CH2CH2CH2CHCl



 





 
 


Chlorine


Nuclear Quadrupole Coupling Constants

in Cyclobutyl Chloride


 







 
 
Calculation of the chlorine nqcc's in equatorial cyclobutyl chloride was made on the effective structure of Kim and Gwinn [1], and on a structure obtained by B3P86/6-31G(3d,3p) optimization (with and without correction of the C-Cl bond length - see below).  These are compared with the experimental nqcc's [1,2] in Tables 1 - 3.  Structure parameters are compared in Table 4.
 
In Tables 1 - 3, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Ø (degrees) is the angle between its subscripted parameters.  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 B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's.
 
 
 
   







Table 1.  35Cl nqcc's in Cyclobutyl Chloride (MHz).  Calculation was made on the ro structure [1].
   








Calc.
Expt. [1]
Expt. [2]
   






Xaa - 58.20 - 56.58(10) - 56.052(3)
Xbb 34.94 32.98 32.667
Xcc 23.26 23.60(10) 23.385
|Xac| 33.85 32.0(6)
 
RMS 1.48 (3.9 %) 1.81 (4.8 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 

 
 
   







Table 2.  35Cl nqcc's in Cyclobutyl Chloride (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure.
   








Calc.
Expt. [1]
Expt. [2]
   






Xaa - 57.74 - 56.58(10) - 56.052(3)
Xbb 33.39 32.98 32.667
Xcc 24.35 23.60(10) 23.385
|Xac| 31.81 32.0(6)
 
RMS 0.83 (2.2 %) 1.20 (3.2 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
 
 
That the calculated nqcc's are uniformly greater (in magnitude) than the experimental values suggests that the optimized CCl bond length 1.7872 Å is too long.  Thus, the structure was optimized at the MP2/6-311+G(2d,p) level of theory and the CCl bond length corrected according to the method of Merke et al. [3].  This corrected CCl bond length is 1.7746 Å.
 
   







Table 3.  35Cl nqcc's in Cyclobutyl Chloride (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure but with CCl = 1.7746 Å.
   








Calc.
Expt. [1]
Expt. [2]
   






Xaa - 57.37 - 56.58(10) - 56.052(3)
Xbb 33.18 32.98 32.667
Xcc 24.18 23.60(10) 23.385
|Xac| 31.77 32.0(6)
 
RMS 0.58 (1.5 %) 0.94 (2.5 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
Xxx 35.10
Xyy 33.18
Xzz - 68.28
ETA 0.028
Øz,a 18.96
Øa,CCl 17.99
Øz,CCl   0.97
 
 
 
 
Table 4.  Cyclobutyl Chloride.  Heavy atom structure parameters (Å and degrees).  ropt is B3P86/6-31G(3d,3p).  Complete ropt structure is given here in Z-matrix format.
 
ro [1]   ropt
ClC(2) 1.775(5) 1.7872
1.7746 *
C(2)C(3) 1.525(5) 1.5331
C(2)C(5) 1.550(5) 1.5473
Cl-C(3)C(2)C(4) 135(1) 131.93
C(3)C(2)C(4) 90.8(5) 89.53
"pucker" 20(1) 29.35
Pucker is the angle between the C(3)C(2)C(4) and C(3)C(5)C(4) planes.
* Corrected MP2/6-311+G(2d,p) CCl bond length.

 
 
[1] H.Kim and W.D.Gwinn, J.Chem.Phys. 44,865(1966).
[2] R.Subramanian, J.M.Szarko, W.C.Pringle, and S.E.Novick, J.Mol.Struct. 742,165(2005).
[3] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).

 








 








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Last Modified 2 Aug 2007