C13H9N





 








 








Nitrogen

Nuclear Quadrupole Coupling Constants

in Benzoquinoline

 


















Nitrogen nqcc's in each of the following conformers of benzoquinoline were determined by McNaughton et al. [1]. 












5,6
 7,8

















 








Calculation of the nitrogen nqcc tensors in each conformer was made here on molecular roptstructures given by B3P86/6-31G(d,p) and B3P86/6-31G(3d,3p) optimization.  Calculated and experimental nqcc's are compared in Tables 1 and 2.  Optimized structure parameters are given in Table 3, rotational constants in Table 4.

 








In Tables 1 and 2, subscripts a,b,c refer to principal axes of the inertia tensor; x,y,z to principal axes of the nqcc tensor.  Ø is angle (degrees) between its subscripted parmeters.  RMS is the root mean square difference between calculated and experimental diagonal nqcc's.  RSD is the residual standard deviation of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.

 








 








   







Table 1.  14N nqcc's in 5,6-Benzoquinoline (MHz).  Calculation was made on molecular structures given by (1) B3P86/6-31G(d,p) and (2) B3P86/6-31G(3d,3p) optimization. 
   









Calc (1)
Calc (2)
Expt. [1]
 








Xaa
0.395
0.389
0.3793(26)

Xbb -
 3.605
 -
 3.615
 -
 3.6130(37) **

Xcc
3.210
3.226
3.2337(37) **

|Xab|
2.405
2.401
2.23(16)










RMS
0.017 (0.70 %)
0.007 (0.30 %)



RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.523
1.513



Xyy
3.210
3.226



Xzz -
 4.733
 -
 4.739



Øz,a
64.87
64.91



Øbi,a *
61.78
61.74



Øz,bi
  3.09
  3.17



 








 








* "bi" is bisector of CNC angle.

** Calculated here from experimental Xaa and (Xbb - Xcc) = -6.8467(26) MHz.

 








 








   







Table 2.  14N nqcc's in 7,8-Benzoquinoline (MHz).  Calculation was made on molecular structures given by (1) B3P86/6-31G(d,p) and (2) B3P86/6-31G(3d,3p) optimization. 
   









Calc (1)
Calc (2)
Expt. [1]
 








Xaa
 -
 0.258
 -
 0.266
 -
 0.2924(16)

Xbb -
 2.931
 -
 2.938
 -
 2.9150(26) **

Xcc
3.190
3.204
3.2074(26) **

|Xab|
2.895
2.892
2.902(26)










RMS
0.024 (1.12 %)
0.020 (0.94 %)



RSD
0.030 (1.3 %)
0.030 (1.3 %)



 







Xxx
1.593
1.584



Xyy
3.190
3.204



Xzz -
 4.783
 -
 4.788



Øz,a
57.39
57.39



Øbi,a *
59.31
59.38



Øz,bi
  1.92
  1.00



 








 








* "bi" is bisector of CNC angle.

** Calculated here from experimental Xaa and (Xbb - Xcc) = -6.1225(20) MHz.

 








 




Table 3. Benzoquinoline.  B3P86/6-31G(d,p) and B3P86/6-31G(3d,3p) optimized structure parameters (Å and degrees).
 





5,6-Benzoquinoline








 C
 N,1,B1
 C,2,B2,1,A1
 C,3,B3,2,A2,1,D1,0
 C,4,B4,3,A3,2,D2,0
 C,5,B5,4,A4,3,D3,0
 C,3,B6,2,A5,1,D4,0
 C,4,B7,3,A6,2,D5,0
 C,8,B8,4,A7,3,D6,0
 C,7,B9,3,A8,2,D7,0
 C,9,B10,8,A9,4,D8,0
 H,11,B11,9,A10,8,D9,0
 C,11,B12,9,A11,8,D10,0
 C,13,B13,11,A12,9,D11,0
 C,14,B14,13,A13,11,D12,0
 H,7,B15,3,A14,2,D13,0
 H,1,B16,2,A15,3,D14,0
 H,5,B17,4,A16,3,D15,0
 H,6,B18,5,A17,4,D16,0
 H,10,B19,7,A18,3,D17,0
 H,13,B20,11,A19,9,D18,0
 H,14,B21,13,A20,11,D19,0
 H,15,B22,14,A21,13,D20,0








