SO2Cl-N=C=O






























 








Nitrogen and Chlorine


Nuclear Quadrupole Coupling Constants


in Sulfonyl Chloride Isocyanate


 








 









The microwave spectrum of sulfonyl chloride isocyanate was observed by Jo et al. [1], a mixed ro- ra (microwave + electron diffraction) structure was derived.  N and Cl nqcc'c were determined.












Calculation of the chlorine nqcc tensors was made here on this ro, ra structure and on a structure given by MP2/6-311+G(3df) optimization (ropt).  Calculated and experimental nqcc's are compared in Tables 1 - 3.  Structure parameters are given in Table 4,  rotational constants in Table 5.


 








In Tables 1 -3, subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its subscript parameters.


RMS is the root mean square difference between calculated and experimental nqcc's.  RSD is the residual standard deviation of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the N efg's/nqcc's; and of the B1LYP/TZV(3df,2p) model for calculation of the Cl efg's/nqcc's.

 








 








 








Table 1.  14N nqcc's in SO235Cl-N=C=O (MHz).  Calculation was made on ro- ra and ropt molecular structures.

 










Calc /ro- ra
Calc /ropt
Expt [1]

 








Xaa
2.254

3.002

2.905(8)


Xbb -
1.194
-
1.844
-
1.709(12)


Xcc -
1.059
-
1.158
-
1.196


Xab
0.940

1.081




Xac -
1.202
-
0.628




Xbc -
0.210

0.321













RMS

0.485 (25. %)

0.098 (5.1 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx -
1.346
-
1.037




Xyy -
1.524
-
2.262




Xzz
2.870

3.300




ETA
0.0618

0.371




Øz,SN
13.49

23.2













   








 








 








Table 2.  35Cl nqcc's in SO235Cl-N=C=O (MHz).  Calculation was made on ro- ra and ropt molecular structures.

 










Calc /ro- ra
Calc /ropt
Expt [1]

 








Xaa
16.98

23.16

15.768(9)


Xbb -
55.65
-
61.45
-
53.641(10)


Xcc
38.67

38.29

37.873


Xab
42.33

34.16




Xac
  0.95

  0.41




Xbc
  1.80

  3.25













RMS

1.43 (4.0 %)

6.22 (17. %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xxx
35.59

34.65




Xyy
39.53

38.95




Xzz -
75.12
-
73.60




ETA
0.0524

0.0584




Øz,SCl
0.59

0.58














 









 









 








Table 3.  14N and 37Cl nqcc's in SO237Cl-N=C=O (MHz).  Calculation was made on ro- ra and ropt molecular structures.

 










Calc /ro- ra
Calc /ropt
Expt [1]

 








Xaa(14N)
2.218

2.959

2.875(19)


Xbb -
1.158
-
1.801
-
1.652(14)


Xcc -
1.060
-
1.158
-
1.223


Xab
1.004

1.173




Xac -
1.198
-
0.634




Xbc -
0.233

0.308













RMS

0.484 (25. %)

0.106 (5.5 %)




RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xaa(37Cl)
12.11

17.20

11.186(20)

Xbb -
42.58
-
47.38
-
41.049(14)


Xcc
30.47

30.18

29.863


Xab
34.42

28.19




Xac
  0.70

  0.29




Xbc
  1.48

  2.54




 








RMS

1.09 (4.0 %)

5.05 (18. %)




RSD

0.44 (1.1 %)

0.44 (1.1 %)













 









 




Table 4.  Sulfonyl Chloride Isocyanate.  Molecular structure parameters, ro- ra and ropt (Å and degrees).  Bond lengths are ra values [2], angles are ro [1].








 ro- ra   ropt







 

SCl
2.0185 2.0196
SO(6)
1.4177 1.4164
SO(7)
1.4177
1.4228
SN
1.6584
1.6472
NC
1.146
1.2329
CO
1.233
1.1590
SN=C
124.00(1)
123.94
NS=O(6)
109.22(1)
106.59
NS=O(7) 109.22(1)
106.92
NSCl
  97.86(3)
100.00
N=C=O
175.63(2)
173.56


ClSN=C
  94.12(3)
  81.43


O(6)=SN=C
206.02(3)
193.15


O(7)=SN=C
342.21(3)
328.96

















 



Table 5.  Sulfonyl Chloride Isocyanate, 35Cl species.  Rotational Constants (MHz). 







Calc /ro- ra Calc /ropt   Expt [1]






A   3078.6
  2985
3078.396(7)

B   1471.9
  1493
1471.985(3)

C   1240.3
  1244
1240.364(2)


 








 









[1] O.L.Jo, J.D.Graybeal, F.J.Lovas, and R.D.Suenram, J.Mol.Spectrosc. 153,261(1992).


[2] J.Brunvoll and I.Hargittal, J.Chem.Soc. Dalton Trans, 299-302(1978).






















Methane Sulphonyl Chloride
Benzene Sulphonyl Chloride SO2ClF


HN=C=O
ClN=C=O






 









 









Table of Contents




Molecules/Chlorine




 








 













SO2ClNCO.html






Last Modified 26 May 2014