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p-CH3-C6H4-Cl
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Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in
p-Chlorotoluene |
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Chlorine nqcc's were calculated here
on a molecular structure determined by B3P86/6-31G(3d,3p) optimization,
assuming a plane of symmetry
perpendicular to the plane of the ring. These are compared with
the
experimental nqcc's [1] in Table 1. Structure parameters are
given
in Table 2, atomic coordinates in Table 3. |
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In Table 1, 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 inertial b-axis, these are perpendicular to the
symmetry 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 diagonal
nqcc's. RSD is the calibration residual standard deviation
for the B1LYP/TZV(3df,2p) model for calculation of the nqcc's. |
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Table 1. Chlorine nqcc's
in p-Chlorotoluene (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
- |
71.73 |
- |
71.155(5) |
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Xbb |
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38.63 |
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37.979(7) *
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Xcc |
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33.10 |
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33.176(7) *
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|Xac| |
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0.22 |
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RMS
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0.45 (0.94 %)
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RSD |
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0.49 (1.1 %) |
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Xxx |
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33.10 |
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37.979(7) |
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Xyy |
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38.63 |
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33.176(7) |
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Xzz |
- |
71.73 |
-
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71.155(5)
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ETA |
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0.077 |
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Øz,a |
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0.12 |
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Øa,CCl |
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0.11 |
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Øz,CCl |
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0.01 |
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37Cl |
Xaa |
- |
56.53 |
- |
56.069(7) |
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Xbb |
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30.45 |
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29.909(9) **
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Xcc |
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26.08 |
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26.160(9) **
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|Xac| |
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0.17 |
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RMS
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0.41 (1.1 %)
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RSD |
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0.44 (1.1 %) |
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*
Calculated here from experimental Xaa and Xbb - Xcc
= 4.802(13) MHz. |
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**
Calculated here from experimental Xaa and Xbb - Xcc
= 3.749(16) MHz. |
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| Table 2. p-Chlorotoluene.
Molecular structure parameters, ropt (Å and
degrees). |
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Ring |
C(1)C(2) |
1.3953 |
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C(2)C(3) |
1.3889 |
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C(3)C(4) |
1.3885 |
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C(4)Cl |
1.7370 |
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C(2)H(2) |
1.0860 |
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C(3)H(3) |
1.0835 |
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C(6)C(1)C(2) |
117.99 |
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C(1)C(2)C(3) |
121.47 |
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C(2)C(3)C(4) |
119.12 |
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C(3)C(4)C(5) |
120.81 |
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C(1)C(2)H(2) |
119.49 |
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C(2)C(3)H(3) |
120.92 |
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Methyl |
C(1)C(7) |
1.5021 |
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C(7)H(8) |
1.0953 |
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C(7)H(9,10) |
1.0923 |
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C(1)C(7)H(8) |
111.06 |
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C(1)C(7)H(9,10) |
111.39 |
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| Table 4. p-Chlorotoluene.
Atomic coordinates, ropt. Normal species. |
| (More figures are shown than
are significant.) |
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a (Å) |
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b (Å) |
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c (Å) |
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C(1) |
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1.918136 |
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0.0 |
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0.008982 |
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C(2,6) |
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1.199437 |
± |
1.195973 |
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0.008869 |
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C(3,5) |
- |
0.189441 |
± |
1.207376 |
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0.003133 |
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C(4) |
- |
0.875142 |
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0.0 |
- |
0.001172 |
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Cl |
- |
2.612126 |
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0.0 |
- |
0.004485 |
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H(2,6) |
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1.734315 |
± |
2.141093 |
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0.015538 |
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H(3,5) |
- |
0.738499 |
± |
2.141458 |
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0.005346 |
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C(7) |
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3.420029 |
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0.0 |
- |
0.015294 |
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H(8) |
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3.797132 |
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0.0 |
- |
1.043616 |
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H(9,10) |
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3.826472 |
± |
0.884469 |
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0.480401 |
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[1]
V.A.Shubert, D.Schmitz, and M.Schnell, Mol.Phys. 111,2189(2013). |
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G.E.Herberich, Z.Naturforsch.
22a,761(1967): Xaa(35Cl)
= -71.7(7) and Xaa(37Cl)
= -56.6(13) MHz
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o-Chlorotoluene |
Chlorobenzene |
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p-Bromotoluene
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p-Iodotoluene
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Table of Contents
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Molecules/Chlorine |
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4ClToluene.html |
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Last
Modified 5 Aug 2013 |
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