Exploiting the versatility of pyridyl ligands for the preparation of diorganotin (IV) adducts: spectral, crystallographic and Hirshfeld surface analysis studies

Diorganotin (IV) complexes SnR2X2 (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′‐Me2bpy) resulted in the formation of [SnMe2Cl2(5,5′‐Me2bpy)] (1). Mo...

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Bibliographic Details
Published in:Applied organometallic chemistry 2019-11, Vol.33 (12), p.n/a
Main Authors: Momeni, Badri Z., Fathi, Nastaran, Abbasi, Reyhaneh, Janczak, Jan
Format: Article
Language:English
Subjects:
Adducts
Chemical analysis
Chemistry
Chloroform
Coordination numbers
Crystal structure
Crystallography
Dichlorides
Hirshfeld surface analysis
Hydrogen bonding
Hydrogen bonds
Infrared analysis
Ligands
Mapping
NMR spectroscopy
NMR, crystal structure
organotin
Pyridyl
Spectrum analysis
Surface analysis (chemical)
Two dimensional analysis
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Summary:Diorganotin (IV) complexes SnR2X2 (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′‐Me2bpy) resulted in the formation of [SnMe2Cl2(5,5′‐Me2bpy)] (1). Moreover, the reaction of SnMe2(NSC)2 with 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (bu2bpy), 1,10‐phenanthroline (phen) and 4,7‐diphenyl‐1,10‐phenanthroline (bphen) affords the hexa‐coordinated complexes [SnMe2(NCS)2(bu2bpy)] (2), [SnMe2(NCS)2(phen)] (3) and [SnMe2(NCS)2(bphen)] (4), respectively. The resulting complexes have been characterized using elemental analysis, IR, multinuclear NMR (1H, 13C, 119Sn) 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 [SnPh2Cl2(4,7‐phen)]n (5) and [SnPh2Cl2(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 [SnMe2Cl2(5,5′‐Me2bpy)] (1), [SnMe2(NCS)2(bu2bpy)] (2) and [SnMe2(NCS)2(bphen)] (4) have been determined which reveal that the geometry around the tin atom is distorted octahedral with trans‐[SnMe2] configuration. Interestingly, the crystal structure of (H2biq)2[SnPh2Cl4]•2CHCl3 (7) was characterized by X‐ray crystallography from a chloroform solution of [SnPh2Cl2(biq)]n (6) indicating the formation of doubly protonated [H2biq]+ and [Ph2SnCl4]2− which are stabilized by a network of hydrogen bonds with a feature of trans‐[SnPh2]. 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. This paper reports the preparation and characterization of some diorganotin (IV) adducts containing a series of pyridyl ligands. The products have been characterized using elemental analysis, IR, NMR (1H, 13C, 119Sn, DEPT‐135°) spectroscopy and X‐ray crystallography. Interconnections in the four crystal structures were analyzed using Hirshfeld surface analysis. The 2D‐fingerprint plots revealed that the H…H and H … C/C … H contacts are more frequent in the crystal structures.
ISSN:0268-2605
1099-0739
DOI:10.1002/aoc.5239