CH2=C(Cl)-CH2Cl
































 









Chlorine


Nuclear Quadrupole Coupling Constants

in gauche-2,3-Dichloropropene


 








 


 





Chlorine nqcc's in anti- and gauche-2,3-dichloropropene were determined by Dikkumbura et al. [1].  The results for gauche are given on this page.  See here for anti


 








Calculation of the chlorine nqcc tensors was made here on molecular structures given by MP2/aug-cc-pVTZ optimization (ropt) and on this same structures but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).  These calculated nqcc's are compared with the experimental values in Tables 1 - 5.  Structure parameters are given in Table 6, rotational constants in Table 7.

 








In Tables 1 - 5, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.   (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 efg's/nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








 








NOTE:  The experimental results given below in Tables 1 - 4 were derived here using Kisiel's program QDIAG.f and data given in Table 4.2 of Ref. [1].

 









 









   








Table 1.  35Cl(2) nqcc's in CH2=C35Cl(2)-CH235Cl(3) (MHz).  

 







Calculation was made on the MP2/aug-cc-pVTZ optimized molecular structure (ropt), and on this same structure but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).

 









 ropt
reemp
 Expt. [1]
   








Xaa

16.15
16.05

15.695(2)


Xbb -
49.06 -
48.86
-
48.901(2)


Xcc
32.92
32.81

33.206(2)


Xab -
44.10 -
44.14

43.68(8)


Xac
  0.23

  0.26

  0.47(15)


Xbc
- 5.89

- 5.86

- 5.62(29)


 







RMS
0.32 (1.0 %)

0.31 (1.0 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
39.72
39.64

38.58(14)


Xyy
31.92
31.80

32.60(12)


Xzz - 71.64 -
71.44
-
71.19(7)


ETA -
0.109 -
0.110
-
0.0841(3)


z,CCl
  0.54
  0.55




 
 






 








 









   








Table 2.  35Cl(3) nqcc's in CH2=C35Cl(2)-CH235Cl(3) (MHz).  

 







Calculation was made on the MP2/aug-cc-pVTZ optimized molecular structure (ropt), and on this same structure but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).

 









 ropt
reemp
 Expt. [1]
   








Xaa
- 15.36 -
15.29
-
15.504(2)


Xbb
12.29
12.25

12.302(3)


Xcc
  3.07

  3.04

  3.202(3)


Xab
36.81
36.75
-
36.79(11)


Xac
42.21

42.13
-
41.80(10)


Xbc -
30.54
-
30.51
-
30.07(13)


 







RMS
0.11 (1.1 %)

0.16 (1.5 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
36.82
36.75

36.58(11)


Xyy
38.61
38.55

38.30(12)


Xzz - 75.43 - 75.30
-
74.88(12)


ETA
0.0237
0.0238

0.0230(21)


z,CCl
  0.60
  0.61




 
 






 









 









   








Table 3.  Cl nqcc's in CH2=C35Cl(2)-CH237Cl(3) (MHz).  

 







Calculation was made on the MP2/aug-cc-pVTZ optimized molecular structure (ropt), and on this same structure but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).

 









 ropt
reemp
Expt. [1]
 








Xaa (35Cl)
16.70

16.61

16.251(3)


Xbb -
49.64
-
49.44
-
49.462(3)


Xcc
32.94

32.83

33.211(3)


Xab -
43.77
-
43.70

43.35(6)


Xac
  0.27

  0.30

  0.12(22)


Xbc
- 5.93
-
- 5.83

- 4.7(5)


 







RMS
0.32 (1.0 %)

0.30 (0.9 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xaa (37Cl) -
12.72
-
12.66
-
12.812(4)


Xbb
  9.99

  9.95

  9.984(4)


Xcc
  2.73

  2.71

  2.828(4)


Xab
29.01

28.96
-
28.93(9)


Xac
33.32

33.26
-
33.39(14)


Xbc -
23.76
-
23.74
-
22.89(26)











RMS
0.08 (0.9 %)

0.11 (1.3 %)




RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








 








   








Table 4.  Cl nqcc's in CH2=C37Cl(2)-CH235Cl(3) (MHz).  

