C5H4ClNO


















 




 








Nitrogen and Chlorine


Nuclear Quadrupole Coupling Constants

in 5-Chloro-2-Hydroxypyridine


 








 








 








Nitrogen and chlorine nqcc's in 5-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 5-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
0.295

0.286

0.282(5)


Xbb -
2.534
-
2.548
-
2.635(4)


Xcc
2.239

2.262

2.352(4)


|Xab|
2.592

2.588




 







RMS
0.087 (5.0 %)

0.072 (4.1 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.834

1.819




Xyy
2.239
2.262



Xzz -
4.073
-
4.082




ETA
0.0996

0.108




z,a
59.31

59.35




bi,a*
59.32

59.33




z,bi
  0.01

  0.02




 








 








* "bi" is bisector of CNC angle.


 








 








   








Table 2.   35Cl nqcc's in 5-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 -
73.90 -
73.36 - 72.772(4)

Xbb
38.66
38.48
37.949(4)

Xcc
35.24
34.88
34.823(4)

|Xab|
  3.46

  3.50




 







RMS
0.60 (1.2 %)
0.46 (0.95 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
38.76
38.59



Xyy
35.24
34.88



Xzz -
74.00 -
73.47



ETA -
0.047 -
0.050



z,a
1.76
1.79



a,CCl
1.99
2.01



z,CCl
0.23
0.22



 








 


















   








Table 3.  14N and 37Cl nqcc's in 5-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)
0.298

0.288

0.281(4)


Xbb -
2.537
-
2.550
-
2.637(5)


Xcc
2.239

2.262

2.356(5)


|Xab|
2.591

2.587




 







RMS
0.089 (5.1 %)

0.074 (4.2 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xaa (37Cl) -
58.24
-
57.82
-
57.363(4)


Xbb
30.47
30.33
29.916(5)


Xcc
27.77

27.49

27.4478(5)


|Xab|
  2.68

  2.72













RMS

0.63 (1.6 %)

0.36 (0.94 %)




RSD

0.44 (1.1 %)

0.44 (1.1 %)



 






































 


Table 4.   5-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
 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,11,B11,5,A10,4,D9,0


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


 B1=1.38813307
 B2=1.39572023
 B3=1.38260763
 B4=1.40018849
 B5=1.32675002
 B6=1.08449237
 B7=1.08675976
 B8=1.73898573
 B9=1.08330279
 B10=1.34424998
 B11=0.96884498
 A1=119.07226309
 A2=118.76698178
 A3=117.75225652
 A4=123.76708581
 A5=120.23468175
 A6=117.05980991
 A7=120.24179625
 A8=122.00977335
 A9=118.7993031
 A10=105.88567203
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 B1=1.38579818
 B2=1.39330942
 B3=1.3804145
 B4=1.39724712
 B5=1.32433339
 B6=1.08362329
 B7=1.08600505
 B8=1.72969945
 B9=1.08271279
 B10=1.34456892
 B11=0.9666323
 A1=119.07181045
 A2=118.74307151
 A3=117.761499
 A4=123.83652052
 A5=120.19010988
 A6=117.04881796
 A7=120.20137247
 A8=122.01301151
 A9=118.69256687
 A10=106.13389391
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=180.
 D7=180.
 D8=180.
 D9=180.
 


 








 



Table 5.  5-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 5808.
5828. 5785.0267(5)

B 1005.
1010. 1006.60906(7)

C   857.
  861.   857.47814(9)


 








 








[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
6-Chloro-2-hydroxypyridine



 








 








Table of Contents




Molecules/Nitrogen




 








 













5Cl2OHP.html






Last Modified 5 Sept 2017