Diorganotin (IV) complexes SnR 2 X 2 (R = Me, Ph; X = Cl, NCS) form a series of versatile complexes when react with bidentate substituted pyridyl ligands. The reaction of dimethyltin dichloride with 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me 2 bpy) resulted in the formation of [SnMe 2 Cl 2 (5,5′-Me 2 bpy)] (1). Moreover, the reaction of SnMe 2 (NSC) 2 with 4,4′-di-tert-butyl-2,2′-bipyridine (bu 2 bpy), 1,10-phenanthroline (phen) and 4,7-diphenyl-1,10-phenanthroline (bphen) affords the hexa-coordinated complexes [SnMe 2 (NCS) 2 (bu 2 bpy)] (2), [SnMe 2 (NCS) 2 (phen)] (3) and [SnMe 2 (NCS) 2 (bphen)] (4), respectively. The resulting complexes have been characterized using elemental analysis, IR, multinuclear NMR ( 1 H, 13 C, 119 Sn) and DEPT-135°NMR spectroscopy. On the other hand, the reaction of diphenyltin dichloride with 2,2′-biquinoline (biq) and 4,7-phenantroline (4,7-phen) led to the formation of polymeric complexes of [SnPh 2 Cl 2 (4,7-phen)] n (5) and [SnPh 2 Cl 2 (biq)] n (6). The NMR spectra, however, reveal the ligand lability in solution and suggest a coordination number of 5. The X-ray crystal structures of complexes [SnMe 2 Cl 2 (5,5′-Me 2 bpy)] (1), [SnMe 2 (NCS) 2 (bu 2 bpy)] (2) and [SnMe 2 (NCS) 2 (bphen)] (4) have been determined which reveal that the geometry around the tin atom is distorted octahedral with trans-[SnMe 2 ] configuration. Interestingly, the crystal structure of (H 2 biq) 2 [SnPh 2 Cl 4 ]•2CHCl 3 (7) was characterized by X-ray crystallography from a chloroform solution of [SnPh 2 Cl 2 (biq)] n (6) indicating the formation of doubly protonated [H 2 biq] + and [Ph 2 SnCl 4 ] 2− which are stabilized by a network of hydrogen bonds with a feature of trans-[SnPh 2 ]. The 3D Hirshfeld surface analysis and 2D fingerprint maps were used for quantitative mapping out of the intermolecular interactions for 1, 2, 4 and 7 which show the presence of π-π and hydrogen bonding interactions which are associated between donor and acceptor atoms (N, S, Cl) in the solid state.