C5H4SNOH

























 





 








Nitrogen

Nuclear Quadrupole Coupling Constants

in N-hydroxypyridine-2(1H)-thione (pyrithione)

 








 








 








Calculation was made of the nitrogen nqcc tensor in pyrithione on a molecular structure given by B3P86/6-31G(3d,3p) optimization.  These are compared with the experimental nqcc's [1] in Tables 1 - 3.  Structure parameters are given in Table 4, rotational constants in Table 5.

 








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

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

 








 








   






Table 1. Nitrogen nqcc's in the normal species of Pyrithione (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure.

 









Calc.
Expt. [1]
   






14N Xaa
1.166
1.15(1)


Xbb
1.895
2.00(1)


Xcc -
 3.062 -
 3.09(1)


|Xab|
1.890



 







RMS
0.06 (3.0 %)




RSD
0.030 (1.3 %)



 






  Xxx -
 0.394




Xyy -
 3.062




Xzz
3.456




ETA
0.772




Øz,a
50.46




Øa,NO
51.14




Øz,NO *
  0.68



 







 








* The z-axis makes an angle of 0.68o with the NO bond axis.

 








 








   






Table 2. Nitrogen nqcc's in the OD species of Pyrithione (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure.

 









Calc.
Expt. [1]
   






14N Xaa
1.220
1.21(2)


Xbb
1.842
1.91(2)


Xcc -
 3.062 -
 3.12(2)


|Xab|
1.899



 







RMS
0.05 (2.5 %)




RSD
0.030 (1.3 %)



 







 








 








   






Table 3. Nitrogen nqcc's in the 34S species of Pyrithione (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure.

 









Calc.
Expt. [1]
   






14N Xaa
1.115
1.09(3)


Xbb
1.946
1.93(3)


Xcc -
 3.062 -
 3.08(3)


|Xab|
1.879



 







RMS
0.02 (1.0 %)




RSD
0.030 (1.3 %)



 







 







 
 


Table 4.  Pyrithione. Selected structure parameters, ropt (Å and degrees).  The complete structure is given here in Z-matrix format.
 




NO 1.3507

OH 1.0185

CS 1.6792

C(1)N
 1.3451

NC(5)
 1.3819

C(5)C(4)
 1.4153

NOH 100.00

C(1)NO 117.09

NC(5)S 128.21

C(1)NC(5) 125.47

NC(5)C(4) 114.22

C(5)C(4)C(3)
 121.75

C(4)C(3)C(2)
 120.37

C(3)C(2)C(1)
 118.41

 



 








 












Table 5.  Pyrithione.  Rotational Constants (MHz).   Normal species.
 




Calc ropt  Expt. [1]





A  3257.4 3212.10(1)

B  1616.2 1609.328(7)

C  1080.2 1072.208(6)



 








 








[1] A.M.Daly, E.G.Mitchell, D.A.Sanchez, E.Block, and S.G.Kukolich, J.Phys.Chem. 115,14526(2011).

 








 








Pyridine


 








 








Table of Contents





Molecules/Nitrogen




 








 













pyrithione.html






Last Modified 14 Nov 2011