CH3CH2-S-CH2CH2Cl


 
 
 


Chlorine


Nuclear Quadrupole Coupling Constants

in 2-Chloroethyl ethyl sulfide


 







 

 


 




Complete nqcc tensors for both 35Cl and 37Cl in both GGT and TGT structural conformations of 2-chloroethyl ethyl sulfide (CEES) have been determined by Tubergen et al. [1].
 
Calculation was made here of the nqcc tensors on PBE1PBE/6-311+G(3d,3p) optimized molecular structures of these two conformers.  Calculated and experimental nqcc's are compared in Tables 1 - 4.  Heavy atom structure parameters and atomic coordinates respectively are given in Tables 5 and 6.  Rotational constants are compared in Table 7.
 
           GGT/CEES I         TGT/CEES II

 
 
In Tables 1 - 4, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Ø (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.  35Cl nqcc's in 2-Chloroethyl ethyl sulfide (MHz).  Calculation was made on the PBE1PBE/6-311+G(3d,3p) optimized structure of the GGT conformer.  Expt. = CEES I.
   






 


Calc.
Expt. [1]

   







35Cl Xaa - 45.42 - 44.8247(15)
 
Xbb
20.70

20.8456(13)

Xcc 24.72 23.9791(20)
Xab * - 35.29 - 34.345(4)
Xac 28.29 29.093(18)
Xbc 12.72 12.77(4)
  
RMS 0.56 (1.9 %)
RSD 0.49 (1.1 %)
  
Xxx 34.67 34.602(17) **
Xyy 36.12 35.618(21)
 
Xzz -
70.79
-
70.220(14)

ETA 0.0204 0.0145(4)
Øz,CCl 0.28 0.96
   
 
* Algebraic signs of the off-diagonal nqcc's depend on the positive/negative sense of the inertial axes, which choice is arbitrary.  The signs given here correspond to the a,b,c coordinates defined in Table 6.  As for the algebraic signs of the experimental components, only the algebraic sign of the product XabXacXbc can be determined, which is reported as negative [1].  I have taken the liberty of signing these to correspond to the calculated nqcc's.
** Calculated here with Z.Kisiel's QDIAG.f [2].
These notes apply also to Tables 2 - 4.
 
 
   







Table 2.  37Cl nqcc's in 2-Chloroethyl ethyl sulfide (MHz).  Calculation was made on the PBE1PBE/6-311+G(3d,3p) optimized structure of the GGT conformer.  Expt. = CEES I.
   






 


Calc.
Expt. [1]

   







37Cl Xaa - 36.06 - 35.589(4)
 
Xbb
16.55

16.6635(28)

Xcc 19.50 18.926(5)
Xab * - 27.59 - 26.84(5)
Xac 22.31 23.00(8)
Xbc   9.92   9.98(4)
  
RMS 0.43 (1.8 %)
RSD 0.44 (1.1 %)
  
Xxx 27.33 27.304(60) **
Xyy 28.47 28.075(36)
 
Xzz -
55.79
-
55.378(56)

ETA 0.0204 0.0139(13)
Øz,CCl 0.28 0.99
   
 
 
   







Table 3.  35Cl nqcc's in 2-Chloroethyl ethyl sulfide (MHz).  Calculation was made on the PBE1PBE/6-311+G(3d,3p) optimized structure of the TGT conformer.  Expt. = CEES II.
   






 


Calc.
Expt. [1]

   







35Cl Xaa - 57.40 - 56.661(2)
 
Xbb
34.57

34.289(18)

Xcc 22.83 22.372(18)
Xab * 11.18 10.31(4)
Xac - 33.54 - 33.70(8)
Xbc   3.41   3.2(16)
  
RMS 0.52 (1.4 %)
RSD 0.49 (1.1 %)
  
Xxx 34.69 34.46(134) **
Xyy 36.18 35.73(123)
 
Xzz -
70.86
-
70.19(12)

ETA 0.0210 0.018(26)
Øz,CCl 0.29 0.79
   
 
 
   







Table 4.  37Cl nqcc's in 2-Chloroethyl ethyl sulfide (MHz).  Calculation was made on the PBE1PBE/6-311+G(3d,3p) optimized structure of the TGT conformer.  Expt. = CEES II.
   






 


Calc.
Expt. [1]

   







37Cl Xaa - 45.32 - 44.757(18)
 
Xbb
27.29

27.079(9)

Xcc 18.02 17.678(20)
Xab *   8.61   7.88(7)
Xac - 26.40 - 26.66(5)
Xbc   2.61   0.4(4)
  
RMS 0.40 (1.3 %)
RSD 0.44 (1.1 %)
  
Xxx 27.34 25.29(39) **
Xyy 28.51 29.99(36)
 
Xzz -
55.85
-
55.281(45)

ETA 0.0210 0.0849(96)
Øz,CCl 0.29 1.20
   
 
 
 
Table 5.   2-Chloroethyl ethyl sulfide.  Heavy atom molecular structure parameters (Å and degrees).  See Z-Matrices for complete structure parameters.
 
 GGT  TGT
  Z-Matrix GGT
ClC(4) 1.7934 1.7930
C(4)C(3) 1.5114 1.5116
  Z-Matrix TGT C(3)S 1.8074 1.8062
SC(2) 1.8129 1.8130
C(2)C(1) 1.5172 1.5180
ClC(4)C(3) 110.84 110.82
C(4)C(3)S 111.46 111.90
C(3)SC(2) 101.64 101.02
SC(2)C(1) 114.42 109.28


 
 
Table 6.   2-Chloroethyl ethyl sulfide.  Heavy atom atomic coordinates.  (More figures are shown than are significant.)
 
  a (Å)   b (Å)   c (Å)
GGT Cl 2.749287 0.369985 - 0.027207
C 1.182246 - 0.310299 0.518452
C 0.192132 - 0.362099 - 0.622322
S - 1.402305 - 1.022067 - 0.084770
C - 2.165977 0.437733 0.671912
C - 2.647051 1.479643 - 0.320540
 
TGT Cl 2.895356 - 0.313137 0.057306
C 1.217978 - 0.110336 - 0.542846
C 0.375673 0.643557 0.460771
S - 1.325643 0.852168 - 0.108874
C - 2.020034 - 0.779534 0.268245
C - 3.495090 - 0.791504 - 0.090088
 
 
Table 7.  2-Chloroethyl ethyl sulfide.  Rotational Constants (MHz).  35Cl Species.
 
  Calc. ropt   Expt. [1] Calc. ropt   Expt. [1]
GGT   CEES I TGT   CEES II
A 4611.2 4550.8330(4) 6846.8 6762.8209(11)
B   919.5   925.74787(8)   796.0   798.25329(15)
C   832.2   835.20092(7)   747.2   747.99297(14)
 
 

[1] M.J.Tubergen, A.Lesarri, R.D.Suenram, A.C.Samuels, J.O.Jensen, M.W.Ellzy, J.M.Lochner, J.Mol.Spectrosc. 233,180(2005).

[2] Z.Kisiel, PROSPE - Programs for ROtational SPEctroscopy, http://info.ifpan.edu.pl/~kisiel/prospe.htm.
 

 







CH3CH2Cl 1-Chloro-2-Fluoroethane 1-Chloropropane
CH3Cl 1-Chloro-1-Fluoroethane 2-Chloroethanol
 

 








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Last Modified 7 Jan 2006