    6-31G(d,p)   6-31G(3d,3p)









 B1=1.31952357
 B2=1.35436084
 B3=1.421549
 B4=1.40770048
 B5=1.37786988
 B6=1.43066893
 B7=1.44950861
 B8=1.42200586
 B9=1.35733935
 B10=1.41042002
 B11=1.08662098
 B12=1.37772582
 B13=1.4040045
 B14=1.3797123
 B15=1.08459718
 B16=1.08902805
 B17=1.08482449
 B18=1.0848428
 B19=1.08664783
 B20=1.08547748
 B21=1.08563545
 B22=1.0846603
 A1=117.91436995
 A2=123.24161926
 A3=116.66516815
 A4=119.86027325
 A5=117.00172395
 A6=119.50301953
 A7=118.82131696
 A8=120.7694954
 A9=119.4920592
 A10=118.55857548
 A11=121.01907326
 A12=119.64891097
 A13=120.3670719
 A14=117.01292706
 A15=116.29098034
 A16=120.50117501
 A17=121.12172484
 A18=120.46014829
 A19=120.31274441
 A20=119.888598
 A21=118.81641286
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=0.
 D7=180.
 D8=180.
 D9=180.
 D10=0.
 D11=0.
 D12=0.
 D13=0.
 D14=180.
 D15=180.
 D16=180.
 D17=180.
 D18=180.
 D19=180.
 D20=180.
  B1=1.31725937
 B2=1.35330521
 B3=1.41909687
 B4=1.40518559
 B5=1.3754373
 B6=1.42948195
 B7=1.4477854
 B8=1.41961085
 B9=1.35512712
 B10=1.40864192
 B11=1.08583667
 B12=1.37573791
 B13=1.40198456
 B14=1.37769169
 B15=1.08403092
 B16=1.08841435
 B17=1.08394328
 B18=1.08422203
 B19=1.08592735
 B20=1.08470644
 B21=1.08484006
 B22=1.08377478
 A1=117.889443
 A2=123.22171811
 A3=116.71340028
 A4=119.81294159
 A5=117.03007977
 A6=119.51416648
 A7=118.83560116
 A8=120.748826
 A9=119.5007657
 A10=118.60218093
 A11=120.99529394
 A12=119.66239232
 A13=120.36754244
 A14=117.12552376
 A15=116.264773
 A16=120.52469453
 A17=121.13286566
 A18=120.44840093
 A19=120.29740897
 A20=119.89443901
 A21=118.82261299
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=0.
 D7=180.
 D8=180.
 D9=180.
 D10=0.
 D11=0.
 D12=0.
 D13=0.
 D14=180.
 D15=180.
 D16=180.
 D17=180.
 D18=180.
 D19=180.
 D20=180.

 




 




7,8-Benzoquinoline








 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
 C,5,B5,4,A4,3,D3,0
 C,3,B6,2,A5,1,D4,0
 C,4,B7,3,A6,2,D5,0
 C,8,B8,4,A7,3,D6,0
 C,7,B9,3,A8,2,D7,0
 C,9,B10,8,A9,4,D8,0
 H,11,B11,9,A10,8,D9,0
 C,11,B12,9,A11,8,D10,0
 C,13,B13,11,A12,9,D11,0
 C,14,B14,13,A13,11,D12,0
 H,7,B15,3,A14,2,D13,0
 H,1,B16,2,A15,3,D14,0
 H,2,B17,1,A16,6,D15,0
 H,6,B18,5,A17,4,D16,0
 H,10,B19,7,A18,3,D17,0
 H,13,B20,11,A19,9,D18,0
 H,14,B21,13,A20,11,D19,0
 H,15,B22,14,A21,13,D20,0








