|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
2-F-4-Cl-C5H3N
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen and Chlorine
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in 2-Fluoro-4-Chloropyridine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation was made of the
nitrogen and chlorine nqcc tensors in 2-fluoro-4-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-4-35Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa |
- |
3.864 |
|
|
|
|
|
Xbb |
|
1.235 |
|
|
|
|
|
Xcc |
|
2.629 |
|
|
|
|
|
|Xab| |
|
1.693 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
1.746 |
|
|
|
|
|
Xyy |
|
2.629 |
|
|
|
|
|
Xzz |
- |
4.375 |
|
|
|
|
|
ETA |
|
0.202 |
|
|
|
|
|
Øz,a |
|
16.79 |
|
|
|
|
|
Øa,bi |
|
16.36 |
|
|
|
|
|
Øz,bi * |
|
0.43 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The
z-axis makes an angle of 0.43o 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-4-35Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
- |
63.26 |
|
|
|
|
|
Xbb |
|
31.45 |
|
|
|
|
|
Xcc |
|
31.81 |
|
|
|
|
|
|Xab| |
|
31.58 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
41.01 |
|
|
|
|
|
Xyy |
|
31.81 |
|
|
|
|
|
Xzz |
- |
72.82 |
|
|
|
|
|
ETA |
- |
0.126 |
|
|
|
|
|
Øz,a |
|
16.85 |
|
|
|
|
|
Øa,CCl |
|
16.92 |
|
|
|
|
|
Øz,CCl |
|
0.07 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 3. Nitrogen and Chlorine nqcc's in 2-F-4-37Cl-Pyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. |
|
| |
|
|
|
|
|
|
|
|
14N |
Xaa |
- |
3.888 |
|
|
|
|
|
Xbb |
|
1.259 |
|
|
|
|
|
Xcc |
|
2.629 |
|
|
|
|
|
|Xab| |
|
1.659 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
37Cl |
Xaa |
- |
50.20 |
|
|
|
|
|
Xbb |
|
25.13 |
|
|
|
|
|
Xcc |
|
25.07 |
|
|
|
|
|
|Xab| |
|
17.56 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RSD |
|
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
| Table 4. 2-Fluoro-4-Chloropyridine. Molecular structure parameters, ropt (Å
and degrees). |
| |
|
|
|
|
|
N(1)C(2) |
1.3093 |
|
|
C(2)C(3) |
1.3896 |
|
|
C(3)C(4) |
1.3846 |
|
|
C(4)C(5) |
1.3921 |
|
|
C(5)C(6) |
1.3856 |
|
|
C(6)N(1) |
1.3367 |
|
|
C(2)F(2) |
1.3327 |
|
|
C(3)H(3) |
1.0816 |
|
|
C(4)Cl(4) |
1.7248 |
|
|
C(5)H(5) |
1.0820 |
|
|
C(6)H(6) |
1.0865 |
|
|
C(6)N(1)C(2) |
116.20 |
|
|
N(1)C(2)C(3) |
126.37 |
|
|
C(2)C(3)C(4) |
115.88 |
|
|
C(3)C(4)C(5) |
120.13 |
|
|
C(4)C(5)C(6) |
117.38 |
|
|
C(5)C(6)N(1) |
124.04 |
|
|
N(1)C(2)F(2) |
116.08 |
|
|
C(2)C(3)H(3) |
121.35 |
|
|
C(3)C(4)Cl(4) |
119.80 |
|
|
C(4)C(5)H(5) |
121.19 |
|
|
C(5)C(6)H(6) |
120.04 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. 2-F-4-35Cl-Pyridine. Atomic coordinates, ropt. |
| |
|
|
|
|
|
|
|
|
a (Å) |
|
b (Å) |
|
|
|
|
|
|
|
N(1) |
-
|
1.8323 |
|
0.8757 |
|
C(2) |
- |
1.4815 |
- |
0.3857 |
|
C(3) |
- |
0.1828 |
- |
0.8799 |
|
C(4) |
|
0.8251 |
|
0.0695 |
|
C(5) |
|
0.5083 |
|
1.4250 |
|
C(6) |
- |
0.8349 |
|
1.7655 |
|
F(2) |
- |
2.4778 |
- |
1.2710 |
|
Cl(3) |
|
0.0146 |
- |
1.9433 |
|
H(4) |
|
2.4752 |
- |
0.4324 |
|
H(5) |
|
1.2820 |
|
2.1813 |
|
H(6) |
- |
1.1310 |
|
2.8109 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 6. 2-F-4-35Cl-Pyridine. Rotational Constants
(MHz). |
| |
|
|
|
|
|
Calc ropt |
Expt. |
|
|
|
|
|
A |
3677.2 |
|
|
B |
1183.0 |
|
|
C |
895.0 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Pyridine |
4-Chloropyridine |
3,4-Dichloropyridine
|
|
3-Fluoro-4-Chloropyridine |
2,4-Dichloropyridine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents
|
|
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
2F4CP.html |
|
|
|
|
|
|
Last
Modified 9 Feb 2004 |
|
|
|
|
|
|
|
|
|
|