C6H5Cl




 






















 









Chlorine


Nuclear Quadrupole Coupling Constants


in Chlorobenzene


 








 








 


 





Measurement of the chlorine nqcc's in chlorobenzene was most recently made by Dorosh et al. [1].   Earlier measurements were made by Drouin et al. [2], Merke et al. [2], Caminati and Mirri [3], Poynter [4], and Seln [5].  A substitution molecular structure was reported by Michel et al. [6].  Cradock et al. [7] report a structure determined by combined analysis of electron diffraction, rotation constant, and liquid crystal NMR data.

 








Chlorine nqcc's were calculated here on the molecular structures of Michel et al. and Cradock et al., and on a structure derived by B3P86/6-31G(3d,3p) optimization.  These calculated nqcc's are compared with the experimental values in Tables 1-3.  Structure parameters are compared in Table 4.  In Table 5, atomic coordinates for the optimized structure are given.

 








In Tables 1-3,  RMS is the root mean square difference between calculated and experimental 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 nqcc's.

 








 








   







Table 1. Chlorine nqcc's in C6H5Cl (MHz).  Calculation was made on the substitution structure of Michel et al. [6].
   










Calc.
Expt. [1]
   







35Cl Xaa - 71.64 - 71.2359(13)


Xbb
39.00
38.2153(15)


Xcc
32.64
33.0205(15)


ETA * - 0.089 - 0.072924(30)

 







RMS
0.55 (1.2 %)




RSD
0.49 (1.1 %)



 






37Cl Xaa - 56.46 - 56.1445(16)


Xbb
30.74
30.1200(27)


Xcc
25.72
26.0244(27)

  ETA * - 0.089 - 0.072948(69)


 






RMS
0.44 (1.2 %)




RSD
0.44 (1.1 %)



 







 








* ETA = (Xbb - Xcc)/Xaa = (Xxx - Xyy)/Xzz.

 









 








   







Table 2. Chlorine nqcc's in C6H5Cl (MHz).  Calculation was made on the roalpha structure of Cradock et al. [8].
   










Calc.
Expt. [1]
   







35Cl Xaa - 71.90 - 71.2359(13)


Xbb
38.93
38.2153(15)


Xcc
32.96
33.0205(15)


ETA * - 0.083 - 0.072924(30)

 







RMS
0.56 (1.2 %)




RSD
0.49 (1.1 %)



 






37Cl Xaa - 56.66 - 56.1445(16)


Xbb
30.68
30.1200(27)


Xcc
25.98
26.0244(27)

  ETA * - 0.083 - 0.072948(69)


 






RMS
0.44 (1.2 %)




RSD
0.44 (1.1 %)




 






 








* ETA = (Xbb - Xcc)/Xaa = (Xxx - Xyy)/Xzz.

 








 








   







Table 3. Chlorine nqcc's in C6H5Cl (MHz).  Calculation was made on the B3P86/6-31G(3d,3p) ropt structure.
   










Calc.
Expt. [1]
   







35Cl Xaa - 71.75 - 71.2359(13)


Xbb
38.91
38.2153(15)


Xcc
32.84
33.0205(15)


ETA * - 0.084 - 0.072924(30)

 







RMS
0.51 (1.1 %)




RSD
0.49 (1.1 %)



 






37Cl Xaa - 56.55 - 56.1445(16)


Xbb
30.67
30.1200(27)


Xcc
25.88
26.0244(27)

  ETA * - 0.084 - 0.072948(69)


 






RMS
0.40 (1.1 %)




RSD
0.44 (1.1 %)




 






 








* ETA = (Xbb - Xcc)/Xaa = (Xxx - Xyy)/Xzz.

 







 
 



Table 4.  C6H5Cl Molecular structure parameters ( and degrees).
 





 rs [7]  roalpha [8]   ropt






C(1)Cl 1.7248 1.7390 1.7364

C(1)C(2) 1.399 1.3908 1.3895

C(2)C(3) 1.386 1.3942 1.3900

C(3)C(4) 1.3976 1.4000 1.3903

C(2)H(2) 1.080 1.0779 1.0833

C(3)H(3) 1.081 1.0872 1.0848

C(4)H(4) 1.081 1.0795 1.0843

C(6)C(1)C(2) 120.16 121.65 121.30

C(1)C(2)C(3) 119.78 119.05 119.00

C(2)C(3)C(4) 120.24 120.24 120.47

C(3)C(4)C(5) 119.80 119.79 119.77

C(1)C(2)H(2) 119.45 119.67 119.87

C(2)C(3)H(3) 119.76 120.41 119.33






For comparison with ropt, the B3P86/6-31G(3d,3p) optimized structure of benzene is CC = 1.3909 and CH = 1.0851 .



 








 














Table 4. C6H535Cl  Atomic coordinates, B3P86/6-31G(3d,3p) ropt 
(More figures are shown than are significant.)
 







  a ()
  b ()







Cl
2.164557
0.0

C(1)
0.428114
0.0

C(2,6) - 0.252998 1.211162

C(3,5) - 1.642982 1.202605

C(4) - 2.340584
0.0

H(2,6)
0.301360 2.141916

H(3,5) - 2.180249 2.145010

H(4) - 3.424922
0.0


 








 








[1] O.Dorosh, E.Białkowska-Jaworska, Z.Kisiel, and L.Pszczłkowski, J.Mol.Spectrosc. 246,228(2007).

[2] B.J.Drouin, T.G.Lavaty, P.A.Cassak, and S.G.Kukolich, J.Chem.Phys. 107(17),6541(1997).

[3] I.Merke, Ch.Keussen, H.Dreizler, and M.Onda, Z.Naturforsch. 45a,1273(1990).

[4] W.Caminati and A.M.Mirri, Chem.Phys.Lett. 12,127(1971).

[5] R.L.Poynter, J.Chem.Phys. 39,1962(1963).

[6] H.Seln, Ark.Fys. 13,81(1957).

[7] F.Michel, H.Nery, P.Nosberger, and G.Roussy, J.Mol. Struct. 30, 409(1976);  G.Roussy and F.Michel, ibid. 30,399(1976).

[8] S.Cradock, J.M.Muir, and D.W.H.Rankin, J.Mol.Struct. 220,205(1990).

 








 








1,2-Dichlorobenzene 1,2-Chlorofluorobenzene

1,3-Dichlorobenzene 1,3-Chlorofluorobenzene

1,4-Dichlorobenzene 1,4-Chlorofluorobenzene

Bromobenzene cis-2-Chlorophenol

Fluorobenzene trans-2-Chlorophenol

Benzonitrile d1-Benzene











 








 








Table of Contents




Molecules/Chlorine




 








 













C6H5Cl.html






Last Modified 3 Oct 2007