    6-31G(d,p)   6-31G(3d,3p)








 B1=1.37703471
 B2=1.40760874
 B3=1.42005605
 B4=1.35021018
 B5=1.32056601
 B6=1.43011748
 B7=1.44745249
 B8=1.41951301
 B9=1.35883573
 B10=1.41051426
 B11=1.08670194
 B12=1.37872236
 B13=1.40565872
 B14=1.37948628
 B15=1.08666637
 B16=1.08481541
 B17=1.08700894
 B18=1.08885902
 B19=1.08662229
 B20=1.08580295
 B21=1.08575467
 B22=1.08421953
 A1=119.52866212
 A2=117.61175185
 A3=122.36019388
 A4=118.29110943
 A5=122.58381288
 A6=119.34075437
 A7=119.16518394
 A8=120.78406724
 A9=118.97144936
 A10=118.84080799
 A11=120.72486724
 A12=120.09345369
 A13=120.32786267
 A14=118.53124071
 A15=121.50652436
 A16=121.07178831
 A17=116.20842351
 A18=120.374636
 A19=120.01232779
 A20=119.76827475
 A21=121.61876794
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=0.
 D7=180.
 D8=180.
 D9=180.
 D10=0.
 D11=0.
 D12=0.
 D13=0.
 D14=180.
 D15=180.
 D16=180.
 D17=180.
 D18=180.
 D19=180.
 D20=180.
  B1=1.37469763
 B2=1.40547107
 B3=1.41747957
 B4=1.34910844
 B5=1.31823076
 B6=1.4288811
 B7=1.44626289
 B8=1.41725626
 B9=1.35657492
 B10=1.40888729
 B11=1.08586267
 B12=1.37652398
 B13=1.40365788
 B14=1.37737216
 B15=1.08591572
 B16=1.08411053
 B17=1.08620864
 B18=1.08841736
 B19=1.08582758
 B20=1.08501219
 B21=1.08498739
 B22=1.08345662
 A1=119.48548598
 A2=117.65652406
 A3=122.34027909
 A4=118.25954478
 A5=122.49810868
 A6=119.30263622
 A7=119.16130081
 A8=120.78300256
 A9=119.01094372
 A10=118.85739366
 A11=120.71471793
 A12=120.09073686
 A13=120.33148041
 A14=118.52966222
 A15=121.53604549
 A16=121.06782612
 A17=116.15571438
 A18=120.38779389
 A19=120.02693946
 A20=119.75477516
 A21=121.51311785
 D1=0.
 D2=0.
 D3=0.
 D4=180.
 D5=180.
 D6=0.
 D7=180.
 D8=180.
 D9=180.
 D10=0.
 D11=0.
 D12=0.
 D13=0.
 D14=180.
 D15=180.
 D16=180.
 D17=180.
 D18=180.
 D19=180.
 D20=180.

 





 








 



Table 4.  Benzoquinoline.  Rotational Constants (MHz).  Calc = (1) B3P86/6-31G(d,p) and (2) B3P86/6-31G(3d,3p) ropt.







Calc (1)
 Calc (2)
     Expt. [1]





   5,6 A
   1650.
   1616.
 1641.346930(25)

B
     558.
     573.
   556.389148(32)

C
     417.
     423.
   415.692066(13)





   7,8 A
   1654.
   1621.
 1609.544506(17)

B
     559.
     574.
   570.697899(14)

C
     418.
     424.
   421.4575900(82)



  








 








[1] M.K.Jahn, J.-U.Grabow, P.Godfrey, M.Travers, and D.Wachsmuth, P.Godfrey, and D.McNaughton, PCCP 19,8970(2017).

 








D.McNaughton, M.K.Jahn, J.-U.Grabow, P.Godfrey, M.Travers, and D.Wachsmuth, Abstract TH13, 71st International Symposium on Molecular Spectroscopy, Champaign-Urbana, Ill 2016.

 








 








Quinoline












 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 17 March 2017