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(CH3)2C2H2S
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Sulfur
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Nuclear
Quadrupole Coupling Constants |
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in 2,2-Dimethylthiirane |
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The diagonal components of the nqcc tensor for 33S in 2,2-dimethylthiirane were determined by Grabow et al. [1]. Heavy atom rs and ro structures were determined by Hartwig and Dreizler [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.
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Calculated and experimental nqcc
tensors are compared in Tables 1 - 4. Structure parameters are
given in Table 5. |
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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. |
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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. |
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Table 1. 33S nqcc's in 2,2-Dimethylthiirane (MHz). Calculation was made on the ro structure with CH parameters given by MP2/6-31G(d,p) partial optimization. |
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Calc [a] B3LYP/6-311G(3df,3p) model. |
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Calc [b] B3LYP/TZV+(3df,3p) model. |
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Calc. [a]
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Calc. [b] |
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Expt. [1] |
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Xaa |
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23.08 |
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23.20 |
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22.6390(23) |
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Xbb |
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47.85 |
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47.95 |
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47.1830(50) |
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Xcc |
- |
24.76 |
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24.75 |
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24.5440(50) |
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|Xac| |
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8.38 |
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8.35 |
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RMS |
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0.49 (1.5 %) |
0.56 (1.8 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
15.50 |
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15.59 |
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Xyy |
- |
32.34 |
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32.36 |
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Xzz |
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47.85 |
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47.95 |
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ETA |
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0.352 |
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0.350 |
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Øy,a |
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47.86 |
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47.66 |
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Øa,SC(2) |
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14.3 |
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14.3 |
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Øy,SC(2) |
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33.5 |
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33.3 |
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Øy,bi* |
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9.1 |
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8.9 |
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* The z-principal axis of the nqcc tensor is normal to the plane of the ring. The y-principal axis makes an angle of 9.6o/9.4o with the bisector ( bi ) of the CSC angle.
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Table 2. 33S nqcc's in 2,2-Dimethylthiirane (MHz). Calculation was made on the ro structure with CH parameters given by MP2/6-311+G(d,p) partial optimization. |
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Calc [a] B3LYP/6-311G(3df,3p) model. |
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Calc [b] B3LYP/TZV+(3df,3p) model. |
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Calc. [a]
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Calc. [b] |
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Expt. [1] |
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Xaa |
- |
23.16 |
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23.27 |
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22.6390(23) |
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Xbb |
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47.85 |
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47.95 |
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47.1830(50) |
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Xcc |
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24.69 |
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24.68 |
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24.5440(50) |
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|Xac| |
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8.39 |
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8.36 |
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RMS |
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0.49 (1.6 %) |
0.56 (1.8 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
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15.50 |
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15.59 |
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Xyy |
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32.34 |
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32.36 |
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Xzz |
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47.85 |
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47.95 |
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ETA |
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0.352 |
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0.350 |
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Øy,a |
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47.61 |
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47.41 |
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Øa,SC(2) |
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14.3 |
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14.3 |
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Øy,SC(2) |
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33.3 |
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33.1 |
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Øy,bi* |
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8.9 |
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8.7 |
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Table 3. 33S nqcc's in 2,2-Dimethylthiirane (MHz). Calculation was made on the rs structure with CH parameters given by MP2/6-31G(d,p) partial optimization. |
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Calc [a] B3LYP/6-311G(3df,3p) model. |
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Calc [b] B3LYP/TZV+(3df,3p) model. |
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Calc. [a]
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Calc. [b] |
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Expt. [1] |
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Xaa |
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22.50 |
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22.59 |
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22.6390(23) |
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Xbb |
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47.50 |
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47.60 |
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47.1830(50) |
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Xcc |
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25.00 |
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25.00 |
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24.5440(50) |
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|Xac| |
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9.55 |
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9.52 |
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RMS |
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0.33 (1.0 %) |
0.36 (1.1 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
14.12 |
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14.20 |
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Xyy |
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33.39 |
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33.40 |
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Xzz |
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47.50 |
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47.60 |
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ETA |
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0.406 |
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0.403 |
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Øy,a |
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48.73 |
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48.61 |
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Øa,SC(2) |
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15.0 |
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15.0 |
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Øy,SC(2) |
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33.7 |
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33.6 |
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Øy,bi* |
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9.7 |
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9.6 |
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Table 4. 33S nqcc's in 2,2-Dimethylthiirane (MHz). Calculation was made on the rs structure with CH parameters given by MP2/6-311+G(d,p) partial optimization. |
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Calc [a] B3LYP/6-311G(3df,3p) model. |
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Calc [b] B3LYP/TZV+(3df,3p) model. |
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Calc. [a]
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Calc. [b] |
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Expt. [1] |
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Xaa |
- |
22.60 |
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22.69 |
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22.6390(23) |
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Xbb |
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47.50 |
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47.59 |
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47.1830(50) |
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Xcc |
- |
24.89 |
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24.90 |
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24.5440(50) |
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|Xac| |
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9.58 |
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9.55 |
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RMS |
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0.27 (0.87 %) |
0.31 (0.99 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
14.10 |
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14.18 |
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Xyy |
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33.40 |
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33.41 |
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Xzz |
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47.50 |
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47.59 |
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ETA |
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0.406 |
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0.404 |
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Øy,a |
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48.41 |
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48.29 |
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Øa,SC(2) |
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15.05 |
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15.05 |
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Øy,SC(2) |
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33.4 |
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33.2 |
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Øy,bi* |
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9.4 |
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9.3 |
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| Table 5. 2,2-Dimethylthiirane. Heavy atom structure parameters, ro and rs [2] (Å and degrees). Complete structures are given here in Z-matrix format. |
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ro |
rs |
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C(4)C(2) |
1.509(4) |
1.518 |
| C(2)C(3) |
1.513(10) |
1.478 |
| SC(2) |
1.838(16) |
1.820 |
| SC(3) |
1.821(7) |
1.822 |
| C(4)C(2)C(3) |
116.8(5) |
117.8 |
| C(4)C(2)S |
116.0(4) |
116.2 |
| C(2)C(3)S |
66.2(4) |
66.0 |
| SC(2)C(3) |
65.0(3) |
66.1 |
| C(2)SC(3) |
48.8 |
47.9 |
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[1] J.-U.Grabow, M.Onda, and H.Dreizler, Z.Naturforsch. 51a,1110(1996). |
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[2] H.Hartwig and H.Dreizler, Z.Naturforsch. 48a,1102(1993). |
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Related ... |
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B.Kirchner, H.Huber, G.Steinebrunner, H.Dreizler, J.-U.Grabow, and I.Merke, Z.Naturforsch. 52a,297(1997).
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Thiirane |
Methylthiirane |
t-2,3-Dimethylthiirane |
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Ethylene Oxide |
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Table of Contents |
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Molecules/Sulfur |
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22MeThiirane.html |
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Last
Modified 11 April 2006 |
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