 







Calculation was made on the MP2/aug-cc-pVTZ optimized molecular structure (ropt), and on this same structure but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).

 









 ropt
reemp
Expt. [1]
 








Xaa (37Cl)
11.46

11.39

11.135(5)


Xbb -
37.40
-
37.24
-
37.300(4)


Xcc
25.94

25.85

26.165(4)


Xab -
35.74
-
35.68

35.52(18)


Xac
  0.09

  0.11

  0.15(28)


Xbc
- 4.66

- 4.64

- 3.8(4)


 







RMS
0.23 (0.9 %)

0.23 (0.9 %)




RSD
0.44 (1.1 %)
0.44 (1.1 %)



 







Xaa (35Cl) -
14.04
-
13.97
-
14.183(5)


Xbb
10.97

10.93

11.000(5)


Xcc
  3.07

  3.04

  3.182(5)


Xab
37.28

37.22
-
37.19(22)


Xac
41.66

41.58
-
41.60(21)


Xbc -
31.28
-
31.26
-
30.73(26)











RMS
0.11 (1.1 %)

0.15 (1.6 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 
 





   








 








   








Table 5.  37Cl nqcc's in CH2=C37Cl(2)-CH237Cl(3) (MHz).  

 







Calculation was made on the MP2/aug-cc-pVTZ optimized molecular structure (ropt), and on this same structure but with empirically corrected bond lenghts for C-C, C=C, and CCl (reemp).

 









 ropt
reemp
Expt.

 








Xaa  Cl(2)
11.93

11.86




Xbb -
37.89
-
37.73




Xcc
25.96

25.87




Xab -
35.39
-
35.33




Xac
  0.12

  0.15




Xbc
- 4.69

- 4.67




 







RMS







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 







Xaa  Cl(3) -
11.70
-
11.64




Xbb
  8.97

  8.94




Xcc
  2.73

  2.71




Xab
29.38

29.33




Xac
32.90

32.84




Xbc -
24.34
-
24.32













RMS







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 
 






 








 












Table 6.  gauche-2,3-Dichloropropene.  MP2/aug-cc-pVTZ optimized molecular structure parameters, ropt ( and degrees).  Corrected reemp C-C, C=C, and CCl bond lengths are given in parentheses.
 




 
 Cl
 C,1,B1
 C,2,B2,1,A1
 C,2,B3,1,A2,3,D1,0
 H,4,B4,2,A3,1,D2,0
 H,4,B5,2,A4,1,D3,0
 Cl,3,B6,2,A5,1,D4,0
 H,3,B7,2,A6,1,D5,0
 H,3,B8,2,A7,1,D6,0

 B1=1.7335261        (1.7303)
 B2=1.48760118      (1.4870)
 B3=1.33397217      (1.3302)
 B4=1.07914092
 B5=1.08073511
 B6=1.7895188         (1.7862)
 B7=1.08655845
 B8=1.08717158
 A1=114.90265408
 A2=121.11421322
 A3=121.56103784
 A4=119.24459342
 A5=111.28304336
 A6=110.03534485
 A7=111.22622248
 D1=-179.18506291
 D2=0.32604627
 D3=-179.49359143
 D4=67.73380961
 D5=-173.41129714
 D6=-50.93853622






 








 













Table 7. gauche-2,3-Dichloropropene.  Rotational constants (MHz).  35,35 species.
 





 ropt reemp     Expt. [1]






A 4819.
4838.
4825.77581(18)

B 2044.
2049.
2027.99973(16)

C 1570.
1574.
1559.15872(16)







 








 








[1] A.S.Dikkumbura, Masters Theses, Eastern Illinois University, 2016.  Faculty Advisor: R.A.Peebles.  Available for download at http://thekeep.elu.edu/theses/2443


 








 








anti-2,3-Dichloropropene 2-Chloropropene
cis-3-Chloropropene

gauche-3-Chloropropene Chloropropenes



 








 








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Molecules/Chlorine




 








 













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Last Modified 15 July 2016