g-CF2Cl-C(=O)Cl



















 





 





 









Chlorine


Nuclear Quadrupole Coupling Constants


in gauche Chlorodifluoroacetyl Chloride


 








 








 








Chlorine nqcc tensors in gauche chlorodifluoroacetyl chloride were determined by Grubbs, et al. [1].  Calculation was made [1] of the nqcc tensors on a molecular structure given by MP2/aug-cc-pVTZ optimization with approximate re correction of the bond lengths.  Calculated and experimental nqcc's are compared 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.  z,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 for the B1LYP/TZV(3df,2p) model for calculation of the efg's/nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








  








   







Table 1.  Chlorine nqcc's in g-CF235Cl(7)-C(=O)35Cl(1) (MHz).  

 









Calc. [1]
Expt. [1]
   







35Cl(1) Xaa - 10.69 - 11.814(15)


Xbb - 13.42 - 13.039(20)


Xcc
24.12
24.853(12)


|Xab|
49.61 *
48.4(25)


|Xac|
20.24
19.6(41)


|Xbc|
  8.35
  8.90(55)

 







RMS
0.80 (4.8 %)




RSD
0.49 (1.1 %)



 







Xxx
42.70
40.9(34)


Xyy
23.50
24.4(19)


Xzz - 66.20 - 65.3(27)


ETA - 0.290 - 0.251(60)


z,CCl
1.34



 






35Cl(7) Xaa
18.12
17.485(14)


Xbb - 22.72 - 22.669(22)


Xcc
  4.60
  5.184(17)


|Xab|
35.41 *
35.6(28)


|Xac|
24.20
22.4(57)


|Xbc|
44.85
44.37(39)


 






RMS
0.50 (3.3 %)




RSD
0.49 (1.1 %)




 






Xxx
36.30
34.4(56)


Xyy
39.26
40.0(38)


Xzz - 75.56 - 74.4(31)


ETA
0.039
0.07(9)


z,CCl
1.62



 






   








* The algebraic sign of the product XabXacXbc is negative.

 








 








   







Table 2.  Chlorine nqcc's in g-CF237Cl(7)-C(=O)35Cl(1) (MHz).  

 









Calc. [1]
Expt. [1]
   







35Cl(1) Xaa
- 9.08 - 10.218(24)


Xbb - 14.96 - 14.507(32)


Xcc
24.04
24.725(20)


|Xab|
49.06 *
50.1(34)


|Xac|
21.04
22.9(56)


|Xbc|
  9.31
10.22(91)

 







RMS
0.81 (4.9 %)




RSD
0.49 (1.1 %)



 






37Cl(7) Xaa
12.76
12.282(25)


Xbb - 18.58 - 18.502(37)


Xcc
  5.82
  6.220(27)


|Xab|
29.38 *
31.5(41)


|Xac|
19.11
20.3(82)


|Xbc|
34.08
33.86(62)


 






RMS
0.36 (2.9 %)




RSD
0.44 (1.1 %)



 







 








* The algebraic sign of the product XabXacXbc is negative.

 








 








   







Table 3.  Chlorine nqcc's in g-CF235Cl(7)-C(=O)37Cl(1) (MHz).  

 









Calc. [1]
Expt. [1]
   







37Cl(1) Xaa
- 9.82 - 10.684(29)


Xbb
- 9.31
- 9.038(39)


Xcc
19.13
19.722(25)


|Xab|
39.18 *
40.9(40)


|Xac|
15.86
17.3(70)


|Xbc|
  6.11
  6.6(12)

 







RMS
0.62 (4.7 %)




RSD
0.44 (1.1 %)



 






35Cl(7) Xaa
19.17
18.534(29)


Xbb - 23.62 - 23.575(41)


Xcc
  4.45
  5.041(29)


|Xab|
34.76 *
34.0(65)


|Xac|
23.60
23(12)


|Xbc|
45.24
44.62(99)


 






RMS
0.50 (3.2 %)




RSD
0.49 (1.1 %)



 







 








* The algebraic sign of the product XabXacXbc is negative.

 








 








   







Table 4.  Chlorine nqcc's in g-CF237Cl(7)-C(=O)37Cl(1) (MHz).  

 









Calc. [1]
Expt. [1]
   







37Cl(1) Xaa
- 8.58
- 9.454(70)


Xbb - 10.50 - 10.171(84)


Xcc
19.09
19.625(45)


|Xab|
38.80 *




|Xac|
16.50




|Xbc|
  6.84



 







RMS
0.62 (4.7 %)




RSD
0.44 (1.1 %)



 






37Cl(7) Xaa
13.66
13.175(66)


Xbb - 19.36 - 19.272(79)


Xcc
  5.70
  6.097(43)


|Xab|
28.86 *




|Xac|
18.64




|Xbc|
34.41




 






RMS
0.36 (2.8 %)




RSD
0.44 (1.1 %)



 







 








* The algebraic sign of the product XabXacXbc is negative.

 








 








 



Table 5.  g-CF2Cl-C(=O)Cl.  Structure parameters, MP2/aug-cc-pVTZ optimization with approximate re bond lengths [2] ( and degrees).  This structure is given here in Z-matrix format.
 










  Cl(1)C(2)
1.7448

C(2)O(3)
1.1818

C(2)C(4)
1.5423

C(4)F(5)
1.3320

C(4)F(6)
1.3265

C(4)Cl(7)
1.7558

Cl(1)C(2)O(3)
124.45

Cl(1)C(2)C(4)
112.22

C(2)C(4)F(5)
110.71

C(2)C(4)F(6)
109.02

C(2)C(4)Cl(7)
108.92

O(3)Cl(1)C(2)C(4) - 179.02

Cl(1)C(2)C(4)F(5)
- 47.30

Cl(1)C(2)C(4)F(6) - 166.33

Cl(1)C(2)C(4)Cl(7)
  73.76







 








 













Table 6.  g-CF235Cl-C(=O)35Cl.  Rotational constants (MHz).  
 



 

 Calc. [1]  Expt. [1]







A 2424.9 2422.40712(62)


B 1470.0 1454.03317(51)


C 1280.3 1266.67027(65)







 








 








[1] G.S.Grubbs III, C.T.Dewberry, A.King, W.Lin, W.C.Bailey, and S.A.Cooke, J.Mol.Spectrosc. 263,127(2010).

 








 








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Molecules/Chlorine




 








 













CF2ClCOCl.html






Last Modified 1 June 2010