s-t-CH2CHCOCl




 





 
 
 


Chlorine


Nuclear Quadrupole Coupling Constants


in s-trans-Acryloyl Chloride


 







 
 
Calculation of the chlorine nqcc's in s-trans-acryloyl chloride was made on a molecular structure derived ab initio (see below).   These are compared with the experimental nqcc's of Onda et al. [1] in Table 1.  Structure parameters are given in Table 2, atomic coordinates in Table 3.
 
In Table 1, 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 for the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's. 
 
Subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the inertia c-axis, these are perpendicular to the molecular plane.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

 







 
 
   






Table 1. Chlorine nqcc's in s-trans-Acryloyl Chloride (MHz).
   









Calc.
Expt. [1]
   





35Cl Xaa   1.41   0.6757(29)
Xbb - 24.86 - 24.4537(25)
Xcc 23.45 23.781(5)
|Xab| 48.51 47.55(31)
 
RMS 0.52 (3.2 %)
RSD 0.49 (1.1 %)
 
Xxx 38.53 33.307(9)
Xyy 23.45 23.781(5)
Xzz - 61.98 - 57.088(9)
ETA - 0.243
Øz,a 52.57 52.59
Øa,CCl 54.52
Øz,CCl   1.95
   
37Cl Xaa - 2.11
Xbb - 16.37
Xcc 18.48
|Xab| 38.96
 

 
 
 
Molecular Structure
The molecular structure was optimized at the MP2/6-311+G(d,p) level of theory assuming Cs symmetry.  The optimized CC bond lengths, single and double,  were corrected using equations obtained from linear regression analysis of the data given in Table IX of Ref. [2].  For C=O, the bond length was corrected using the equation derived from the data in Table 2 of Ref. [3].  For the CCl bond, the structure was optimized at the MP2/6-311+G(2d,p) level and corrected by linear regression analysis of the data given in Table 4 of Ref. [4].  The CH bond lengths were corrected using r = 1.001 ropt, where ropt is obtained by MP2/6-31G(d,p) optimization [5].  Interatomic angles used in the calculation are those given by MP2/6-311+G(d,p) optimization.
Table 2.  Structure parameters (Å and degrees).  Structure is given here in Z-matrix format.
C(3)Cl 1.792
C(3)=O 1.191
C(2)-C(3) 1.3335
C(1)=C(2) 1.474
C(2)H 1.083
C(1)Hc 1.080
C(1)H 1.081
C(2)C(3)Cl 115.28
C(2)C(3)O 124.77
CCC 125.49
C(3)C(2)H 113.03
C(2)C(1)Hc 121.66
C(2)C(1)H 120.03
 
Hc is cis with Cl.
 
Table 3. Atomic coordinates ropt 
(More figures are shown than are significant.)
   a (Å)    b (Å)
Cl - 1.084356 - 0.817606
O - 0.539592 1.724838
C 1.406400 0.380750
C - 0.044316 0.641703
C 1.976130 - 0.824916
H 1.999842 1.286684
H 3.053437 - 0.914192
H 1.387174 - 1.730195
 
 

[1] M.Onda, K.Kuratomi, M.Mori, H.Miyazaki, I.Yamaguchi, and Y.Niide, J.Mol.Spectrosc. 171,565(1995).
[2] J.Demaison, J.Cosléou, R.Bocquet, and A.G.Lesarri, J.Mol.Spectrosc. 167,400(1994).
[3] J.Demaison, G.Wlodarczak, H.Rück, K.H.Wiedenmann, and H.D.Rudolph, J.Mol.Struct. 376,399(1996).
[4] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).
[5] J.Demaison and G.Wlodarczak, Structural Chem. 5,57(1994).
 
R.Kewley, D.C.Hemphill, and R.F.Curl Jr., J.Mol.Spectrosc. 44,443(1972):  For 35Cl, (Xaa, Xbb, Xcc) = (0.6, -24.4, 23.8 MHz); and for 37Cl, (0.3, -17.2, 16.9 MHz).

 








 








HCOCl FCOCl CH3COCl
OCCl2 SCCl2 SCFCl
 

 








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Molecules/Chlorine



 

 













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Last Modified 13 May 08