Psuedo-Pelletierine:  9-Methyl-9-Azabicyclo[3.3.1]nonan-3-one

 








 








 








Nitrogen

Nuclear Quadrupole Coupling Constants


in Pseudo-Pelletierine


 








 








 








Calculation of the N nqcc tensors was made here on molecular structures of axial and equatorial boat-chair conformers of pseudo-pelletierine optimized at the B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) levels of theory.  Calculation of the molecular PE at the B3PW91/6-311+G(df,pd) level of theory on these optimized structures gives Eax < Eeq by about 7.8 kJ/mol.  Calculated and nqcc's are given in Tables 1 and 2; rotational constants in Table 3.

 









ax

eq












































 








In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.   Ø (degrees) is the angle between its subscripted parameters.  Øz,N-Me is the angle between the N-CH3 bond direction and the external z-axis.

RSD is the 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 axial Pseudo-Pelletierine (MHz).  Calculation was made on the (1) B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) opt structures.
   









Calc (1)
Calc (2)
Expt
   







Xaa -
 4.234 -
 4.214



Xbb
1.586
1.571



Xcc
2.648
2.642



|Xab|
3.172
3.179



 







RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
2.981
2.977



Xyy
2.648
2.642



Xzz - 5.628 -
 5.619



ETA - 0.0591 -
 0.0596



Øz,a
  23.7
  23.9



Øa,N-Me
  81.0
  80.9



Øz,N-Me
104.7
104.8



 







   








 








   







Table 1. 14N nqcc's in equatorial Pseudo-Pelletierine (MHz).  Calculation was made on the (1) B3P86/6-31G(3d,3p) and PBE1PBE/6-31G(3d,3p) opt structures.
   









Calc (1)
Calc (2)
Expt
   







Xaa
1.275
1.310



Xbb -
 4.052 -
 4.083



Xcc
2.776
2.773



|Xab|
3.631
3.601



 







RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
3.115
3.112



Xyy
2.776
2.773



Xzz - 5.891 -
 5.885



ETA - 0.0575 -
 0.0576



Øz,a
116.9
116.6



Øa,N-Me
  14.0
  13.8



Øz,N-Me
102.8
102.8



 








 








 








Optimized structures of these conformers are given in Z-matrix format here:  axial and equatorial.

 













Table 3.  Pseudo-Pelletierine .  Rotational Constants (MHz) and Dipole Moments (D).  Calc (1) = B3P86/6-31G(3d,3p) and Calc (2) = PBE1PBE/6-31G(3d,3p) opt structures.

 



______________axial_______________

 




Calc (1)
 Calc (2)   Expt

 



A   1415.
   1417.

B   1182.
   1184.

C   1026.
   1028.

 



|µa|   2.7
   2.7

|µb|   1.8
   1.8

 



____________equatorial_____________

 



A   1656.
   1657.

B   1016.
   1021.

C     998.
   1001.

 



|µa|   3.4
   3.4

|µb|   0.9
   0.9







 








 








M.Vallejo-López, P.Ecija, E.J.Cocinero, A.Lesarri, F.J.Basterretxea, and J.A.Fernández, Abstract MI08, 71st International Symposium on Molecular Spectroscopy, Champaign-Urbana, Ill 2016.

 








 








Tropinone
 Tropane
 1-Asabicyclo[2.2.2]octane

chair-chair Pseudo-Pelletierine





 








 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 30 May 2016