(CH3)2SO

























 








 








Sulfur

Nuclear Quadrupole Coupling Constants


in Dimethylsulfoxide


 








 








 








The diagonal components of the nqcc tensor for 33S in dimethylsulfoxide were determined by Kretschmer [1].  Substitution structures were determined in 1969 by Feder et al. [2], and in 1996 by Typke [3].  An reSE equilibrium structure was derived by Vogt et al. [4].  Calculation of the nqcc tensor was made here on these structures.  Calculated and experimental nqcc's are compared in Tables 1 - 3.  Structure parameters are compared in Table 4.

 








In Tables 1 - 3, subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts x,y,z to the principal axes of the nqcc tensor.  The y-axis is chosen coincident with the inertia a-axis, these are perpendicular to the symmetry plane of the molecule.  Ø (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.

RMS is the root mean square difference between calculated and experimental nqcc's (percentage of average experimental nqcc).  RSD is the residual standard deviation of calibration of the model for calculation of the sulfur efg's/nqcc's.

 








 








   







Table 1.  33S nqcc's in Dimethylsulfoxide (MHz).  Calculation was made on the rs structure of Feder et al. [2].
   









Calc [a] B3LYP/6-311G(3df,3p) model.



Calc [b] B3LYP/TZV+(3df,3p) model.

 









Calc. [a]
Calc. [b]
Expt. [1]
   







Xaa - 15.51 - 15.03 - 15.720(18)

Xbb - 17.37 - 17.56 - 17.045(23)

Xcc
32.88
32.59
32.765(25)

|Xbc|
  2.37
  3.15



 







RMS
0.23 (1.1 %) 0.50 (2.3 %)


RSD
0.39 (1.7 %) 0.35 (1.5 %)


 







Xxx - 17.48 - 17.75



Xyy - 15.51 - 15.03



Xzz
33.00
32.78



ETA - 0.060 - 0.083



Øz,c
    2.73
    3.62



Øc,SO
121.92
121.92



Øz,SO
119.19
118.30



 








 








 








   







Table 2.  33S nqcc's in Dimethylsulfoxide (MHz).  Calculation was made on the rs structure of Typke [3].
   









Calc [a] B3LYP/6-311G(3df,3p) model.



Calc [b] B3LYP/TZV+(3df,3p) model.

 









Calc. [a]
Calc. [b]
Expt. [1]
   







Xaa - 15.35 - 14.86 - 15.720(18)

Xbb - 17.31 - 17.50 - 17.045(23)

Xcc
32.66
32.36
32.765(25)

|Xbc|
  2.39
  3.17



 







RMS
0.27 (1.2 %) 0.61 (2.8 %)


RSD
0.39 (1.7 %) 0.35 (1.5 %)


 







Xxx - 17.42 - 17.70



Xyy - 15.35 - 14.86



Xzz
32.78
32.56



ETA - 0.063 - 0.087



Øz,c
    2.69
    3.58



Øc,SO
121.91
121.91



Øz,SO
119.22
118.33



 








 








 








   







Table 3.  33S nqcc's in Dimethylsulfoxide (MHz).  Calculation was made on the reSE structure of Vogt et al. [4].
   









Calc [a] B3LYP/6-311G(3df,3p) model.



Calc [b] B3LYP/TZV+(3df,3p) model.

 









Calc. [a]
Calc. [b]
Expt. [1]
   







Xaa - 15.37 - 14.88 - 15.720(18)

Xbb - 17.25 - 17.44 - 17.045(23)

Xcc
32.62
32.32
32.765(25)

|Xbc|
  2.38
  3.15



 







RMS
0.25 (1.1 %) 0.59 (2.7 %)


RSD
0.39 (1.7 %) 0.35 (1.5 %)


 







Xxx - 17.37 - 17.64



Xyy - 15.37 - 14.88



Xzz
32.73
32.52



ETA - 0.061 - 0.085



Øz,c
    2.72
    3.60



Øc,SO
122.30
122.30



Øz,SO
119.57
118.69



 








 













Table 3.  Dimethylsulfoxide.  Heavy atom structure parameters, rs [2,3] and reSE [4] (Å and degrees).  Complete structures are given here in Z-matrix format.
 





    rs [2]     rs [3]reSE [4]






SC 1.799(5) 1.799(2)1.7964(4)

SO 1.485(6) 1.485(2)1.4804(5)

OSC
 106.65
 106.65(15)
 106.55(2)

CSC   96.56(3)   96.56(20)  96.01(2)


 








 








[1] U.Kretschmer, Z.Naturforsch. 50a,666 (1995).

[2] W.Feder, H.Dreizler, H.D.Rudolph, and V.Typke, Z.Naturforsch. 24a,266(1969).

[3] V.Typke, J.Mol. Struct. 384,35(1996).

[4] N.Vogt, J.Demaison, and H.D.Rudolph,  J.Mol.Spectrosc.  297,11(2014).












V.Typke and M.Dakkouri, J.Mol. Struct. 599,177(2001):  rz structure

 








(CH3)2S S=SF2


 








 








Table of Contents




Molecules/Sulfur




 








 













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Last Modified 18 Jan 2014