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(CH3)2C2H2S
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Sulfur
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Nuclear
Quadrupole Coupling Constants |
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in trans-2,3-Dimethylthiirane |
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The diagonal components of the nqcc tensor for 33S in t-2,3-dimethylthiirane were determined by Grabow and Dreizler [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 t-2,3-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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8.45 |
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8.42 |
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8.3871(93) |
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Xbb |
- |
32.90 |
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32.88 |
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32.3291(174) |
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Xcc |
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24.45 |
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24.46 |
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23.9420(174) |
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|Xac| |
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29.07 |
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29.12 |
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RMS |
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0.44 (2.1 %) |
0.44 (2.0 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
13.70 |
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13.77 |
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Xyy |
- |
32.90 |
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32.88 |
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Xzz |
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46.61 |
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46.65 |
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ETA |
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0.412 |
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0.410 |
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Øz,a |
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52.69 |
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52.70 |
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Øa,n* |
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54.45 |
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54.45 |
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Øz,n |
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1.76 |
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1.75 |
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Øy,bi* |
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0 |
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0 |
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* n is normal to CSC-plane, bi is bisector of CSC-angle.
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Table 2. 33S nqcc's in t-2,3-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 |
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8.36 |
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8.33 |
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8.3871(93) |
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Xbb |
- |
32.94 |
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32.92 |
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32.3291(174) |
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Xcc |
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24.58 |
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24.58 |
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23.9420(174) |
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|Xac| |
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29.02 |
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29.07 |
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RMS |
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0.51 (2.4 %) |
0.50 (2.3 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
13.66 |
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13.72 |
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Xyy |
- |
32.94 |
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32.92 |
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Xzz |
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46.60 |
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46.64 |
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ETA |
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0.414 |
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0.412 |
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Øz,a |
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52.81 |
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52.81 |
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Øa,n* |
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54.44 |
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54.44 |
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Øz,n |
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1.63 |
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1.63 |
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Øy,bi* |
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0 |
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0 |
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Table 3. 33S nqcc's in t-2,3-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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9.25 |
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9.21 |
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8.3871(93) |
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Xbb |
- |
33.18 |
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33.15 |
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32.3291(174) |
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Xcc |
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23.93 |
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23.94 |
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23.9420(174) |
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|Xac| |
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28.86 |
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28.91 |
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RMS |
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0.70 (3.2 %) |
0.67 (3.1 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
13.19 |
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13.26 |
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Xyy |
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33.18 |
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33.15 |
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Xzz |
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46.37 |
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46.40 |
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ETA |
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0.431 |
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0.429 |
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Øz,a |
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52.14 |
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52.14 |
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Øa,n* |
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53.97 |
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53.97 |
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Øz,n |
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1.83 |
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1.83 |
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Øy,bi* |
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0 |
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0 |
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Table 4. 33S nqcc's in t-2,3-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 |
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9.16 |
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9.13 |
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8.3871(93) |
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Xbb |
- |
33.22 |
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33.19 |
- |
32.3291(174) |
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Xcc |
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24.06 |
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24.06 |
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23.9420(174) |
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|Xac| |
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28.80 |
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28.85 |
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RMS |
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0.69 (3.2 %) |
0.66 (3.0 %) |
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RSD |
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0.39 (1.7 %) |
0.35 (1.5 %) |
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Xxx |
- |
13.14 |
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13.21 |
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Xyy |
- |
33.22 |
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33.19 |
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Xzz |
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46.36 |
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46.40 |
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ETA |
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0.433 |
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0.431 |
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Øz,a |
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52.25 |
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52.25 |
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Øa,n* |
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53.96 |
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53.96 |
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Øz,n |
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1.71 |
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1.71 |
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Øy,bi* |
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0 |
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0 |
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| Table 5. t-2,3-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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| Point Group: C2 |
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ro |
rs |
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C(4)C(2) |
1.509(6) |
1.514(3) |
| C(2)C(3) |
1.467(2) |
1.487(9) |
| SC(2,3) |
1.830(3) |
1.822(2) |
| C(4)C(2)C(3) |
120.93(13) |
120.70(30) |
| C(4)C(2)S |
118.02(32) |
117.83(17) |
| C(2)C(3)S |
66.02(13) |
66.26(10) |
| C(2)SC(3) |
47.96(25) |
47.49(7) |
| C(4)C(2)C(3)S |
109.44(20) |
109.39(17) |
| C(4)C(2)C(3)C(5) |
141.12(40) |
141.23(19) |
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[1] J.-U.Grabow and H.Dreizler, Z.Naturforsch. 51a,1107(1996). |
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[2] H.Hartwig and H.Dreizler, Z.Naturforsch. 51a,1099(1996). |
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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 |
2,2-Dimethylthiirane |
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Ethylene Oxide |
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Table of Contents |
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Molecules/Sulfur |
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23MeThiirane.html |
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Last
Modified 12 April 2006 |
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