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CH2CClCN |
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Chlorine and Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in 2-Chloroacrylonitrile |
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Calculation of the chlorine and
nitrogen nqcc's in 2-chloroacrylonitrile was made on a molecular structure
derived ab initio (see below).
These nqcc's are compared in Tables 1-4 with the experimental values of
Kisiel and Pszczólkowski [1]. Structure parameters are given
in Table 5. |
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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. 35Cl nqcc's
in CH2CClCN (MHz). |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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33.21 |
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31.8093(13) |
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Xbb |
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- 1.39 |
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- 3.1730(16) |
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Xcc |
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34.60 |
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34.9823(16) |
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|Xab| |
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57.20 |
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57.173(12) |
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RMS |
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1.33 (5.7 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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42.07 |
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41.447(12) |
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Xyy |
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34.60 |
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34.982(2) |
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Xzz |
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76.67 |
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76.430(12) |
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ETA |
- |
0.097 |
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0.0846(2) |
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Øz,a |
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37.23 |
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37.970(2) |
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Øa,CCl |
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38.17 |
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38.17 * |
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Øz,CCl |
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0.95 |
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0.20 * |
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* Calculated here. |
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Table 2. 37Cl nqcc's
in CH2CClCN (MHz). |
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Calc. |
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Expt. [1] |
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37Cl |
Xaa |
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27.68 |
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26.6099(25) |
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Xbb |
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0.40 |
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- 0.9497(35) |
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Xcc |
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27.27 |
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27.5596(35) |
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|Xab| |
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44.64 |
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44.70(15) |
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RMS |
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1.01 (5.5 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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33.16 |
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32.73(15) |
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Xyy |
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27.27 |
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27.56(1) |
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Xzz |
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60.43 |
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60.29(15) |
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ETA |
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0.097 |
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0.086(2) |
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Øz,a |
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36.27 |
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36.99 |
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Øa,CCl |
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37.22 |
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37.22 * |
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Øz,CCl |
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0.95 |
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0.23 * |
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* Calculated here. |
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Table 3. Nitrogen nqcc's
in CH2C35ClCN (MHz). |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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3.087 |
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3.0609(19) |
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Xbb |
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1.073 |
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1.0228(20) |
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Xcc |
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2.014 |
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2.0380(20) |
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|Xab| |
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2.621 |
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2.611(12) |
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RMS |
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0.036 (1.7 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.339 |
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2.296(10) |
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Xyy |
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2.014 |
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2.038(2) |
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Xzz |
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4.352 |
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4.336(10) |
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ETA |
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0.075 |
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0.060(2) |
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Øz,a |
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25.78 |
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25.99(7) |
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Øa,CN |
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26.32 |
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26.32 * |
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Øz,CN |
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0.54 |
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0.33 * |
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* Calculated here. |
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Table 4. Nitrogen nqcc's
in CH2C37ClCN (MHz). |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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2.998 |
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2.9691(33) |
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Xbb |
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0.984 |
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0.9329(33) |
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Xcc |
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2.014 |
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2.0362(33) |
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|Xab| |
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2.689 |
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RMS |
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0.036 (1.8 %) |
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RSD |
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0.030 (1.3 %) |
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Molecular Structure |
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The molecular structure was optimized
at the MP2/6-311G(d,p) level of theory assuming Cs symmetry.
The optimized C=C, C-CN, and CN bond lengths were
corrected using equations obtained from linear regression analyses
of the data given in Tables VIII and IX of Ref.[2]. For the CCl
bond, the structure was optimized at the MP2/6-311+G(2d,p) level and corrected
by linear regression analysis of the data given in Table 4 of Ref.[3].
The CH bond lengths were corrected using r = 1.001 ropt,
where ropt is obtained by MP2/6-31G(d,p) optimization [4].
Interatomic angles used in the calculation are those given by MP2/6-311+G(d,p)
optimization. |
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| Table 5. Structure parameters (Å and degrees). |
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and Ht are with respect to Cl. CN tilts away from Cl. |
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C(1)Cl |
1.723 |
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C=C |
1.334 |
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C=CCl |
122.7 |
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C(1)C |
1.431 |
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CN |
1.158 |
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C=CC |
122.0 |
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C(1)CN |
179.8 |
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C(2)Hc |
1.080 |
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C(2)Ht |
1.081 |
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CCHc |
120.8 |
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CCHt |
119.7 |
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[1] Z.Kisiel and L.Pszczólkowski,
J.Mol.Spectrosc. 184,215(1997). |
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[2] J.Demaison, J.Cosléou, R.Bocquet,
and A.G.Lesarri, J.Mol.Spectrosc. 167,400(1994). |
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[3] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou,
and J.Demaison, J.Mol.Spectrosc. 177,232(1996). |
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[4] J.Demaison and G.Wlodarczak, Structural
Chem. 5,57(1994). |
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CH2CHCN |
CH2C(CN)2 |
CH2CHCl |
CH2CCl2 |
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Table of Contents |
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Molecules/Chlorine |
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Molecules/Nitrogen |
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CH2CClCN.html |
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Last
Modified 28 Sept 2005 |
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