C7H13N





 









Nitrogen


Nuclear Quadrupole Coupling Constants

in 1-Asabicyclo[2.2.2.]octane


 











 





 








The nitrogen nqcc in 1-asabicyclo[2.2.2.]octane (aka quinuclidine) was measured by Vormann and Dreizler [1].  A heavy atom substitution structure was determined by Consalvo and Stahl [2].  Calculation of the nqcc was made here on this structure complemented here with MP2/6-31G(d,p) optimization for the C-H geometry, and on several ab initioand HF-DFT optimized structures.  These are compared with the experimental nqcc in Table 1.  Parameters for the substitution and B3P86/6-31G(3d,3p) optimized structures are given in Table 2.

 
   









   





Table 1.  Nitrogen nqcc's in 1-Asabicyclo[2.2.2.]octane, and Rotational Constant B.  Calculation was made on the substitution structure [2], and on structures given by Method/Basis optimization (column 1).

 


   

eQq (MHz) B (MHz)

   





Experimental [1] - 5.1915(36) 2425.56577(33)
 
Substitution Structure - 5.174 2440.5

 
  Method/6-31G(d,p) Calc. Calc.
  HF - 5.293 2443.9
  B3LYP - 5.217 2533.9
  B1LYP - 5.227 2535.5

  B3P86 - 5.205 2559.3

  B3PW91 - 5.209 2552.6
    mPW1PW91  -
5.208
2561.8

  PBE1PBE - 5.204 2563.3
  MP2 - 5.121 2563.4
 
Method/6-31G(3d,3p)
  HF - 5.278 2445.9
  B3LYP - 5.244 2417.1
  B1LYP - 5.248 2418.4
  B3P86 - 5.200 2563.4
  B3PW91 - 5.223 2556.6
  mPW1PW91 - 5.219 2565.8
  PBE1PBE - 5.214 2567.2
 
Method/6-311G(3d,3p)
  HF - 5.275 2448.6
  B3P86 - 5.214 2444.3
  mPW1PW91 - 5.207 2447.1
  PBE1PBE - 5.201 2448.2
 

   








 
Several optimization models give structures - most importantly, NC bond lengths and CNC angles - on which good agreement is obtained between calculated and experimental nqcc's.
 
   
Table 2.  1-Asabicyclo[2.2.2.]octane.  Substitution, rs and B3P86/6-31G(3d,3p) optimized, ropt structures.  Heavy atom parameters (Å and degrees).  Complete structures are given here in Z-matrix format.
 
 rs [2]   ropt

NC(2) 1.466(7) 1.4619
C(2)C(5) 1.552(14) 1.5534
C(5)C(8) 1.529(7) 1.5326
N - - - C(8) 2.5798 * 2.5692
C(2)NC(3) 109.11 * 109.40
NC(2)C(5) 111.85(53) 111.80
  C(2)C(5)C(8) 108.32(55) 107.90
* Derived here.
 
 

[1] K.Vormann and H.Dreizler, J.Mol.Struct. 190,489(1988).
[2] D.Consalvo and W.Stahl, J.Mol.Struct. 447,119(1998).

 








 







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Last Modified 25 March 2006