O=SCl2























 









Chlorine


Nuclear Quadrupole Coupling Constants


in Thionyl Chloride


 








 








 








The complete 35Cl nqcc tensor in thionyl chloride was determined by Müller and Gerry [1].  Diagonal components of the Cl nqcc's were determined in the mixed species by Merke and Dreizler [2].  Molecular ro and reSE structures were derived by Martin-Drumel et al. [3].  Earlier measurements of the nqcc's were made by Mata and Carballo [4] and Wenger et al. [5].

 








Calculations of the nqcc's were made here on the ro and reSE structures.  These are compared with available experimental nqcc's in Tables 1 - 3.  Structure parameterrs are given in Table 4.

 








In Tables 1 - 3, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Øz,SCl (degrees) is the angle between the z-principal axes of the nqcc tensor and the SCl bond direction.

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 efg's/nqcc's. 

 








 








 








Table 1. Chlorine nqcc's in O=S35Cl2 (MHz).  Calculation was made on the ro and reSE
structures [3].
 










Calc /ro
Calc /reSE
Expt. [1]
 








Xaa - 25.52 -
 25.24
 - 25.13085(19)

Xbb
- 0.64
- 0.59
- 0.32455(18)

Xcc
26.16
25.83
25.45540(18)

Xab
 ± 43.49
 ± 43.34
42.978(29) *

Xac ± 18.61 ± 19.04
19.309(73) *

Xbc -
 14.01 -
 14.35
13.949(30) *










RMS
0.50 (2.9 %)
0.27 (1.6 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xxx
32.14
32.12
32.362(40)

Xyy
32.17
32.16
31.452(38)

Xzz - 64.31 -
 64.28
 -
 63.814(40)

ETA
0.00045
0.00066
 -
 0.0143(11)

Øz,SCl
2.07
2.07













 








* Absolute value.

 








 







 
 








Table 2. Chlorine nqcc's in O=S35Cl37Cl (MHz).  Calculation was made on the ro and reSE structures [3].
 










Calc /ro
Calc /reSE
  Expt [2]
 








Xaa(35Cl) - 23.33 -
 23.05
 -
 23.008(50)

Xbb
- 2.81
- 2.75
- 2.454(99)

Xcc
26.14
25.80
25.462(49)

Xab ± 44.04
 ± 43.88



Xac ± 18.28 ± 18.71



Xbc - 14.50 -
 14.84



 







RMS
0.48 (2.8 %)
0.25 (1.5 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xaa(37Cl) - 21.81 -
 21.59
 -
 21.442(57)

Xbb
  1.11
  1.15
  1.33(12)

Xcc
20.70
20.44
20.112(60)

Xab ± 33.80
 ± 33.68



Xac ± 14.80 ± 15.15



Xbc - 10.68 -
 10.85



 







RMS
0.42 (2.9 %)
0.23 (1.6 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)













 








 








 








Table 3. Chlorine nqcc's in O=S37Cl2 (MHz).  Calculation was made on the ro and reSE
structures [3].
 










Calc /ro
Calc /reSE
Expt [3]
 








Xaa - 20.11 -
 19.89



Xbb
- 0.57
- 0.53



Xcc
20.68
20.42
20.1452(99)

Xab ± 34.32
 ± 34.20



Xac ± 14.56 ± 14.90



Xbc - 10.98 -
 11.25












RSD
0.44 (1.1 %)
0.44 (1.1 %)












Xxx
25.33
25.31



Xyy
25.35
25.35



Xzz - 50.68 -
 50.66



ETA
0.00045
0.00066



Øz,CCl
2.07
2.07













 








 


Table 4.  O=SCl2  Molecular structure parameters [3] (Å and degrees).  Angle ClSCl is derived value.






   ro    reSE





O=S 1.434(9)1.4330(7)

SCl 2.072(3)2.0700(3)

OSCl 108.00(6)107.703(6)

ClSCl   97.08  96.929

ClSOCl
 104.0(3)
 103.58(3)


 








 








[1] H.S.P.Müller and M.C.L.Gerry, J.Chem.Soc. Faraday Trans. 90,3473(1994).

[2] I.Merke and H.Dreizler, Z.Naturforsch. 47a,1150(1992).

[3] M.A.Martin-Drumel, A.Roucou, G.G.Brown, S.Thornwirth, O.Pirali, G.Mouret, F.Hindle, M.C.McCarthy, and A.Cuisset, J.Chem.Phys. 144,084305(2016).

[4] F.Mata and N.Carballo, Z.Naturforsch. 38a,769(1983).

[5] H.U.Wenger, A.Bauder, and Hs.H.Günthard, Chem.Phys. 1,441(1973).

 








S.Suzuki, M.Yamaguchi, M.Onda, T.Sakaizumi, O.Ohashi and I.Yamaguchi, J.Mol.Struct. 73,41(1981): ro structure.

 








 








O=CCl2 S=CCl2 SO2Cl2 SO2ClF

 








 








Table of Contents




Molecules/Chlorine




 








 













SOCl2.html






Last Modified 26 Feb 2016