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Exploiting the versatility of pyridyl ligands for the preparation of diorganotin (IV) adducts: spectral, crystallographic and Hirshfeld surface analysis studies
Author(s) -
Momeni Badri Z.,
Fathi Nastaran,
Abbasi Reyhaneh,
Janczak Jan
Publication year - 2019
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5239
Subject(s) - chemistry , denticity , ligand (biochemistry) , crystallography , stereochemistry , nuclear magnetic resonance spectroscopy , adduct , bipyridine , crystal structure , proton nmr , medicinal chemistry , organic chemistry , biochemistry , receptor
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.