C5H10NC(=O)H

















 





 
































Nitrogen


Nuclear Quadrupole Coupling Constants

in N-Formylpiperidine


 








 








 








Nitrogen nqcc's in N-formylpiperidine 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-Formylpiperidine (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
1.369
1.392
1.361(2)


Xbb
2.059
2.099
2.119(3)


Xcc - 3.428 - 3.492 -
3.480(4)


Xab
0.323
0.314



Xac
1.614

1.612




Xbc -
0.646
-
0.630




 







RMS
0.046 (1.3 %)

0.022 (0.64 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.818
1.835



Xyy
2.186
2.219



Xzz - 4.004 - 4.054



ETA
0.092
0.095



 








 








 









 



Table 2. N-Formylpiperidine: B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ structure parameters ( and degrees).
 









 N
 C,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 C,4,B4,3,A3,2,D2,0
 C,1,B5,2,A4,3,D3,0
 H,2,B6,1,A5,6,D4,0
 H,2,B7,1,A6,6,D5,0
 H,3,B8,2,A7,1,D6,0
 H,3,B9,2,A8,1,D7,0
 H,4,B10,3,A9,2,D8,0
 H,4,B11,3,A10,2,D9,0
 H,5,B12,4,A11,3,D10,0
 H,5,B13,4,A12,3,D11,0
 H,6,B14,1,A13,2,D12,0
 H,6,B15,1,A14,2,D13,0
 C,1,B16,6,A15,5,D14,0
 H,17,B17,1,A16,6,D15,0
 O,17,B18,1,A17,6,D16,0







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







 B1=1.45122595
 B2=1.52519096
 B3=1.52779013
 B4=1.52812643
 B5=1.4473617
 B6=1.09939697
 B7=1.09068187
 B8=1.09423579
 B9=1.09591565
 B10=1.09816589
 B11=1.09393169
 B12=1.09443257
 B13=1.09623065
 B14=1.09997994
 B15=1.09354343
 B16=1.35498885
 B17=1.1075096
 B18=1.21504324
 A1=110.55967399
 A2=111.04740872
 A3=110.85698447
 A4=116.56515279
 A5=108.90087787
 A6=107.04730841
 A7=109.30286058
 A8=108.91474451
 A9=109.32978794
 A10=110.50063115
 A11=110.7931758
 A12=109.73817317
 A13=109.33651093
 A14=108.36656109
 A15=122.4507002
 A16=111.69837635
 A17=125.71883745
 D1=52.6529974
 D2=-54.34235218
 D3=-54.48366889
 D4=66.34664376
 D5=-177.06301761
 D6=175.03032035
 D7=-68.33612186
 D8=66.11007999
 D9=-177.01380552
 D10=175.84227236
 D11=-65.96215849
 D12=-65.95142239
 D13=177.36713157
 D14=-124.49609714
 D15=-0.06487281
 D16=179.8243314
 B1=1.45858335
 B2=1.52962235
 B3=1.53233043
 B4=1.5327394
 B5=1.45404401
 B6=1.09666404
 B7=1.08679672
 B8=1.09173316
 B9=1.09317362
 B10=1.09527414
 B11=1.09130075
 B12=1.09193125
 B13=1.09341489
 B14=1.09716867
 B15=1.09013538
 B16=1.35785556
 B17=1.10464979
 B18=1.21505722
 A1=110.7158537
 A2=111.28605601
 A3=110.98159825
 A4=116.4741109
 A5=108.89015811
 A6=107.26228101
 A7=109.23275091
 A8=108.87701165
 A9=109.30778223
 A10=110.41680426
 A11=110.68030734
 A12=109.66022624
 A13=109.34917847
 A14=108.47858478
 A15=122.38880519
 A16=111.8450523
 A17=125.89577141
 D1=52.34478434
 D2=-53.80363988
 D3=-54.12958434
 D4=66.69554168
 D5=-176.68390791
 D6=174.71591847
 D7=-68.68263491
 D8=66.70582387
 D9=-176.39662409
 D10=175.29404668
 D11=-66.61355465
 D12=-66.37923651
 D13=176.8675324
 D14=-125.6437068
 D15=0.56443661
 D16=-179.6040122

 





 








 



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






     B3P86
 B3LYP
   Expt. [1]






A     3932.
   3923.
3876.798(12)

B     1555.
   1540.
1557.7934(4)

C     1233.
   1220.
1237.4982(4)


 








 








N-Formylmorpholine
N-Formylpyrrolidine




 









 









[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 13 Nov 2017