Structural differences in eight- and ten-membered heterocyclic tin compounds displaying transannular interactions O⋯Sn: An experimental and theoretical study

• Published in: Polyhedron Vol. 40; no. 1; pp. 1 - 10
• Main Authors: Martínez-Otero, Diego, Flores-Chávez, Benito, Alvarado-Rodríguez, José G., Andrade-López, Noemí, Cruz-Borbolla, Julián, Pandiyan, Thangarasu, Jancik, Vojtech, González-Jiménez, Enrique, Jardinez, Christiaan
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 19.06.2012; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Crystallography; DFT studies; Dithioligands; Hypercoordinated compounds; Non-bonded interactions; Organotin compounds; Physical Sciences; Science & Technology; Organotin compounds; Dithioligands; DFT studies; Non-bonded interactions; Hypercoordinated compounds; 8-MEMBERED RING; 5-COORDINATE; TIN(IV); SULFUR; DERIVATIVES; PENTACOORDINATION
• ISSN: 0277-5387; 1873-3719
• DOI: 10.1016/j.poly.2012.04.004

The study of the hipervalence in some heterocyclic tin compounds of general formula [(S{C6H3(CH2)nS}2O)SnR1R2] (n = 1, 0) with different central ring sizes is reported. The conformation of the central ring is strongly influenced by the ring size. The possible conformers in the gas state of some selected compounds were investigated by MMFF, LSDA, BLYP, B3LYP, and M06 functionals using the DGDZVP and TZVP basis sets. Two series of heterocyclic tin compounds of general formula [(S{C6H3(CH2)nS}2O)SnR1R2] with different central ring sizes were prepared. The ten-membered series includes the compounds with n=1 and R1=R2=Ph (5); R1=Cl, R2=Ph (6); R1=Cl, R2=n-Bu (7); R1=R2=Cl (8); the eight-membered series includes the compounds with n=0 and R1=R2=Ph (10); R1=Cl, R2=n-Bu (11) and R1=R2=Cl (12). The compounds 5, 7, 8, 10, and 11 were investigated by single-crystal X-ray diffraction. The chloro compounds 7, 8, and 11 displayed a bipyramidal geometry at the tin atom with different degrees of distortion ranging from 57% to 62%. The diphenyl compounds 5 and 10 displayed a tetrahedral geometry at Sn. The conformation of the central ring in the ten-membered series is similar and is described as boat; the other series displayed two different conformations described as boat–chair and boat–boat. The possible conformers in the gas state of compounds 5, 7, 8, 10, 11, and 12 were investigated by MMFF, LSDA, BLYP, B3LYP, and M06 functionals using the DGDZVP and TZVP basis sets. The structural data of the total optimization agreed with the experimental results. The topological analysis indicated that bond critical points are present along the O⋯Sn direction in the compounds 7, 8, 11, and 12.