The Molecular Structures of the Polysulfuryl Fluorides by Vapor Phase Electron Diffraction: S2O5F2 and S3O8F2

• Published in: Canadian journal of chemistry 1973-06, Vol.51 (12), p.2047-2054
• Main Authors: Hencher, J. Lawrence, Bauer, S. H
• Format: Article
• Language: English
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v73-305

The molecular structures of the polysulfuryl fluorides, S 2 O 5 F 2 and S 3 O 8 F 2 , were determined by vapor phase electron diffraction. In each case it was assumed that a single rotomer was more stable than all others, by at least 2.5 kcal mol −1 . The possibility that the sample consisted of a mixture of conformations of comparable stabilities was not explored.The thermally averaged r g parameters for S 2 O 5 F 2 are as follows: S=O = 1.398 ±.002 Å; SF = 1.525 ± 0.005 Å; SO = 1.611 ± 0.005 Å; ∠SOS = 123.6 ± 0.5°; ∠OS=O = 106.1 ± 0.9°; ∠FS=O = 106.6 ± 0.6°; ∠O=S=O = 126.8 ± 1.2°; ∠OSF = 102.4 ± 1.8°; τ FS/OS′  = 53.8 ± 2.7°; τ F′S′/OS  = 73.7 ± 2.4°. The r g parameters for S 3 O 8 F 2 are: S=O = 1.402 ± 0.003 Å; SF = 1.525 ± 0.012 Å; SO = 1.613 ± 0.006 Å; ∠OSO = 97.8 ± 1.0°; ∠SOS = 123.6 ± 1.2°; ∠OS=O = 106.5 ± 0.8°; ∠FS=O = 105.5 ± 1.2°; ∠O=S=O (bridge) = 128.8 ± 1.4°; ∠O=S=O = 128.5 ± 1.4°; ∠OSF = 101.3 ± 1.5°; τ SO/SO  = 295.3 ± 0.9°; τ FS/OS  = 319.4 ± 2.2°. The standard errors listed are three times the calculated values and are believed to encompass the non-random errors in the analysis.