Intramolecular Chalcogen−Tin Interactions in [(o-MeEC₆H₄)CH₂]₂SnPh_2−nCl_n (E = S, O, CH₂; n = 0, 1, 2) and Intermolecular Chlorine−Tin Interactions in the meta- and para-Methoxy Isomers

Abstract

Organotin(IV) compounds of the type [(o-MeE-C 6 H 4 )CH 2 ] 2 SnPh 2-n Cl n were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3), E = S, n = 0 (4), n = 1 (5), n = 2 (6) and E = CH 2 , n = 0 (7), n = 1 (8), n = 2 (9). The dichloro compounds 3 and 6 have been investigated by single crystal X-ray diffraction and exhibit bi-capped tetrahedral geometry at the tin atom as a consequence of significant intramolecular Sn⋯O (3) and Sn⋯S (6) secondary bonding, in monomolecular units. Compound 3 when crystallized from a hexane/thf solvent mixture shows two different conformers, 3′ and 3″, in the crystal structure, 3′ has two equivalent Sn⋯O interactions, while 3″ has two non-equivalent Sn⋯O interactions. Upon recrystallization of 3 from hexane only a single structural form is observed, 3′. The Sn⋯E distances in 3′, 3″, and 6 are 71.3; 73.5, 72.9; and 76.3% of the ΣvdW radii, respectively. The meta and para-substituted isomers of 3 (10, 11) exhibit a distortion at the tin atom due to self-association via intermolecular Sn⋯Cl interactions resulting in polymeric structures. 119 Sn NMR spectroscopy suggests that the intramolecular Sn⋯E interactions persist in solution for the dichloride compounds 3 and 6.

Experimental and computational exploration of photophysical and electroluminescent properties of modified 2,2′:6′,2″‐terpyridine, 2,6‐di(thiazol‐2‐yl)pyridine and 2,6‐di(pyrazin‐2‐yl)pyridine ligands and their Re(I) complexes

“…To explore the impact of the triimine modification on the local geometry, the sum of bond angles around the Re(I) centre has also been calculated. For structures 1 – 6 , the calculated values of 1604.11°, 1596.78°, 1600.37°, 1602.67°, 1599.47° and 1603.56°, slightly lower than the 1620° for an ideal octahedral ligand arrangement, are comparable to each other and indicate a negligible effect of the pyrrolidine substituent and peripheral rings of L n on the local geometry around the rhenium centre.…”

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

“…However, it may be worth mentioning that other heteroatoms (e.g., sulfur [127][128][129] and phosphorus [130][131][132]) also form similar interactions. Ether and carbonyl oxygens as well as amine, pyridine, and cyano nitrogens can all be involved in such interactions, and the geometries observed indicate that the lone pair of the heteroatom is directed towards the germanium/tin atom independent of the hybridization of the oxygen/nitrogen atom (which can be sp 3 , sp 2 , or sp).…”

Supramolecular Signatures of Adenine-Containing Organostannoxane Assemblies

“…Another aspect of interest is the ability of some of these compounds to serve as scaffolds for supporting a functional periphery that is electrochemically, photochemically, or catalytically active . Also, a number of supramolecular frameworks have been found in the crystal structures of organostannoxanes which were formed with the help of noncovalent interactions such as H-bonding, C–H···π and π···π interactions . One of the most aesthetically pleasing supramolecular architectures realized in these systems is the Rangoli pattern in the hexaferrocenyl derivative [ n -[BuSn­(O)­(O 2 CCH 2 C 5 H 4 FeC 5 H 5 )] 6 .…”