C6H5-N=S=O
























 






Nitrogen


Nuclear Quadrupole Coupling Constants


in Thionyl Aniline


 








 








14N nqcc's in thionyl analine were determined by Heineking et al. [1].

 








Calculation of the N nqcc's was made here on a ropt structure given by B3P86/6-31G(3d,3p) optimization, and on a rpopt structure given by MP2/6-311+G(3d,3p) partial optimization with the benzene ring parameters held fixed at the B3P86/6-31G(3d,3p) values.











Calculated and experimental nqcc's are compared in Table 1.  Structure parameters are given in Table 2, rotational constants in Table 3. In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its subscripted parameters.  RMS is the root measn square difference between calculated and experimental diagonal nqcc's.  RSD is the residual standard deviation of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.











 








 








Table 1.  14N nqcc's in Thionyl Aniline (MHz).  Calculation was made on ropt and rpopt structures.
 










Calc /ropt
Calc /rpopt
Expt. [1]
 








Xaa
1.699
1.652
1.5730(14)

Xbb -
 3.800
 -
 3.670
 - 3.6115(13)

Xcc
2.101
2.018
2.0384(14)

|Xab|
0.481
0.570












RMS
0.136 (5.6 %)
0.058 (2.4 %)



RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
1.741
1.712



Xyy
2.101
2.018



Xzz -
 3.842
 -
 3.730



ETA
0.0939
0.0820



Øz,b
4.96
6.04



Øb,bi
0.23
0.41



Øz,bi
4.73
5.63













 








* Angle between z-principal axis and bisector (bi) of the CNS angle.

 









 







 



Table 2. Thionyl Aniline: ropt and rpopt structure parameters (Å and degrees).






 C
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 C,4,B4,3,A3,2,D2,0
 C,1,B5,2,A4,3,D3,0
 H,1,B6,6,A5,5,D4,0
 H,2,B7,1,A6,6,D5,0
 H,3,B8,2,A7,1,D6,0
 H,4,B9,3,A8,2,D7,0
 H,5,B10,4,A9,3,D8,0
 N,6,B11,1,A10,2,D9,0
 S,12,B12,6,A11,1,D10,0
 O,13,B13,12,A12,6,D11,0


   ropt    rpopt

 B1=1.38477311
 B2=1.39241614
 B3=1.39222016
 B4=1.38640701
 B5=1.40250162
 B6=1.08410593
 B7=1.08456902
 B8=1.08474536
 B9=1.08476172
 B10=1.08247485
 B11=1.38994085
 B12=1.51749888
 B13=1.46577821
 A1=119.94570539
 A2=120.08286777
 A3=120.64056688
 A4=120.18973222
 A5=118.30026727
 A6=119.90893509
 A7=119.99978584
 A8=119.92823249
 A9=121.18430443
 A10=115.94302245
 A11=132.2365089
 A12=120.75291482
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 D10=180.
 D11=0.
  B1=1.38477311
 B2=1.39241614
 B3=1.39222016
 B4=1.38640701
 B5=1.40250162
 B6=1.08410593
 B7=1.08456902
 B8=1.08474536
 B9=1.08476172
 B10=1.08247485
 B11=1.40413757
 B12=1.53838266
 B13=1.47708084
 A1=119.94570539
 A2=120.08286777
 A3=120.64056688
 A4=120.18973222
 A5=118.30026727
 A6=119.90893509
 A7=119.99978584
 A8=119.92823249
 A9=121.18430443
 A10=115.62876422
 A11=130.21335838
 A12=121.52459409
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 D10=180.
 D11=0.



 













Table 3. Thionyl Aniline:  Rotational Constants (MHz).







 ropt rpopt   Expt [1]






A
 4049.
 4004.
 4026.7215(4)

B
   864.
   863.
   860.64732(8)

C
   712.
  710.
   709.52027(7)



 








 








[1] N.Heineking, J.-U.Grabow, K.Vormann, and W.Stahl, Z.Naturforsch. 46a,989(1991).

 








 








CH3N=S=O
 HN=S=O



 








 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 27 Dec 2015