|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
2,4-Cl2-C5H3N
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen and Chlorine
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in 2,4-Dichloropyridine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation was made of the
nitrogen and chlorine nqcc tensors in 2,4-dichloropyridine on a
molecular structure given by B3P86/6-31G(3d,3p) optimization.
These are shown 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 of the model for
calculation of the nqcc's.
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Nitrogen nqcc's in 2,4-Dichloropyridine, normal species (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa |
- |
3.190 |
|
|
|
|
|
Xbb |
|
0.340 |
|
|
|
|
|
Xcc |
|
2.850 |
|
|
|
|
|
|Xab| |
|
2.689 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
1.792 |
|
|
|
|
|
Xyy |
|
2.850 |
|
|
|
|
|
Xzz |
- |
4.642 |
|
|
|
|
|
ETA |
|
0.228 |
|
|
|
|
|
Øz,a |
|
28.36 |
|
|
|
|
|
Øa,bi |
|
28.19 |
|
|
|
|
|
Øz,bi * |
|
0.17 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The
z-axis makes an angle of 0.17o with the external bisector
( 'bi' ) of the C(6)N(1)C(2) angle, and tilts toward C(6). |
|
|
|
|
|
|
|
|
|
|
|
|
Note: In 2-monochloropyridine,
the calculated Xxx, Xyy, and Xzz are respectively
1.716, 3.012, and -4.728 MHz. In 4-monochloropyridine, these
are respectively 1.517, 3.322, and -4.839 MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Cl(2) nqcc's in 2,4-Dichloropyridine, normal species (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
35Cl(2) |
Xaa |
- |
43.60 |
|
|
|
|
|
Xbb |
|
13.17 |
|
|
|
|
|
Xcc |
|
30.43 |
|
|
|
|
|
|Xab| |
|
48.76 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
41.21 |
|
|
|
|
|
Xyy |
|
30.43 |
|
|
|
|
|
Xzz |
- |
71.64 |
|
|
|
|
|
ETA |
- |
0.150 |
|
|
|
|
|
Øz,a |
|
29.90 |
|
|
|
|
|
Øa,CCl |
|
30.16 |
|
|
|
|
|
Øz,CCl |
|
0.26 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 3. Cl(4) nqcc's in 2,4-Dichloropyridine, normal species (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
35Cl(4) |
Xaa |
- |
46.91 |
|
|
|
|
|
Xbb |
|
14.99 |
|
|
|
|
|
Xcc |
|
31.92 |
|
|
|
|
|
|Xab| |
|
47.69 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
40.90 |
|
|
|
|
|
Xyy |
|
31.92 |
|
|
|
|
|
Xzz |
- |
72.81 |
|
|
|
|
|
ETA |
- |
0.123 |
|
|
|
|
|
Øz,a |
|
28.51 |
|
|
|
|
|
Øa,CCl |
|
28.59 |
|
|
|
|
|
Øz,CCl |
|
0.08 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
| Table 4. 2,4-Dichloropyridine. Molecular structure parameters, ropt (Å
and degrees). |
| |
|
|
|
|
|
N(1)C(2) |
1.3170 |
|
|
C(2)C(3) |
1.3928 |
|
|
C(3)C(4) |
1.3857 |
|
|
C(4)C(5) |
1.3904 |
|
|
C(5)C(6) |
1.3865 |
|
|
C(6)N(1) |
1.3352 |
|
|
C(2)Cl(2) |
1.7358 |
|
|
C(3)H(3) |
1.0811 |
|
|
C(4)Cl(4) |
1.7253 |
|
|
C(5)H(5) |
1.0821 |
|
|
C(6)H(6) |
1.0866 |
|
|
C(6)N(1)C(2) |
116.80 |
|
|
N(1)C(2)C(3) |
125.22 |
|
|
C(2)C(3)C(4) |
116.47 |
|
|
C(3)C(4)C(5) |
120.16 |
|
|
C(4)C(5)C(6) |
117.30 |
|
|
C(5)C(6)N(1) |
124.05 |
|
|
N(1)C(2)Cl(2) |
116.76 |
|
|
C(2)C(3)H(3) |
121.54 |
|
|
C(3)C(4)Cl(4) |
119.69 |
|
|
C(4)C(5)H(5) |
121.23 |
|
|
C(5)C(6)H(6) |
120.13 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. 2,4-Dichloropyridine. Atomic coordinates, ropt. Normal species. |
| |
|
|
|
|
|
|
|
|
a (Å) |
|
b (Å) |
|
|
|
|
|
|
|
N(1) |
- |
1.2405 |
- |
1.3577 |
|
C(2) |
- |
1.1622 |
- |
0.0431 |
|
C(3) |
|
0.0213 |
|
0.6910 |
|
C(4) |
|
1.2001 |
- |
0.0375 |
|
C(5) |
|
1.1622 |
- |
1.4274 |
|
C(6) |
- |
0.0866 |
- |
2.0295 |
|
Cl(2) |
- |
2.6630 |
|
0.8291 |
|
H(3) |
|
0.0163 |
|
1.7721 |
|
Cl(4) |
|
2.7150 |
|
0.7881 |
|
H(5) |
|
2.0719 |
- |
2.0134 |
|
H(6) |
- |
0.1699 |
- |
3.1129 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 6. 2,4-Dichloropyridine. Rotational Constants
(MHz). Normal species. |
| |
|
|
|
|
|
Calc ropt |
Expt. |
|
|
|
|
|
A |
3004.0 |
|
|
B |
869.2 |
|
|
C |
674.1 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Pyridine |
2-Chloropyridine |
3-Chloropyridine
|
|
1,2-Dichlorobenzene |
2,3-Dichloropyridine |
2,5-Dichloropyridine |
|
2,6-Dichloropyridine |
3,4-Dichloropyridine |
3,5-Dichloropyridine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents
|
|
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
24DCP.html |
|
|
|
|
|
|
Last
Modified 15 Nov 2003 |
|
|
|
|
|
|
|
|
|
|