FULL PAPER Exploiting the versatility of pyridyl ligands for the preparation of diorganotin (IV) adducts: spectral, crystallographic and Hirshfeld surface analysis studies Badri Z. Momeni 1 | Nastaran Fathi 1 | Reyhaneh Abbasi 1 | Jan Janczak 2 1 Faculty of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315‐ 1618, Tehran 15418, Iran 2 Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50‐950 Wrocław, Poland Correspondence Badri Z. Momeni, Faculty of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315‐1618. Tehran 15418, Iran. Email: momeni@kntu.ac.ir 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, mul- tinuclear 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, how- ever, 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 deter- mined which reveal that the geometry around the tin atom is distorted octahe- dral 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 net- work of hydrogen bonds with a feature of trans‐[SnPh 2 ]. The 3D Hirshfeld sur- face 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. KEYWORDS Hirshfeld surface analysis, NMR, crystal structure, organotin, Pyridyl Received: 7 May 2019 Revised: 26 August 2019 Accepted: 26 August 2019 DOI: 10.1002/aoc.5239 Appl Organometal Chem. 2019;e5239. https://doi.org/10.1002/aoc.5239 © 2019 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/aoc 1 of 18