OC2H3CH2Cl













 








Chlorine


Nuclear Quadrupole Coupling Constants

in (Chloromethyl)oxirane


 








 








Complete nqcc tensors were determined by Heineking et al. [1] for both 35Cl and 37Cl in the two conformers of (chloromethyl)oxirane shown below:

 








CMO gauche I

CMO gauche II































 








Calculation of the nqcc's was made here on molecular structures obtained by MP2/6-311+G(d,p) optimization.  These are compared with the experimental nqcc's in Tables 1 and 2.  Structure parameters are given in Table 3, atomic coordinates in Table 4, and rotational constants in Table 5.

 








In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Øz,CCl (degrees) is the angle between the principal z-axis of the nqcc tensor and the CCl bond axis.  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 nqcc's.

 








 








   







Table 1.  Chlorine nqcc's in CMO, gauche I (MHz).  Calculation was made on the MP2/6-311+G(d,p) optimized structure.
   










Calc.
Expt. [1]
   







35Cl Xaa - 37.13 - 38.193(3)


Xbb
  2.65
  4.0835


Xcc
34.48
34.1095


Xab * - 50.82 - 49.79(9)


Xac *
11.72
12.13(90)


Xbc *
  9.08
  8.87(29)

   






RMS
1.05 (4.1 %)




RSD
0.49 (1.1 %)



 







Xxx
35.94
35.81(78)


Xyy
37.90
37.43(66)


Xzz - 73.84 - 73.24(34)


ETA
0.027




Øz,CCl
0.45



 






37Cl Xaa
29.50 - 30.326(3)


Xbb
  2.32
  3.431


Xcc
27.18
26.895


Xab * - 39.96 - 39.13(4)


Xac *
  9.24
  9.04(48)


Xbc *
  7.12
  7.12(33)

 







RMS
0.81 (4.0 %)




RSD
0.44 (1.1 %)



 







Xxx
28.32
27.77(56)


Xyy
29.87
29.84(51)


Xzz - 58.19 - 57.62(19)


ETA
0.027




Øz,CCl
0.45



 







 








* The algebraic signs of the off-diagonal components depend on the orientation of the molecule with respect to the positive/negative sense of the a,b,c axes.  Here, the algebraic signs correspond to the atomic a,b,c coordinates given in Table 4.

 








   







Table 2.  Chlorine nqcc's in CMO, gauche II (MHz).  Calculation was made on the MP2/6-311+G(d,p) optimized structure.
   










Calc.
Expt. [1]
   







35Cl Xaa - 41.39 - 41.0538(13)


Xbb
  8.20
  8.0246


Xcc
33.19
33.0292


Xab * - 47.26 - 46.91(4)


Xac *
15.58
15.17(24)


Xbc *
10.39
10.07(10)

   






RMS
0.24 (0.87 %)




RSD
0.49 (1.1 %)



 







Xxx
35.80
35.53(25)


Xyy
37.46
37.05(20)


Xzz - 73.26 - 72.59(12)


ETA
0.023




Øz,CCl
0.30



 






37Cl Xaa
32.84
32.5791(23)


Xbb
  6.66
  6.53155


Xcc
26.18
26.04755


Xab * - 37.15 - 36.85(2)


Xac *
12.26
12.13(32)


Xbc *
  8.13
  7.77(20)

 







RMS
0.18 (0.85 %)




RSD
0.44 (1.1 %)



 







Xxx
28.21
27.13(40)


Xyy
29.52
31.19(36)


Xzz - 57.74 - 58.32(19)


ETA
0.023




Øz,CCl
0.30



 







 








 

Table 3.  Heavy atom structure parameters, MP2/6-311+G(d,p) ropt (Å and degrees).  Complete molecular structure parameters are given here in Z-matrix format.
 

CMO gauche I


C(1)C(2) 1.4699
C(2)O 1.4301
OC(1) 1.4377
C(2)C(7) 1.4966
C(7)Cl 1.7843
OC(2)C(1)   59.42
C(2)C(1)O   58.91
C(1)OC(2)   61.67
C(1)C(2)C(7) 120.41
C(2)C(7)Cl 110.42
H(6)C(2)C(7)Cl   57.79
 

 

CMO gauche II

C(1)C(2) 1.4652
C(2)O 1.4343
OC(1) 1.4420
C(2)C(7) 1.5005
C(7)Cl 1.7845
OC(2)C(1)   59.64
C(2)C(1)O   59.12
C(1)OC(2)   61.25
C(1)C(2)C(7) 120.66
C(2)C(7)Cl 109.54
H(6)C(2)C(7)Cl   60.55


 








 
















Table 4.  (Chloromethyl)oxirane.  Heavy atom coordinates, ropt.  35Cl species.
 






CMO gauche I
  a (Å)
  b (Å)
  c (Å)









C(1)
2.2098
0.3499 - 0.0501

C(2)
0.8494
0.1964
0.4848

O
1.4918 - 0.8877 - 0.1914

C(7) - 0.3164
0.8158 - 0.2204

Cl - 1.7821 - 0.1751
0.0111
 






CMO gauche II














C(1) - 1.6734
0.9014
0.2028

C(2) - 0.8158 - 0.0850 - 0.4591

O - 2.1228 - 0.4539
0.0020

C(7)
0.3175 - 0.7328
0.2810

Cl
1.8252
0.1707 - 0.0266


 








 













Table 5. (Chloromethyl)oxirane.  Rotational constants (MHz).  35Cl species.








Calc., ropt       Expt. [1]






CMO gauche I A 13 258.0 13 372.7536(16)


B   2 101.5   2 080.4258(5)


C   1 947.3   1 932.4577(4)

 



CMO gauche II A 13 202.5 13 143.9390(6)


B   2 029.0   2 031.06521(17)


C   1 889.4   1 889.75326(9)


 








 








[1] N.Heineking, J.-U.Grabow, and I.Merke, J.Mol.Struct. 612,231(2002).

 









M.A.Mohammadi and W.V.F.Brooks, J.Mol.Spectrosc. 78,89(1979).


 








 








(Chloromethyl)cyclopropane



 








 








Table of Contents




Molecules/Chlorine




 








 













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Last Modified 22 Jan 2006