Microwave Spectrum and Structure of Sulfuryl Fluoride

Abstract

The microwave spectrum of sulfuryl fluoride, SO2F2, has been reinvestigated. The spectra of the S32 and S34 species in natural abundance have been analyzed, and the structure has been determined with the aid of the S34 isotope shift. The correction for zero-point vibration was shown to be small. The structural parameters are: rSO=1.405±0.003 A, rSF=1.530±0.003 A, <OSO=123°58′±12′, and <FSF=96°7′±10′. The molecular dipole moment is 1.110±0.015 Debye units. A number of satellite lines were observed and assigned to excited vibrational states. Some anomalies in the measured rotational constants for the excited states have been interpreted in terms of a Coriolis-type interaction between the fundamentals ν4(A1) and ν5(A2). From an analysis of this interaction the frequency of the hitherto unobserved ν4(A1) fundamental was found to be 388±15 cm—1.

Sulfonyl Chloride Kinetics. Part II. Solvolysis of a Series of Benzenesulfonyl Chlorides: An Unexpected Heat Capacity Variation

“…(24). Similar conclusions can be drawn from data for S02F2 (25). From the above evidence we conclude that the stereochemistry of the RS02CI molecules may be considered as a distorted tetrahedron but with shortened S-0 bonds due to pn-dn interaction (26).…”

The crystal structures of two sulphur–nitrogen compounds with (S-N)3rings. I. α-Sulphanuric chloride, α(NSOCl)3

“…The small difference between the endo-and exocyclic angles in ~(NSOCI)3 may be due to the double bond character of the S = O exocyclic bond. For a free molecule such as SO2F2 (Lide, Mann & Fristrom, 1957) the repulsion between two double bonds is greater than that between a double and a single bond, which in turn is greater than the repulsion between two single bonds, and so OSO> OSF> FSF. Assuming that the same holds for the ring systems one would then expect NSN ~ NSO > C1SO___ NSCI and for the nitrilics NPN > NPX > XPX, which would result in a greater discrepancy between the endocyclic and exocyclic angles.…”

Centrifugal Distortion Analysis of a Near-Spherical Top, SO2F2: The First Determination of All Six Quartic Centrifugal Distortion Constants for an Asymmetric Top

“…In principle any of the distortion constants T except T 202 can be constrained, but in practice the most often used constraint is T 004 ϭ 0, [12] called A Reduction, which leads to simple tridiagonal Hamiltonian matrices. This reduction blows up if the asymmetric rotor is accidentally close to a symmetric rotor and…”

“…If such a constraint, say Eq. [12], is attempted, and Eq. [13] is fulfilled, the parameter s 111 is assigned a value with order of magnitude 4-p , which is at least by one order larger than a limit 4 , set by Eq.…”