|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
2-F-5-Cl-C5H3N
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen and Chlorine
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in 2-Fluoro-5-Chloropyridine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation was made of the
nitrogen and chlorine nqcc tensors in 2-fluoro-5-chloropyridine on a
molecular structure giveen 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-F-5-35Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa |
|
0.200 |
|
|
|
|
|
Xbb |
- |
2.984 |
|
|
|
|
|
Xcc |
|
2.785 |
|
|
|
|
|
|Xab| |
|
2.647 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
1.697 |
|
|
|
|
|
Xyy |
|
2.785 |
|
|
|
|
|
Xzz |
- |
4.481 |
|
|
|
|
|
ETA |
|
0.243 |
|
|
|
|
|
Øz,a |
|
60.51 |
|
|
|
|
|
Øa,bi |
|
59.11 |
|
|
|
|
|
Øz,bi * |
|
1.40 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The
z-axis makes an angle of 1.40o with the external bisector
( 'bi' ) of the C(6)N(1)C(2) angle, and tilts toward C(6). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Chlorine nqcc's in 2-F-5-35Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
73.69 |
|
|
|
|
|
Xbb |
|
39.19 |
|
|
|
|
|
Xcc |
|
34.49 |
|
|
|
|
|
|Xab| |
|
3.19 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
39.28 |
|
|
|
|
|
Xyy |
|
34.49 |
|
|
|
|
|
Xzz |
- |
73.78 |
|
|
|
|
|
ETA |
- |
0.065 |
|
|
|
|
|
Øz,a |
|
1.62 |
|
|
|
|
|
Øa,CCl |
|
1.81 |
|
|
|
|
|
Øz,CCl |
|
0.19 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 3. Nitrogen and Chlorine nqcc's in 2-F-5-37Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa |
|
0.202 |
|
|
|
|
|
Xbb |
- |
2.986 |
|
|
|
|
|
Xcc |
|
2.785 |
|
|
|
|
|
|Xab| |
|
2.646 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
37Cl |
Xaa |
- |
58.08 |
|
|
|
|
|
Xbb |
|
30.89 |
|
|
|
|
|
Xcc |
|
27.18 |
|
|
|
|
|
|Xab| |
|
2.48 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
| Table 4. 2-Fluoro-5-Chloropyridine. Molecular structure parameters, ropt (Å
and degrees). |
| |
|
|
|
|
|
N(1)C(2) |
1.3087 |
|
|
C(2)C(3) |
1.3898 |
|
|
C(3)C(4) |
1.3835 |
|
|
C(4)C(5) |
1.3921 |
|
|
C(5)C(6) |
1.3880 |
|
|
C(6)N(1) |
1.3340 |
|
|
C(2)F(2) |
1.3338 |
|
|
C(3)H(3) |
1.0827 |
|
|
C(4)H(4) |
1.0834 |
|
|
C(5)Cl(5) |
1.7281 |
|
|
C(6)H(6) |
1.0856 |
|
|
C(6)N(1)C(2) |
117.23 |
|
|
N(1)C(2)C(3) |
125.71 |
|
|
C(2)C(3)C(4) |
116.94 |
|
|
C(3)C(4)C(5) |
118.40 |
|
|
C(4)C(5)C(6) |
119.36 |
|
|
C(5)C(6)N(1) |
122.35 |
|
|
N(1)C(2)F(2) |
116.06 |
|
|
C(2)C(3)H(3) |
120.64 |
|
|
C(3)C(4)H(4) |
121.23 |
|
|
C(4)C(5)Cl(5) |
120.59 |
|
|
C(5)C(6)H(6) |
120.57 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. 2-F-5-35Cl-Pyridine. Atomic coordinates, ropt. |
| |
|
|
|
|
|
|
|
|
a (Å) |
|
b (Å) |
|
|
|
|
|
|
|
N(1) |
-
|
1.1405 |
- |
1.1666 |
|
C(2) |
- |
1.7494 |
- |
0.0082 |
|
C(3) |
- |
1.1279 |
|
1.2349 |
|
C(4) |
|
0.2556 |
|
1.2441 |
|
C(5) |
|
0.9259 |
|
0.0240 |
|
C(6) |
|
0.1934 |
- |
1.1550 |
|
F(2) |
- |
3.0826 |
- |
0.0470 |
|
H(3) |
- |
1.7144 |
|
2.1451 |
|
H(4) |
|
0.8112 |
|
2.1742 |
|
Cl(5) |
|
2.6530 |
- |
0.0305 |
|
H(6) |
|
0.6961 |
- |
2.1172 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 6. 2-F-5-35Cl-Pyridine. Rotational Constants
(MHz). |
| |
|
|
|
|
|
Calc ropt |
Expt. |
|
|
|
|
|
A |
5880.6 |
|
|
B |
986.1 |
|
|
C |
844.5 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Pyridine |
3-Chloropyridine |
3,5-Dichloropyridine |
|
2-Fluoro-3-Chloropyridine |
2,3-Dichloropyridine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents
|
|
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
2F5CP.html |
|
|
|
|
|
|
Last
Modified 10 Feb 2004 |
|
|
|
|
|
|
|
|
|
|