|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
4-Cl-C6H4OH
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine, Hydroxyl Deuterium, and Oxygen
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in 4-Chlorophenol |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of chlorine, deuterium (OD),
and oxygen nqcc's in 4-chlorophenol was made on the B3P86/6-31G(3d,3p)
optimized molecular structure. These calculated coupling
constants are given in Tables 1-3. Structure parameters are given in Table
4, atomic coordinates in Table 5, and rotational constants in Table 6. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1-3, subscripts a,b,c
refer to the principal axes of the inertia tensor; 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
molecular plane. Ø (degrees) is the angle between its
subscripted parameters. ETA = (Xxx - Xyy)/Xzz. RSD is the calibration residual standard deviation for the model for calculation of the chlorine nqcc's.
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Chlorine
nqcc's in 4-Cl-C6H4OH (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
72.32 |
|
|
|
|
|
Xbb |
|
38.33 |
|
|
|
|
|
Xcc |
|
33.99 |
|
|
|
|
|
|Xab| |
|
0.19 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
38.33 |
|
|
|
|
|
Xyy |
|
33.99 |
|
|
|
|
|
Xzz |
- |
72.32 |
|
|
|
|
|
ETA |
- |
0.060 |
|
|
|
|
|
Øz,a |
|
0.10 |
|
|
|
|
|
Øa,CCl |
|
0.09 |
|
|
|
|
|
Øz,CCl |
|
0.01 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Deuterium
nqcc's in 4-Cl-C6H4OD (kHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
2H |
Xaa |
|
- 60.8 |
|
|
|
|
|
Xbb |
|
223.8 |
|
|
|
|
|
Xcc |
- |
163.0 |
|
|
|
|
|
|Xab| |
|
147.6 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
1.1 (0.86 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
123.5 |
|
|
|
|
|
Xyy |
- |
163.0 |
|
|
|
|
|
Xzz |
|
286.5 |
|
|
|
|
|
ETA |
|
0.138 |
|
|
|
|
|
Øz,a |
|
66.98 |
|
|
|
|
|
Øa,OD |
|
67.73 |
|
|
|
|
|
Øz,OD |
|
0.75 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
In solid 4-chlorophenol, Batchelder et al. [1] observed in the
pure nuclear quadrupole spectra (NQR) two pairs of deuteron lines corresponding
to two crystallographically inequivalent sites. The z-principal axis
coupling constants and asymmetry parameters for these are 217.43 kHz and 0.132,
and 210.37 kHz and 0.161. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 3. Oxygen nqcc's in 4-Cl-C6H4OH (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
17O |
Xaa |
- |
7.047 |
|
|
|
|
|
Xbb |
- |
1.856 |
|
|
|
|
|
Xcc |
|
8.903 |
|
|
|
|
|
|Xab| |
|
4.520 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.041 (1.4 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
0.760 |
|
|
|
|
|
Xyy |
|
8.903 |
|
|
|
|
|
Xzz |
- |
9.663 |
|
|
|
|
|
ETA |
|
0.843 |
|
|
|
|
|
Øz,a |
|
30.07 |
|
|
|
|
|
Øa,OH |
|
68.14 |
|
|
|
|
|
Øz,OH |
|
38.07 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 4. Molecular structure parameters, ropt (Å
and degrees). |
| |
|
|
|
|
|
C(4)Cl |
1.7366 |
C(3)C(4)Cl |
119.72 |
|
C(1)C(2) |
1.3928 |
C(1)C(2)C(3) |
120.22 |
|
C(2)C(3) |
1.3889 |
C(2)C(3)C(4) |
119.56 |
|
C(3)C(4) |
1.3879 |
C(3)C(4)C(5) |
120.56 |
|
C(4)C(5) |
1.3905 |
C(4)C(5)C(6) |
119.78 |
|
C(5)C(6) |
1.3862 |
C(5)C(6)C(1) |
120.05 |
|
C(6)C(1) |
1.3935 |
C(6)C(1)C(2) |
119.82 |
|
C(1)O(1) |
1.3585 |
C(2)C(1)O(1) |
122.75 |
|
O(1)H |
0.9620 |
C(1)O(1)H |
109.29 |
|
C(2)H(2) |
1.0867 |
C(1)C(2)H(2) |
120.09 |
|
C(3)H(3) |
1.0834 |
C(2)C(3)H(3) |
120.48 |
|
C(5)H(5) |
1.0834 |
C(4)C(5)H(5) |
119.79 |
|
C(6)H(6) |
1.0838 |
C(5)C(6)H(6) |
120.81 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. Atomic coordinates, ropt. Normal species. |
| (More figures are shown than are significant.) |
| |
|
|
|
|
|
|
|
|
a (Å) |
|
b (Å) |
|
|
|
|
|
|
|
Cl |
|
2.635876 |
|
0.001134 |
|
C(1) |
- |
1.875426 |
- |
0.002458 |
|
C(2) |
- |
1.175653 |
- |
1.206728 |
|
C(3) |
|
0.213288 |
- |
1.208213 |
|
C(4) |
|
0.899308 |
- |
0.001706 |
|
C(5) |
|
0.207990 |
|
1.204803 |
|
C(6) |
- |
1.178205 |
|
1.204086 |
|
O(1) |
- |
3.232535 |
|
0.058908 |
|
H |
- |
3.591060 |
- |
0.833777 * |
|
H(2) |
- |
1.714870 |
- |
2.150245 |
|
H(3) |
|
0.761749 |
- |
2.142487 |
|
H(5) |
|
0.756161 |
|
2.139311 |
|
H(6) |
- |
1.733849 |
|
2.134580 |
| |
|
|
|
|
|
|
* The rs b-coordinate of the hydroxyl hydrogen was reported by Onda et al. [2]. It is |b| = 0.833(2) Å. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 6. Rotational Constants
(MHz). Normal species. |
|
|
|
|
|
|
Calc ropt |
Expt [2] |
|
|
|
|
|
A |
5674.9 |
5632.78(7) |
|
B |
978.5 |
975.573(4) |
|
C |
834.6 |
831.655(4) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] L.S.Batchelder, J.Clymer, and J.L.Rangle, J.Chem.Phys.
74,4791(1981). |
|
|
[2] M.Onda, T.Motoda, and I.Yamaguchi, Bull.Chem.Soc.Jpn. 58,242(1985). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorobenzene
|
Phenol
|
|
|
1,2-Dichlorobenzene |
1,2-Chlorofluorobenzene |
|
1,3-Dichlorobenzene |
1,3-Chlorofluorobenzene |
|
1,4-Dichlorobenzene |
1,4-Chlorofluorobenzene |
|
Bromobenzene |
cis-2-Chlorophenol |
|
Fluorobenzene |
trans-2-Chlorophenol |
|
|
Benzonitrile |
d1-Benzene |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents
|
|
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
Molecules/Deuterium |
|
|
|
|
|
Molecules/Oxygen |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
4chlorophenol.html |
|
|
|
|
|
|
Last
Modified 30 Dec 2008 |
|
|
|
|
|
|
|
|
|
|