CH3C2H3S

 

Sulfur

Nuclear Quadrupole Coupling Constants


in Methylthiirane


 







 
 
The diagonal components of the nqcc tensor for 33S in methylthiirane were determined by Lorenzo, Alonso, et al. [1].  Heavy atom rs and ro structures were determined by Lorenzo, López, et al. [2].  Calculation of the nqcc tensor was made here on these structures, each with CH parameters determined by MP2/6-31G(d,p) and MP2/6-311+G(d,p) partial optimization.
Calculated and experimental nqcc tensors are compared in Tables 1 - 4.  Structure parameters are given in Table 5.  Atomic coordinates in Table 6, and the eigenvectors (direction cosines) of the nqcc tensor in this coordinate system are given in Table 7.
 
In Tables 1 - 4, 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.  Ø (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.
RMS is the root mean square difference between calculated and experimental nqcc's (percentage of average experimental nqcc).  RSD is the residual standard deviation of calibration of the model for calculation of the nqcc's.
 
 
   






Table 1.  33S nqcc's in Methylthiirane (MHz).  Calculation was made on the ro structure with CH parameters given by MP2/6-31G(d,p) partial optimization.
   





Calc [a] B3LYP/6-311G(3df,3p) model.
Calc [b] B3LYP/TZV+(3df,3p) model.
 


Calc. [a]
Calc. [b]
Expt. [1]
   





Xaa - 12.67 - 12.68 - 12.7731(82)
Xbb - 20.44 - 20.44 - 20.3366(118)
Xcc 33.11 33.13 33.1097(273)
Xab* 15.89 15.86
Xac* 23.59 23.62
Xbc* 13.18 13.22
 
RMS 0.08 (0.38 %) 0.08 (0.36 %)
RSD 0.39 (1.7 %) 0.35 (1.5 %)
 
Xxx - 14.78 - 14.85
Xyy - 33.31 - 33.28
Xzz 48.09 48.13
ETA 0.385 0.383
Øz,n** 1.22 1.22
Øy,bi** 5.46 5.44
 
 
Here and in Tables 2 - 4,
* the algebraic signs of the off-diagonal nqcc's correspond to the atomic coordinate given in Table 6.  The product XabXacXbc, which is independent of coordinate system, is positive.
**  the z-principal axis makes an angle of Øz,n with the normal (n) to the C(2)33S(1)C(3) plane, the y-axis makes an angle of Øy,bi with the bisector (bi) of the C(2)33S(1)C(3) angle.
 
 
   






Table 2.  33S nqcc's in Methylthiirane (MHz).  Calculation was made on the ro structure with CH parameters given by MP2/6-311+G(d,p) partial optimization.
   





Calc [a] B3LYP/6-311G(3df,3p) model.
Calc [b] B3LYP/TZV+(3df,3p) model.
 


Calc. [a]
Calc. [b]
Expt. [1]
   





Xaa - 12.75 - 12.77 - 12.7731(82)
Xbb - 20.38 - 20.38 - 20.3366(118)
Xcc 33.13 33.15 33.1097(273)
Xab* 15.96 15.92
Xac* 23.52 23.55
Xbc* 13.16 13.20
 
RMS 0.03 (0.14 %) 0.03 (0.15 %)
RSD 0.39 (1.7 %) 0.35 (1.5 %)
 
Xxx - 14.68 - 14.75
Xyy - 33.37 - 33.34
Xzz 48.05 48.09
ETA 0.389 0.386
Øz,n** 1.15 1.14
Øy,bi** 5.32 5.30
 
 
 
   






Table 3.  33S nqcc's in Methylthiirane (MHz).  Calculation was made on the rs structure with CH parameters given by MP2/6-31G(d,p) partial optimization.
   





Calc [a] B3LYP/6-311G(3df,3p) model.
Calc [b] B3LYP/TZV+(3df,3p) model.
 


