C4H8NN=O

















 





 
































Nitrogen


Nuclear Quadrupole Coupling Constants

in N-Nitrosopyrrolidine


 








 








 








Nitrogen nqcc's in N-nitrosopyrrolidine were determined by Lou et al. [1].

 








Calculation of the nqcc's was made here on molecular structures derived by B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ optimization.  Calculated and experimental nqcc's are compared in Tables 1 and 2. Structure parameters are given in Table 3, rotational constants in Table 4.

 








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.

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 the efg's/nqcc's.


 








 








   








Table 1.  Amino 14N nqcc's in N-Nitrosopyrrolidine (MHz).  Calculation was made on ropt structures given by (1) B3P86/6-31G(3d,3p) and (2) B3LYP/cc-pVTZ optimization.
   










Calc. (1)

Calc. (2)
Expt. [1]
   








Xaa
2.113
2.128
2.136(7)


Xbb
1.785
1.808
1.863(21)


Xcc - 3.899 - 3.936 -
3.999(22)


Xab
0.391
0.395



Xac -
0.429 -
0.411




Xbc
0.299

0.300




 







RMS
0.074 (2.8 %)

0.049 (1.8 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.566
1.583



Xyy
2.380
2.399



Xzz - 3.946 - 3.982



ETA
0.206
0.205



 








 








 








   








Table 2.  Nitroso 14N nqcc's in N-Nitrosopyrrolidine (MHz).  Calculation was made on ropt structures given by (1) B3P86/6-31G(3d,3p) and (2) B3LYP/cc-pVTZ optimization.
   










Calc. (1)

Calc. (2)
Expt. [1]
   








Xaa
1.791
1.821
1.787(8)


Xbb -
5.438 -
5.470 -
5.362(27)


Xcc
3.647
3.649
3.575(28)


Xab -
1.580 -
1.542



Xac
0.024
0.014




Xbc -
0.273
-
0.301




 







RMS
0.060 (1.7 %)

0.078 (2.2 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
2.117
2.130



Xyy
3.658
3.661



Xzz - 5.775 - 5.791



ETA
0.267
0.264



 








 









 



Table 3. N-Nitrosopyrrolidine: B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ structure parameters ( and degrees).
 









 C
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 N,4,B4,3,A3,2,D2,0
 H,1,B5,5,A4,4,D3,0
 H,1,B6,5,A5,4,D4,0
 H,2,B7,1,A6,5,D5,0
 H,2,B8,1,A7,5,D6,0
 H,3,B9,2,A8,1,D7,0
 H,3,B10,2,A9,1,D8,0
 H,4,B11,3,A10,2,D9,0
 H,4,B12,3,A11,2,D10,0
 N,5,B13,4,A12,3,D11,0
 O,14,B14,5,A13,4,D12,0







B3P86/6-31G(3d,3p)
B3LYP/cc-pVTZ







 B1=1.52718159
 B2=1.53440146
 B3=1.53038059
 B4=1.46023311
 B5=1.09039999
 B6=1.09650368
 B7=1.09398598
 B8=1.09110012
 B9=1.09091076
 B10=1.09382614
 B11=1.09547821
 B12=1.09232148
 B13=1.3128116
 B14=1.22486024
 A1=103.13787238
 A2=104.21643995
 A3=102.63384421
 A4=109.99166285
 A5=110.4031736
 A6=109.79612134
 A7=112.52196493
 A8=112.95805706
 A9=109.95884988
 A10=113.46444344
 A11=114.34316511
 A12=124.09005096
 A13=114.17440901
 D1=37.16192961
 D2=-25.74457099
 D3=140.28331426
 D4=-100.11910919
 D5=84.27775113
 D6=-155.45087139
 D7=159.22859957
 D8=-80.63239091
 D9=91.63520867
 D10=-145.25942193
 D11=177.74213399
 D12=3.95350957
 B1=1.53095524
 B2=1.53885646
 B3=1.53403549
 B4=1.46741313
 B5=1.08746798
 B6=1.09384432
 B7=1.09137059
 B8=1.08842586
 B9=1.08834569
 B10=1.09128455
 B11=1.0923893
 B12=1.089176
 B13=1.31458424
 B14=1.22634295
 A1=103.22132511
 A2=104.23657086
 A3=102.75138828
 A4=110.07321268
 A5=110.41498735
 A6=109.79836927
 A7=112.51570035
 A8=112.9214374
 A9=109.93081578
 A10=113.2128364
 A11=114.13593131
 A12=124.51118684
 A13=114.68105052
 D1=36.99430834
 D2=-25.85862908
 D3=139.71098571
 D4=-100.67213572
 D5=84.58852078
 D6=-155.13400627
 D7=159.0306784
 D8=-80.81866889
 D9=91.60831124
 D10=-145.46043942
 D11=178.15846181
 D12=4.00859468

 





 








 



Table 4.  N-Nitrosopyrrolidine: Rotational Constants (MHz); B3P86/6-31G(3d,3p), B3LYP/cc-pVTZ, and Experimental.






     B3P86
 B3LYP
   Expt. [1]






A   6143.   6126.
6061.41(20)

B   2082.   2063.
2077.557(5)

C   1650.   1636.
1650.531(5)


 








 








N-Formylpyrrolidine
N-Nitrosomorpholine




 









 









[1] Q.Lou, K.W.Hwang, X.Z.Liu, C.Sahi, R.K.Bohn, and C.W.Bock, J.Mol.Struct. 445,117(1998).


 








 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 11 Nov 2017