CH2=NCl


















 





 








Chlorine and Nitrogen

Nuclear Quadrupole Coupling Constants

in N-Chloromethylenimine

 








 








 








35Cl nqcc's in CH2=NCl were determined by Sugie et al. [1].

 








Calculation of the chlorine - and nitrogen - nqcc tensors was made here on ropt structures given by MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimization.  These are compared with the experimental chlorine nqcc's in Table 1.  Calculated nitrogen nqcc's are given in Table 2.  Structure parameters are given in Table 3; rotational constants and dipole moments in Table 4; centrifugal distortion constants in Table 5.

 








In Tables 1 and 2, 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 subscripted parameters. 

RMS is the root mean square difference between calculated and experimental nqcc's (percentage of the average experimental nqcc).  RSD is the residual standard deviation of calibration of the model for calculation of the efg's/nqcc's (see Chlorine, Nitrogen).

 








 








 








Table 1.  Cl nqcc's in CH2=NCl (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized structures.
 










Calc (1)
Calc (2)
Expt [1]
 








Xaa (35Cl) - 72.04
 -
 72.07
 - 72.7(4)

Xbb
30.33
30.01
30.1(6)

Xcc
41.71
42.06
42.6(5)

|Xab|
49.44
49.68












RMS
0.65 (1.3 %)
0.48 (1.0 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xxx
50.31
50.19



Xyy
41.71
42.06



Xzz - 92.02
 -
 92.25



ETA -
 0.0934
 -
 0.0882



Øz,a
22.00
22.11



Øa,NCl
22.21
22.22



Øz,NCl
  0.21
  0.11












Xaa (37Cl) -
 56.94
 -
 56.96



Xbb
24.06
23.81



Xcc
32.87
33.15



|Xab|
38.80
38.98



 







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 








 








Table 2.  14N nqcc's in (CH3)2N35Cl (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ(G03) optimized structure.
 










Calc (1)
Calc (2)
Expt
 








Xaa
3.492
3.525



Xbb -
 4.962
 -
 4.923



Xcc
1.470
1.398



|Xab|
2.277
2.325












RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
4.066
4.123



Xyy
1.470
1.398



Xzz -
 5.536
 -
 5.521



ETA -
 0.469
 -
 0.494



Øz,a
75.85
75.58



Øa,NCl
22.21
22.22



Øz,NCl
98.06
97.80



 








 








 








 


Table 3.  CH2=NCl  Structure parameters (Å and degrees).  ropt(1) = MP2/6-311+G(3df,3pd) and ropt(2) = MP2/aug-cc-pVTZ optimized structure.
 




ropt(1)ropt(2)





C=N
 1.2769
 1.2785

NCl
 1.7252
 1.7391

C=NCl
 113.20
 112.59

CHc
 1.0856
 1.0857

CHt
 1.0829
 1.0836

N=CHc 124.50
 124.58

N=CHt 115.22
 115.12

 



 








 



Table 4.  CH3N35Cl  Rotational constants (MHz) and dipole moments (D):  ropt(1) = MP2/6-311+G(3df,3pd) and ropt(2) = MP2/aug-cc-pVTZ optimized structures.
 





  ropt(1)   ropt(2) Expt [1]






A   62960.
   61886.
 62434.90(10)

B     6737.
     6698.
   6676.389(13)

C     6086.
     6044.
   6022.843(11)






|µa|
   1.82
   1.87
 1.873(8)

|µb|   1.55
   1.56
 1.441(11)







 








 








 



Table 5.  CH3N35Cl  Quartic Centrifugal Distortion Constants (MHz).  Calc = B3LYP/cc-pVTZ.
 





  Calc   Expt [1]






Delta_J
 0.00398
 0.00403(13)

Delta_JK
 - 0.0131
 - 0.0160(33)

Delta_K
 1.618
 1.587(28)

delta_j
 0.000483
 0.0005167(59)

delta_k
 0.0264
 0.02736(23)







 








 








[1]  M.Sugie, H.Takeo, and C.Matsumura, J.Am.Chem.Soc. 111(3), 906(1989).

 








 








CH2=NH CF2=NCl
 NH2Cl (CH3)2NCl

 








 








Table of Contents




Molecules/Chlorine




Molecules/Nitrogen




 








 













CH2NCl.html






Last Modified 10 May 2016