Calc. [a]
Calc. [b]
Expt. [1]
   





Xaa - 12.55 - 12.56 - 12.7731(82)
Xbb - 20.78 - 20.79 - 20.3366(118)
Xcc 33.33 33.34 33.1097(273)
Xab* 15.41 15.37
Xac* 23.27 23.29
Xbc* 13.08 13.12
 
RMS 0.31 (1.4 %) 0.32 (1.4 %)
RSD 0.39 (1.7 %) 0.35 (1.5 %)
 
Xxx - 14.94 - 15.01
Xyy - 32.94 - 32.90
Xzz 47.88 47.91
ETA 0.376 0.373
Øz,n** 1.06 1.06
Øy,bi** 6.62 6.63
 
 
 
   






Table 4.  33S nqcc's in Methylthiirane (MHz).  Calculation was made on the rs structure with CH parameters given by MP2/6-311+G(d,p) partial optimization.
   





Calc [a] B3LYP/6-311G(3df,3p) model.
Calc [b] B3LYP/TZV+(3df,3p) model.
 


Calc. [a]
Calc. [b]
Expt. [1]
   





Xaa - 12.64 - 12.64 - 12.7731(82)
Xbb - 20.72 - 20.72 - 20.3366(118)
Xcc 33.35 33.37 33.1097(273)
Xab* 15.47 15.43
Xac* 23.19 23.22
Xbc* 13.06 13.10
 
RMS 0.27 (1.2 %) 0.28 (1.3 %)
RSD 0.39 (1.7 %) 0.35 (1.5 %)
 
Xxx - 14.84 - 14.91
Xyy - 33.00 - 32.96
Xzz 47.84 47.87
ETA 0.380 0.377
Øz,n** 0.99 1.00
Øy,bi** 6.46 6.48
 
 
 
Table 5. Methylthiirane.  Heavy atom structure parameters, ro and rs [2] (Å and degrees).  Complete structures are given here in Z-matrix format.
 
    ro     rs

C(4)C(2) 1.5169(16) 1.5128(62)
C(2)C(3) 1.4846(28) 1.479(11)
SC(2) 1.8268(16) 1.8124(61)
SC(3) 1.8202(25) 1.8176(52)
C(4)C(2)C(3) 119.84(70) 119.96(55)
C(4)C(2)S 117.52(16) 118.22(28)
C(2)C(3)S   66.21(39)   65.78(97)
SC(2)C(3)   65.75(8)   66.14(97)
C(2)SC(3)   48.04(47)   48.08(95)
 
 
Table 6.  Methylthiirane, 33S species.  Heavy atom coordinates, ro / MP2/6-311+G(d,p).
 
a (Å) b (Å) c (Å)
S 1.0181 - 0.4258 - 0.0408
C(2) - 0.6196 0.1730 0.5041
C(3) 0.2135 1.2021 - 0.1675
C(4) - 1.8406 - 0.3871 - 0.2003
H(5) 0.6551 1.9858 0.4391
H(6) - 0.0773 1.4938 - 1.1726
H(7) - 0.6967 0.2606 1.5851
H(8) - 1.6527 - 0.4506 - 1.2754
H(9) - 2.0801 - 1.3880 0.1676
H(10) - 2.7050 0.2648 - 0.0306
 
 
[1] F.Lorenzo, J.L.Alonso, J.-U.Grabow, and H.Dreizler, Z.Naturforsch. 51a,1096(1996).
[2] F.J.Lorenzo, J.C.López, J.L.Alonso, and H.Dreizler, J.Chem.Soc., Faraday Trans., 93,1863(1997).
Related ...
B.Kirchner, H.Huber, G.Steinebrunner, H.Dreizler, J.-U.Grabow, and I.Merke, Z.Naturforsch. 52a,297(1997).

 







 
Thiirane 2,2-Dimethylthiirane t-2,3-Dimethylthiirane
Ethylene Oxide
 

 








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Last Modified 18 April 2006