|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
c-2-Cl-C6H4OH
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine and Hydroxyl Deuterium
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in cis-2-Chlorophenol |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
35Cl nqcc's in cis-2-chlorophenol were measured by
Onda, Okada, Fujita, and Odaka [1]. (Chlorine is 'cis'
with respect to the hydroxyl hydrogen.) |
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the chlorine and hydroxyl
deuterium nqcc's was made here on the molecular structure given by B3P86/6-31G(3d,3p)
optimization. These nqcc's are compared with the experimental values
in Tables 1 and 2. Structure parameters and atomic coordinates are given
in Tables 3 and 4, respectively. Rotational constants are given in
Table 5. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 and 2, 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.
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS is the root mean square
difference between calculated and experimental nqcc's (percentage of
the average of the magnitudes of the experimental nqcc's). RSD is
the calibration residual standard deviation of the model for
calculation of the nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Chlorine
nqcc's in c-2-Cl-C6H4OH (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
68.39 |
- |
68.2429 |
|
|
|
Xbb |
|
33.19 |
|
33.660 * |
|
|
|
Xcc |
|
35.19 |
|
34.582 * |
|
|
|
|Xab| |
|
9.94 |
|
11.4(19) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.45 (0.99 %) |
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
34.16 |
|
34.8936(58) |
|
|
|
Xyy |
|
35.19 |
|
34.5824(59) |
|
|
|
Xzz |
- |
69.35 |
- |
69.4758(84) |
|
|
|
ETA |
- |
0.015 |
- |
0.0045(2) |
|
|
|
Øz,a |
|
5.53 |
|
6.2(36) |
|
|
|
Øa,CCl |
|
5.23 |
|
|
|
|
|
Øz,CCl |
|
0.30 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Derived here from Xaa and Xbb - Xcc
= -0.922(20) MHz [1]. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Deuterium
nqcc's in c-2-Cl-C6H4OD (kHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
2H |
Xaa |
|
236.7 |
|
|
|
|
|
Xbb |
|
- 83.1 |
|
|
|
|
|
Xcc |
- |
153.5 |
|
|
|
|
|
|Xab| |
|
98.9 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
1.1 (0.86 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
111.3 |
|
|
|
|
|
Xyy |
- |
153.5 |
|
|
|
|
|
Xzz |
|
264.8 |
|
|
|
|
|
ETA |
|
0.160 |
|
|
|
|
|
Øz,a |
|
15.87 |
|
|
|
|
|
Øa,OD |
|
17.43 |
|
|
|
|
|
Øz,OD |
|
1.56 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
In solid 2-chlorophenol, Batchelder et al. [2] observed the pure
nuclear quadrupole spectra. They determined for the hydroxyl deuterium,
Xzz = 210.05 kHz and ETA = 0.148. |
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 3. Molecular structure parameters, ropt (Å
and degrees). |
| |
|
|
|
|
|
C(2)Cl |
1.7409 |
C(1)C(2)Cl |
117.90 |
|
C(1)C(2) |
1.3981 |
C(1)C(2)C(3) |
121.48 |
|
C(2)C(3) |
1.3871 |
C(2)C(3)C(4) |
119.42 |
|
C(3)C(4) |
1.3884 |
C(3)C(4)C(5) |
119.69 |
|
C(4)C(5) |
1.3917 |
C(4)C(5)C(6) |
120.69 |
|
C(5)C(6) |
1.3886 |
C(5)C(6)C(1) |
120.25 |
|
C(6)C(1) |
1.3938 |
C(6)C(1)C(2) |
118.47 |
|
C(1)O(1) |
1.3478 |
C(2)C(1)O(1) |
122.68 |
|
O(1)H |
0.9679 |
C(1)O(1)H |
108.19 |
|
C(3)H(3) |
1.0835 |
C(2)C(3)H(3) |
119.34 |
|
C(4)H(4) |
1.0837 |
C(3)C(4)H(4) |
119.74 |
|
C(5)H(5) |
1.0845 |
C(4)C(5)H(5) |
119.99 |
|
C(6)H(6) |
1.0839 |
C(5)C(6)H(6) |
121.54 |
| |
|
|
|
|
| Onda et al. determined substitution coordinates for the hydroxyl
hydrogen and chlorine atoms, and therefore the H···Cl
distance - namely, 2.373 Å. The ropt value of the
H···Cl distance is 2.3553 Å. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 4. Atomic coordinates, ropt. Normal species. |
| (More figures are shown than are significant.) |
| |
|
|
|
|
|
|
|
|
a (Å) |
|
b (Å) |
|
|
|
|
|
|
|
Cl |
|
2.065808 |
|
0.511457 |
|
C(1) |
- |
0.206560 |
- |
0.937522 |
|
C(2) |
|
0.332125 |
|
0.352617 |
|
C(3) |
- |
0.480473 |
|
1.476774 |
|
C(4) |
- |
1.860119 |
|
1.321049 |
|
C(5) |
- |
2.409425 |
|
0.042322 |
|
C(6) |
- |
1.593239 |
- |
1.078598 |
|
O(1) |
|
0.559873 |
- |
2.046209 |
|
H |
|
1.488045 |
- |
1.771887 |
|
H(2) |
- |
0.026045 |
|
2.460419 |
|
H(3) |
- |
2.499913 |
|
2.195784 |
|
H(5) |
- |
3.486399 |
- |
0.085044 |
|
H(6) |
- |
2.006379 |
- |
2.080722 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. Rotational Constants
(MHz). Normal species. |
| |
|
|
|
|
|
Calc ropt |
Expt [1] |
|
|
|
|
|
A |
3012.7 |
2985.4479(22) |
|
B |
1553.4 |
1549.8591(3) |
|
C |
1024.9 |
1020.1915(1) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] M.Onda, N.Okada, Y.Fujita, and T.Odaka, J.Mol.Specctrosc.
214,129(2002). |
|
|
[2] L.S.Batchelder, J.Clymer, and J.L.Rangle, J.Chem.Phys.
74,4791(1981). |
|
|
|
|
|
|
|
|
|
|
|
|
M.Onda and I.Yamaguchi, Bull.Chem.Soc. Japan, 51,3121(1978). |
|
|
M.Onda, Y.Oshima, and I.Yamaguchi, Bull.Chem.Soc. Japan, 51,65(1978). |
|
|
|
|
|
|
|
|
|
|
|
|
Chlorobenzene
|
Phenol
|
|
|
1,2-Dichlorobenzene |
1,2-Chlorofluorobenzene |
|
1,3-Dichlorobenzene |
1,3-Chlorofluorobenzene |
|
1,4-Dichlorobenzene |
1,4-Chlorofluorobenzene |
|
Bromobenzene |
4-Chlorophenol |
|
Fluorobenzene |
trans-2-Chlorophenol |
|
|
Benzonitrile |
d1-Benzene |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents
|
|
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
Molecules/Deuterium |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
c2chlorophenol.html |
|
|
|
|
|
|
Last
Modified 15 Oct 2004 |
|
|
|
|
|
|
|
|
|
|