1:1 resulted in the formation of [SnBu2(NCS)2(bu2bpy)] (2). The products were characterized using elemental analysis, IR, and multinuclear NMR (1H, 13C, 119Sn) spectroscopy. The X-ray crystal structure determination of the complex [SnBu2(NCS)2(bu2bpy)] (2) revealed that the geometry around the Sn(IV) atom is highly distorted octahedral with trans-[SnBu2] configuration. On the other hand, the new single crystals of bu2bpy (3) were characterized by X-ray crystallography from the crystallization of 2 in diethyl ether. The various types of weak interactions in their networks have been assessed using the 3D Hirshfeld surface analysis and 2D fingerprint maps for 2, and 3 which show the major contribution of intermolecular interactions is related to H…H interactions. The thermal properties analysis showed that the complex [SnBu2(NCS)2] (1) is stable up to 153 °C while the complex [SnBu2(NCS)2(bu2bpy)] (2) is stable up to 190 °C.