The Sulphur–oxygen Bond in Sulphuryl and Thionyl Compounds: Correlation of Stretching Frequencies and Force Constants With Bond Lengths, Bond Angles, and Bond Orders

Abstract

I t is shown that the bond length of a n SO bond and the bond angle of an SO2 group may be very satisfactorily correlated with the SO stretching frequency. The bond-length -stretching-frequency relationship is used to predict some bond lengths that have not been measured and the OSO angles in some sulphuryl compounds are also calculated. The problem of defining and measuring the bond order of sulphur-oxygen bonds is discussed. I t is shown that there is a linear relationship between the force constant and the bond order and a non-linear relationship between the bond length and the bond order.

The crystal structure of ammonium pyrosulphite

“…This can be applied to the -SO2 group in S2Os z-where there is a double bond resonating in two S-O bonds (any double-bond character in the S-S bond can be ignored), giving a bond order of 1.50. Making use of the relation between bond order and bond distance found by Gillespie & Robinson (1963) a distance of 1.49 A is obtained for the S-O bond in good agreement with experimental values. The effect of unshared electrons can also explain the low value obtained for the S-S-O angle in the thionite group.…”

“…The crystal structure determination of ammonium pyrosulphite was undertaken in order to provide more accurate data on the dimensions of the pyrosulphite ion, which are relevant to the discussion of n-bonding in compounds of second row elements (Cruickshank, 1961;Gillespie & Robinson, 1963).…”

A Linear Relationship Between Bond Orders and Stretching Force Constants

“…plus some interaction terms is probably the most useful approach. More approximate and simpler methods have also been used quite successfully in cases when group frequencies can be assigned to a diatomic or triatomic group in a more complex molecule (1). At least it is to be hoped that the S.V.F.F.…”

Isolierung und Charakterisierung eines nicht‐starren Hexamethylbenzol‐SO2+‐Komplexes

“…[10] The sulfur-oxygen bond length of 1.424(2) Å is characteristic for a relatively short S-O double bond. [11] This value is lower compared to the double bond in free SO (1.481 Å, triplet ground state, isovalence-electronic to O2), [12] but higher than the calculated literature value of 1.39 Å for a triple bond in free SO 2+ , [13] …”