OC4H8NC(=O)H

















 





 
































Nitrogen


Nuclear Quadrupole Coupling Constants

in N-Formylmorpholine


 








 








 








Nitrogen nqcc's in N-formylmorpholine 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. Structure parameters are given in Table 2, rotational constants in Table 3.

 








In Table 1, 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. 14N nqcc's in N-Formylmorpholine (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
1.477
1.501
1.479(2)


Xbb
2.131
2.175
2.196(4)


Xcc - 3.608 - 3.676 -
3.675(5)


Xab
0.297
0.286



Xac -
1.522

1.520




Xbc
0.619
-
0.592




 







RMS
0.054 (2.2 %)

0.014 (0.58 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.856
1.875



Xyy
2.246
2.280



Xzz - 4.102 - 4.155



ETA
0.095
0.097



 








 








 









 



Table 2. N-Formylmorpholine: 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
 C,1,B13,5,A12,4,D11,0
 H,14,B14,1,A13,5,D12,0
 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=1.4504487
 B2=1.51988358
 B3=2.42428157
 B4=1.44714916
 B5=1.09753899
 B6=1.09138766
 B7=1.09168307
 B8=1.10062847
 B9=1.09211683
 B10=1.10141123
 B11=1.09816423
 B12=1.09374696
 B13=1.35554993
 B14=1.10723021
 B15=1.21421826
 B16=1.41621037
 A1=109.25138805
 A2=90.5859043
 A3=115.54779821
 A4=109.54490684
 A5=107.68812418
 A6=110.71730571
 A7=109.81411974
 A8=144.56016738
 A9=94.34420781
 A10=109.97570574
 A11=109.10042372
 A12=123.14107027
 A13=111.75354059
 A14=125.43827247
 A15=111.20903744
 D1=-23.15813521
 D2=-50.49976635
 D3=69.61649459
 D4=-172.22241052
 D5=171.86870946
 D6=-68.10210578
 D7=12.17453809
 D8=-119.31251262
 D9=-69.07295725
 D10=172.28435713
 D11=-128.34392858
 D12=-0.28379271
 D13=179.5735838
 D14=53.66136997
 B1=1.4575392
 B2=1.52366066
 B3=2.43580895
 B4=1.45350733
 B5=1.09498577
 B6=1.08773072
 B7=1.08892506
 B8=1.09755627
 B9=1.08934387
 B10=1.09832581
 B11=1.09556282
 B12=1.09059549
 B13=1.35860802
 B14=1.10440639
 B15=1.21407399
 B16=1.42359163
 A1=109.42213192
 A2=90.61146225
 A3=115.44658303
 A4=109.51607307
 A5=107.94887591
 A6=110.66136341
 A7=109.78969074
 A8=144.38199083
 A9=94.60925393
 A10=109.97800447
 A11=109.22233966
 A12=123.06486085
 A13=111.87486511
 A14=125.62069116
 A15=111.35165907
 D1=-23.30594974
 D2=-50.5458748
 D3=69.59825615
 D4=-172.25442538
 D5=171.479758
 D6=-68.5205036
 D7=12.86835233
 D8=-118.88942044
 D9=-69.11850984
 D10=172.24244928
 D11=-130.10477638
 D12=1.02626688
 D13=-179.21771511
 D14=53.28101112

 





 








 



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






     B3P86
 B3LYP
   Expt. [1]






A     4268.
   4256.
4226.363(20)

B     1556.
   1540.
1551.8643(3)

C     1247.
   1232.
1244.2501(3)


 








 








N-Nitrosomorpholine
N-Formylpyrrolidine N-Formylpiperidine




 









 









[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