C5H4ClNO


















 




 








Nitrogen and Chlorine


Nuclear Quadrupole Coupling Constants

in 6-Chloro-2-Hydroxypyridine


 








 








 








Nitrogen and chlorine nqcc's in 6-chloro-2-hydroxypyridine 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 - 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.  (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 B3PW91/6-311+G(df,pd) model 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 6-Chloro-2-Hydroxypyridine, 35Cl species (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
1.746

1.730

1.628(4)


Xbb -
3.594
-
3.592
-
3.627(4)


Xcc
1.848

1.862

1.999(4)


|Xab|
1.374

1.372

1.37(6)


 







RMS
0.112 (4.6 %)

0.100 (4.2 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
2.078

2.063




Xyy
1.848
1.862



Xzz -
3.927
-
3.925




ETA -
0.0587

0.0511




z,a
103.62

103.64




bi,a*
104.76

104.63




z,bi
    1.14

    0.99




 








 








* "bi" is bisector of CNC angle.


 








 








   








Table 2.   35Cl nqcc's in 6-Chloro-2-Hydroxypyridine (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 -
61.09 -
60.59 - 60.227(4)

Xbb
30.28
30.18
29.149(4)

Xcc
30.81
30.41
31.077(4)

|Xab|
33.20

33.10

32.83(4)


 







RMS
0.84 (2.1 %)
0.74 (1.8 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
41.07
40.97



Xyy
30.81
30.41



Xzz -
71.88 -
71.38



ETA -
0.143 -
0.148



z,a
18.00
18.05



a,CCl
17.80
17.85



z,CCl
  0.20

  0.20



 








 


















   








Table 3.  14N and 37Cl nqcc's in 6-Chloro-2-Hydroxypyridine (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 (14N)
1.724

1.708

1.608(6)


Xbb -
3.572
-
3.570
-
3.606(6)


Xcc
1.848

1.862

1.998(6)


|Xab|
1.416

1.413

1.42(7)


 







RMS
0.112 (4.6 %)

0.099 (4.1 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xaa (37Cl) -
48.55
-
48.15
-
47.8733(8)


Xbb
24.27
24.18
23.379(4)


Xcc
24.28

23.97

24.495(4)


|Xab|
25.60

25.53

25.37(4)











RMS

0.64 (2.1 %)

0.56 (1.8 %)




RSD

0.44 (1.1 %)

0.44 (1.1 %)



 






































 


Table 4.   6-Chloro-2-Hydroxypyridine.  B3P86/6-31G(d,p) and B3P86/6-31G(3d,3p) structure parameters ( 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,5,B5,4,A4,3,D3,0
 H,3,B6,2,A5,1,D4,0
 Cl,1,B7,6,A6,5,D5,0
 H,2,B8,1,A7,6,D6,0
 H,4,B9,3,A8,2,D7,0
 O,5,B10,4,A9,3,D8,0
 H,11,B11,5,A10,4,D9,0


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


 B1=1.38807507
 B2=1.39543477
 B3=1.38478606
 B4=1.39855192
 B5=1.3293626
 B6=1.08556253
 B7=1.7471954
 B8=1.08190068
 B9=1.08265865
 B10=1.34255932
 B11=0.96891416
 A1=116.57720731
 A2=120.31392774
 A3=117.10970494
 A4=123.775222
 A5=119.66495832
 A6=116.15653122
 A7=121.07555705
 A8=122.76444412
 A9=119.09077032
 A10=106.26399318
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 B1=1.38598221
 B2=1.39259042
 B3=1.38272489
 B4=1.39571496
 B5=1.32672754
 B6=1.08480529
 B7=1.73732598
 B8=1.08116837
 B9=1.08208182
 B10=1.34274597
 B11=0.96674192
 A1=116.67679648
 A2=120.24028834
 A3=117.11635266
 A4=123.88770162
 A5=119.70424033
 A6=116.18038664
 A7=120.88250059
 A8=122.74103335
 A9=118.97469259
 A10=106.45773271
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 


 








 



Table 5.  6-Chloro-2-Hydroxypyridine.  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 3429.
3442. 3422.7097(1)

B 1284.
1291. 1286.3294(1)

C   934.
  939.   934.90405(7)


 








 








[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-pyridone
5-Chloro-2-hydroxypyridine



 








 








Table of Contents




Molecules/Nitrogen




 








 













6Cl2OHP.html






Last Modified 6 Sept 2017