C5H4ClNO


















 




 








Nitrogen and Chlorine

Nuclear Quadrupole Coupling Constants

in 5-Chloro-2-Pyridone

 








 








 








Nitrogen and chlorine nqcc's in 5-chloro-2-pyridone were determined by Calabrese et al. [1].

 








Calculation of the nqcc's was made here on a molecular structures derived by B3P86/6-31G(d,p) and B3P86/6-31G(3d,3p) optimization.  Calculated and experimental nqcc's are compared in Tables 1 - 4.  Structure parameters are given in Table 5, rotational constants in Table 6.

 








In Tables 1 - 4, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  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 (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation of the (1) B3PW91/6-311+G(df,pd) and (2) B3PW91/6-311+G(d,p) models for calculation of nitrogen efg's/nqcc's; and of the B1LYP/TZV(3df,2p) model for calculation of the chlorine efg's/nqcc's.

 








 








   







Table 1.  14N nqcc's in 5-Chloro-2-Pyridone, 35Cl species (MHz).  Calculation was made on the B3P86/6-31G(d,p) optimized structure with both (1) B3PW91/6-311+G(df,pd) and (2) B3PW91/6-311+G(d,p) models.
   









Calc. (1)
Calc. (2)
Expt. [1]
   







Xaa
1.545
1.643
1.636(5)

Xbb
1.158
1.213
1.241(7)

Xcc - 2.703 - 2.856 - 2.876(7)

|Xab|
0.062
0.045



 







RMS
0.123 (6.4 %)
0.020 (1.1 %)



RSD
0.030 (1.3 %)
0.086 (3.8 %)



 







Xxx
1.148
1.208



Xyy
1.555
1.647



Xzz - 2.703 - 2.855



ETA
0.150
0.153



Øz,c*
   0
   0



 








 








* The principal z-axis of the nqcc tensor is perpendicular to the plane of the molecule (ab-plane).

 








 








   







Table 2.  14N nqcc's in 5-Chloro-2-Pyridone, 35Cl species (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) optimized structure with both (1) B3PW91/6-311+G(df,pd) and (2) B3PW91/6-311+G(d,p) models.
   









Calc. (1)
Calc. (2)
Expt. [1]
   







Xaa
1.529
1.627
1.636(5)

Xbb
1.164
1.219
1.241(7)

Xcc - 2.693 - 2.846 - 2.876(7)

|Xab|
0.074
0.056



 







RMS
0.130 (6.8 %)
0.022 (1.1 %)



RSD
0.030 (1.3 %)
0.086 (3.8 %)



 







Xxx
1.149
1.212



Xyy
1.543
1.635



Xzz - 2.693 - 2.846



ETA
0.146
0.149



Øz,c*
   0
   0



 








 








* The principal z-axis of the nqcc tensor is perpendicular to the plane of the molecule (ab-plane).

 








 








   







Table 3.   35Cl nqcc's in 5-Chloro-2-Pyridone (MHz).  Calculation was made on (1) B3P86/6-31G(d,p) and (2) B3P86/6-31G(3d,3p) optimized structures.
   









Calc. (1)
Calc. (2)
Expt. [1]
   







Xaa -
 75.50 -
 74.97 - 74.30(2)

Xbb
38.62
38.42
37.991(9)

Xcc
36.88
36.55
36.312(9)

|Xab|
  0.88
  0.93



 







RMS
0.85 (1.7 %)
0.48 (0.97 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
38.62
38.43



Xyy
36.88
36.55



Xzz -
 75.51 -
 74.98



ETA -
 0.023 -
 0.025



Øz,a
0.44
0.47



Øa,CCl
0.76
0.78



Øz,CCl
0.32
0.31



 








 








 


Table 4.   5-Chloro-2-Pyridone.  B3P86/6-31G(d,p) and B3P86/6-31G(3d,3p) 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
 N,1,B5,2,A4,3,D3,0
 H,3,B6,2,A5,1,D4,0
 H,1,B7,6,A6,5,D5,0
 Cl,2,B8,1,A7,6,D6,0
 H,4,B9,3,A8,2,D7,0
 O,5,B10,4,A9,3,D8,0
 H,6,B11,1,A10,2,D9,0


B3P86/6-31G(d,p)
 B3P86/6-31G(3d,3p)


 B1=1.36118719
 B2=1.42240894
 B3=1.36136257
 B4=1.44990981
 B5=1.35888691
 B6=1.085518
 B7=1.08299272
 B8=1.73660444
 B9=1.08320861
 B10=1.22291336
 B11=1.01169103
 A1=119.08886989
 A2=120.55695724
 A3=122.11849922
 A4=119.47244939
 A5=118.79231357
 A6=117.37569056
 A7=120.47223597
 A8=121.5975429
 A9=127.08841943
 A10=119.89602704
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
  B1=1.35917117
 B2=1.42051734
 B3=1.35947639
 B4=1.4473421
 B5=1.35718736
 B6=1.08479826
 B7=1.08232284
 B8=1.72728474
 B9=1.0826526
 B10=1.220154
 B11=1.01148602
 A1=119.0283423
 A2=120.61013003
 A3=121.99842463
 A4=119.52646116
 A5=118.69822191
 A6=117.29700299
 A7=120.48905476
 A8=121.70095797
 A9=126.978023
 A10=119.81575528
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 


 








 



Table 5.   5-Chloro-2-Pyridone.  Rotational Constants (MHz).  35Cl Species.
 




Calc (1) = B3P86/6-31G(d,p) optimization.

Calc (2) = B3P86/6-31G(3d,3p) optimization.






  Calc (1)
 Calc (2)   Expt. [1]






A 5656.
 5672. 5612.110(1)

B 1005.
 1011. 1009.4284(2)

C   853.
   858.   855.6732(2)


 








 








[1] C.Calabrese, A.Maris, I.Uriarte, E.J.Cocinero, and S.Melandri, Chem.Eur.J. 23,3595(2017).

 








 








Pyridine 2-Pyridone
2-Hydroxypyridine

5-Chloro-2-hydroxypyridine
 6-Chloro-2-hydroxypyridine



 








 








Table of Contents




Molecules/Nitrogen




 








 













5Cl2Pyridone.html






Last Modified 5 Sept 2017