OC4H8NN=O

















 





 
































Nitrogen


Nuclear Quadrupole Coupling Constants

in N-Nitrosomorpholine


 








 








 








Nitrogen nqcc's in N-nitrosomorpholine 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-Nitrosomorpholine (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
1.914
1.952
1.930(3)


Xbb
1.454
1.501
1.534(6)


Xcc - 3.368 - 3.453 -
3.464(7)


Xab -
0.260 -
0.280



Xac -
1.708
-
1.680




Xbc
0.653

0.618




 







RMS
0.073 (3.2 %)

0.027 (1.2 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.338
1.370



Xyy
2.591
2.612



Xzz - 3.929 - 3.982



ETA
0.319
0.312



 








 








 








   








Table 2.  Nitroso 14N nqcc's in N-Nitrosomorpholine (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
2.060
2.081
2.059(3)


Xbb -
5.373 -
5.412 -
5.282(6)


Xcc
3.313
3.330
3.223(7)


Xab
1.041
1.024



Xac
0.579
0.559




Xbc -
1.397
-
1.339




 







RMS
0.074 (2.1 %)

0.098 (2.8 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
2.105
2.122



Xyy
3.648
3.643



Xzz - 5.753 - 5.765



ETA
0.268
0.264



 








 









 



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









 N
 C,1,B1
 C,2,B2,1,A1
 C,1,B3,2,A2,3,D1,0
 C,1,B4,2,A3,3,D2,0
 H,2,B5,1,A4,5,D3,0
 H,2,B6,1,A5,5,D4,0
 H,3,B7,2,A6,1,D5,0
 H,3,B8,2,A7,1,D6,0
 H,4,B9,1,A8,5,D7,0
 H,4,B10,1,A9,5,D8,0
 H,5,B11,1,A10,2,D9,0
 H,5,B12,1,A11,2,D10,0
 N,1,B13,5,A12,4,D11,0
 O,14,B15,1,A14,5,D13,0
 O,3,B16,2,A15,1,D14,0







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







 B1=1.45010481
 B2=1.52264322
 B3=2.41699213
 B4=1.44515583
 B5=1.09623858
 B6=1.09156969
 B7=1.091499
 B8=1.10033347
 B9=1.09167403
 B10=1.10078074
 B11=1.0970199
 B12=1.0919059
 B13=1.33007251
 B15=1.21748966
 B16=1.41440148
 A1=108.70253913
 A2=91.54060605
 A3=117.78963247
 A4=109.23223707
 A5=107.19419588
 A6=110.46946793
 A7=109.68043031
 A8=144.44754229
 A9=94.86827502
 A10=109.5863715
 A11=107.56233032
 A12=117.89520643
 A14=115.7615631
 A15=111.44261024
 D1=-21.38975891
 D2=-48.00129937
 D3=72.31620198
 D4=-169.7192788
 D5=170.41742333
 D6=-69.84511756
 D7=13.91258365
 D8=-118.48510613
 D9=-71.07954336
 D10=170.47246842
 D11=-128.11117843
 D13=178.88472765
 D14=52.0825215
 B1=1.45800094
 B2=1.52660025
 B3=2.42830436
 B4=1.45133415
 B5=1.09381286
 B6=1.08758777
 B7=1.08871561
 B8=1.09731403
 B9=1.08886353
 B10=1.09773922
 B11=1.09453074
 B12=1.08870076
 B13=1.3329739
 B15=1.21846638
 B16=1.42148985
 A1=108.87515617
 A2=91.54404897
 A3=117.6072496
 A4=109.2148516
 A5=107.64509707
 A6=110.38963621
 A7=109.64298572
 A8=144.28655365
 A9=95.07139195
 A10=109.62062504
 A11=107.76660171
 A12=117.87885523
 A14=116.12699523
 A15=111.63140145
 D1=-21.49788464
 D2=-48.05293222
 D3=72.29022907
 D4=-169.70710226
 D5=170.03926649
 D6=-70.27625159
 D7=14.35511049
 D8=-118.2257979
 D9=-71.00099861
 D10=170.5625164
 D11=-130.01822117
 D13=-179.85863397
 D14=51.68084618

 





 








 



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






     B3P86
 B3LYP
   Expt. [1]






A     4288.
   4278.
4265.625(31)

B     1624.
   1604.
1610.5746(9)

C     1289.
   1271.
1277.8064(8)


 








 








N-Formylmorpholine
N-Nitrosopyrrolidine




 









 









[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 12 Nov 2017