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Isothiazole
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PDF
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Nitrogen and Sulfur
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Nuclear
Quadrupole Coupling Constants |
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in Isothiazole |
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Calculation of the 14N and 33S
nqcc's in isothiazole was made on a structure obtained by mPW1PW91/aug-cc-pVTZ
(G03) optimization. These are compared with the experimental
nqcc's of Gripp et al. [1] in Tables 1 - 4. Structure parameters are
given in Table 5, atomic coordinates in Table 6. |
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In Tables 1 and 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.
The nqcc y-axis is chosen coincident with the inertia c-axis, these
are perpendicular to the plane of the molecule. 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 stand deviation
of calibration of the model for calculation of
the nqcc's. |
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Table 1. Nitrogen
nqcc's in Isothiazole-33S (MHz). Calculation was made
on the mPW1PW91/aug-cc-pVTZ ropt structure. |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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1.103 |
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1.0732(19) |
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Xbb |
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2.397 |
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2.4753(46) |
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Xcc |
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1.294 |
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1.4021 |
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|Xab| |
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2.919 |
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RMS |
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0.079 (4.8 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.756 |
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Xyy |
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1.294 |
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Xzz |
- |
4.050 |
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ETA |
- |
0.361 |
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Øz,a |
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60.47 |
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Øa,bi |
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75.84 |
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Øz,bi* |
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15.37 |
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* Angle between the z-axis and the bisector ('bi') of
the CNC angle.
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Table 2. Nitrogen
nqcc's in Isothiazole-32S (MHz). Calculation was made
on the mPW1PW91/aug-cc-pVTZ ropt structure. |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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1.095 |
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1.0668(47) |
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Xbb |
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2.388 |
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2.465 |
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Xcc |
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1.294 |
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1.398 |
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|Xab| |
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2.924 |
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RMS |
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0.075 (4.6 %) |
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RSD |
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0.030 (1.3 %) |
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Table 3. Nitrogen
nqcc's in Isothiazole-34S (MHz). Calculation was made
on the mPW1PW91/aug-cc-pVTZ ropt structure. |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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1.111 |
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1.0807(15) |
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Xbb |
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2.404 |
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2.478 |
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Xcc |
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1.294 |
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1.397 |
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|Xab| |
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2.914 |
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RMS |
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0.075 (4.6 %) |
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RSD |
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0.030 (1.3 %) |
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Table 4.
33S nqcc's in Isothiazole (MHz). Calculation was made
on the mPW1PW91/aug-cc-pVTZ ropt structure. |
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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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8.75 |
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8.78 |
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8.7015(57) |
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Xbb |
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33.03 |
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33.16 |
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32.9696(60) |
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Xcc |
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24.28 |
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24.38 |
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24.2681 |
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|Xab| |
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5.45 |
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5.66 |
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RMS |
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0.05 (0.2 %) |
0.13 (0.6 %) |
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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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9.45 |
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9.53 |
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9.43 * |
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Xyy |
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24.28 |
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24.38 |
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24.2681 |
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Xzz |
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33.73 |
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33.91 |
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33.70 |
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ETA |
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0.440 |
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0.438 |
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0.440 |
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Øx,a |
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7.31 |
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7.54 |
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7.46 |
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Øa,bi |
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2.03 |
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2.03 |
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2.03 |
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Øx,bi** |
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9.34 |
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9.57 |
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9.49 |
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* Calculated here from the experimental diagonal nqcc's and 5.55 MHz for |Xab|. |
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** Angle between the x-axis and the bisector ( 'bi' ) of
the CSN angle. |
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| Table 5. Molecular structure parameters, mPW1PW91/aug-cc-pVTZ ropt (Å and degrees). |
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SN |
1.6481 |
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NC(3) |
1.3116 |
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C(3)C(4) |
1.4137 |
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C(4)C(5) |
1.3643 |
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C(5)S |
1.6998 |
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C(3)H(3) |
1.0823 |
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C(4)H(4) |
1.0787 |
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C(5)H(5) |
1.0777 |
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C(5)SN |
95.42 |
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SNC(3) |
108.84 |
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NC(3)C(4) |
116.82 |
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C(3)C(4)C(5) |
110.10 |
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C(4)C(5)S |
108.83 |
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NC(3)H(3) |
118.40 |
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C(3)C(4)H(4) |
124.94 |
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C(4)C(5)H(5) |
128.62 |
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| Table 6. Atomic coordinates,
mPW1PW91/aug-cc-pVTZ ropt, normal species. |
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than are significant.) |
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a (Å) |
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b (Å) |
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S |
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1.095257 |
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0.035142 |
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N |
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0.031981 |
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1.224068 |
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C |
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1.189694 |
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0.746784 |
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C |
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1.324738 |
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0.660423 |
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C |
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0.094118 |
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1.249450 |
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H |
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2.015659 |
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1.446129 |
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H |
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2.264028 |
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1.190886 |
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H |
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0.149158 |
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2.299343 |
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[1] J.Gripp, U.Kretschmer, and H.Dreizler,
Z.Naturforsch. 49a,1059(1994).
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J.Wiese and D.H.Sutter, Z.Naturforsch. 35a,712(1980): Xaa = 1.037(23), Xbb = -2.404(27), Xcc = 1.367(27) MHz. |
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1,2,4-Thiadiazole |
1,2,5-Thiadiazole |
1,3,4-Thiadiazole |
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Thiazole |
Oxazole |
Isoxazole |
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Thiophene |
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Table of Contents |
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Molecules/Nitrogen |
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Molecules/Sulfur |
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Isothiazole.html |
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Last
Modified 10 Feb 2005 |
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