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

Abstract

The molecular structures of the polysulfuryl fluorides, S z 0 5 F z and S3O8F2, 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-'. The possibility that the sample consisted of a mixture of conformations of comparable stabilities was not explored. Can.

Disulfuryl Dichloride ClSO2OSO2Cl: A Conformation and Polymorphism Chameleon

“…[2] Ap hotochemical reaction yielding the peroxo-bridged disulfuryl dichloride, ClSO 2 OOSO 2 Cl,c onfirms this [3] andp rovides an explanation of the relatively low concentrationo fo xygen in Venus' atmos-phere. Contraryt ot hat, the corresponding disulfuryl difluoride, FSO 2 OSO 2 F, has been characterized spectroscopically [1,6] and structurally-first in the gas phase [7] and later also in the solid state. Contraryt ot hat, the corresponding disulfuryl difluoride, FSO 2 OSO 2 F, has been characterized spectroscopically [1,6] and structurally-first in the gas phase [7] and later also in the solid state.…”

“…Although the title compound is known for more than a century no complete elucidation of its spectroscopic or structural features was undertaken. Contrary to that, the corresponding disulfuryl difluoride, FSO 2 OSO 2 F, has been characterized spectroscopically and structurally—first in the gas phase and later also in the solid state . In the gas phase the difluoride solely consists of an anti ‐conformer with a torsional angle φ (FS⋅⋅⋅SF) of 119.1(6)°, whereas in the solid state this torsional angle measures 144.9(1)° while no pronounced individual interactions amongst the molecules can be identified.…”

Structure of disulfuryl difluoride at 100 K

“…Each S atom has contacts to two O atoms, one from the other tetrahedron in the same molecule and one from a neighbouring molecule [at (1 +y, 1 -x, -z)] at distances of 3.094 (2) and 3.134 (2) A, respectively, slightly less than the sum of the van der Waals radii for S and O (1.85 + 1.40 A; Pauling, 1952). The molecules possess crystallographic twofold symmetry and the [SQF] groups are staggered by 144.97 (5) ° about the S...S vector, in contrast to the structure of the molecule as determined by gas-phase electron diffraction (GPED) (Hencher & Bauer, 1973) (2) and 1.514(2) in SO2F2 (solid state), 1.408 (3) and 1.538 (1) in SO2C1F (solid state) (Mootz & Merschenz-Quack, 1988) and 1.403 (3) and 1.552 (4) (equatorial), 1.575 (4) A (axial) in SOU4 (GPED) (Gunderson & Hedberg, 1969). The S--O bridging distances in 5205F2 and 5308F2 are rather short, presumably less than the single-bond distance.…”

“…324 K) and is sensitive to moisture. Although the structure of the free molecule is known from gas-phase electron diffraction (Hencher & Bauer, 1973), its solid-state structure was unknown. We undertook the determination of the crystal structure in part to allow comparison between the molecule in the two phases.…”

“…The S--O bridging distances in 5205F2 and 5308F2 are rather short, presumably less than the single-bond distance. The shortening is ascribed to delocalization (3) 0(1) 0.5 0.0 0.21942 (19) 0.0209 (9) 0(2) 0.70643 (22) and back donation of free-electron pairs on the O atom to an S atom polarized by its halogen substituents (Hencher & Bauer, 1973). This effect is even more pronounced in FsSOSF5 (solid state) (Oberhammer & Seppelt, 1978), where a short S--O bridging distance [1.586 (11) Introduction.…”