CH3-O-CH2Cl
































 









Chlorine


Nuclear Quadrupole Coupling Constants

in gauche-Chloromethyl Methyl Ether

 








 

 





Chlorine nqcc's in g-chloromethyl methyl ether were determined by Ikeda et al. [1].

 








Calculation of the nqcc tensor was made here on molecular structures given by MP2/aug-cc-pVTZ and MP2/6-311+G(3df,3pd) optimizations; and on these same structures but with empirically corrected CCl bond lengths.  These calculated nqcc's are compared with the experimental values in Tables 1 - 4.  Structure parameters are given in Table 5, rotational constants in Table 6.

 








In Tables 1 - 4, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Øz,CCl (degrees) is the angle between the z-principal axis and the CCl bond direction.  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 nqcc's.  

 








 








   







Table 1.  35Cl nqcc's in Chloromethyl Methyl Ether (MHz).  

 







Calc (1) was made on the MP2/aug-cc-pVTZ(G03) optimized molecular structure.

Calc (2) was made on this same structure but with empirically corrected CCl bond length.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 27.73 - 27.61 - 27.4(2)

Xbb
- 3.06
- 3.14
- 3.1(1)

Xcc
30.79
30.75
30.5(2)

|Xab|
45.67  *
45.64  *



|Xac|
14.04
14.04



|Xbc|
13.62
13.67



 







RMS
0.26 (1.3 %)
0.19 (0.95 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
30.66
30.62



Xyy
35.92
35.91



Xzz - 66.58 - 66.52



ETA
0.0791
0.0795



Øz,CCl
0.52
0.53



 
 






 








* The algabraic sign of the product XabXacXbc is negative.

 








 








   







Table 2.  37Cl nqcc's in Chloromethyl Methyl Ether (MHz).  

 







Calc (1) was made on the MP2/aug-cc-pVTZ(G03) optimized molecular structure.

Calc (2) was made on this same structure but with empirically corrected CCl bond length.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 22.29 - 22.19 - 21.7(3)

Xbb
- 2.02
- 2.08
- 2.2(2)

Xcc
24.31
24.28
23.9(3)

|Xab|
35.90  *
35.88  *



|Xac|
11.05
11.05



|Xbc|
10.62
10.65



 







RMS
0.43 (2.7 %)
0.36 (2.3 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








* The algabraic sign of the product XabXacXbc is negative.

 








 








   







Table 3.  35Cl nqcc's in Chloromethyl Methyl Ether (MHz).  

 







Calc (1) was made on the MP2/6-311+G(3df,3pd) optimized molecular structure.

Calc (2) was made on this same structure but with empirically corrected CCl bond length.

 









Calc (1)
Calc (2)
Expt. [2]
   







Xaa - 27.63 - 27.94 - 27.4(2)

Xbb
- 3.14
- 2.93
- 3.1(1)

Xcc
30.78
30.87
30.5(2)

|Xab|
45.59  *
45.66  *



|Xac|
13.97
13.98



|Xbc|
13.62
13.53



 







RMS
0.21 (1.0 %)
0.40 (1.9 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
30.56
30.67



Xyy
35.90
35.94



Xzz - 66.46 - 66.61



ETA
0.0802
0.0791



Øz,CCl
0.53
0.53



 
 





   








* The algabraic sign of the product XabXacXbc is negative.

 








 








   







Table 4.  37Cl nqcc's in Chloromethyl Methyl Ether (MHz).  

 







Calc (1) was made on the MP2/6-311+G(3df,3pd) optimized molecular structure.

Calc (2) was made on this same structure but with empirically corrected CCl bond length.

 









Calc (1)
Calc (2)
Expt. [1]
   







Xaa - 22.21 - 22.45 - 21.7(3)

Xbb
- 2.08
- 1.92
- 2.2(2)

Xcc
24.30
24.37
23.9(3)

|Xab|
35.84  *
35.89  *



|Xac|
11.00
11.00



|Xbc|
10.62
10.54



 







RMS
0.38 (2.4 %)
0.54 (3.4 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 
 






 








* The algabraic sign of the product XabXacXbc is negative.

 








 












Table 5.  Chloromethyl Methyl Ether.  Heavy atom structure parameters (Å and degrees).  Complete structures are given here in Z.matrix format.
 



r (1) = MP2/aug-cc-pVTZ(G03) opt.

r (2) = r (1) but with corrected Cl bond length.
 


Point Group C1
  r (1)   r (2)





ClC(2) 1.8141 1.8108
C(2)O 1.3732
OC(4) 1.4242
ClC(2)O 112.88
C(2)OC(4) 112.95
C(4)OC(2)Cl
   70.12
 

r (1) = MP2/6-311+G(3df,3pd) opt.
r (2) = r (1) but with MP2/6-311+G(2d,p) opt corrected CCl bond length.




  r (1)   r (2)



ClC(2) 1.8038 1.8119
Click on image to enlarge. C(2)O 1.3707

OC(4) 1.4193

ClC(2)O 113.03

C(2)OC(4) 113.32

C(4)OC(2)Cl   70.44


 








 













Table 6.  Chloromethyl Methyl Ether.  Rotational constants (MHz).  35Cl species.
 




r (1) = MP2/aug-cc-pVTZ(G03) opt.

r (2) = r (1) but with corrected CCl bond length.







  r (1)   r (2)     Expt. [1]






A 14 194.6 14 209.0 14 233.873(13)

B   3 520.2   3 526.2   3 481.650(2)

C   3 062.2   3 067.3   3 032.799(3)
 
 


r (1) = MP2/6-311+G(3df,3pd) opt.

r (2) = r (1) but with corrected CCl bond length.







  r (1)   r (2)     Expt. [1]






A 14 347.3 14 311.6 14 233.873(13)

B   3 526.0   3 511.5   3 481.650(2)

C   3 072.0   3 059.5   3 032.799(3)


 








 








[1] T.Ikeda, R.F.Curl, and H.Karlsson, J.Mol.Spectrosc. 53,101(1974).

 








M.Hayashi, K.Kuwada, and H.Imaishi, Chemistry Letters (Chem. Soc. Jpn.) 913(1974).  Chloro- and Bromo- methyl methyl ether.

 








M.Hayashi and H.Kato, J.Mol.Spectrosc. 76,412(1979): rs structure.











 








CH3-O-CH2I




 








 








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Last Modified 3 April 2008