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3-Cl-4-F-C5H3N
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in 3-Chloro-4-Fluoropyridine
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Calculation was made of the
nitrogen and chlorine nqcc tensors in 3-chloro-4-fluoropyridine 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. |
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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.
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Table 1. Nitrogen nqcc's in 3-35Cl-4-Fluoropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. |
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14N |
Xaa |
- |
0.466 |
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Xbb |
- |
2.706 |
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Xcc |
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3.172 |
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|Xab| |
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2.982 |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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1.600 |
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Xyy |
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3.172 |
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Xzz |
- |
4.772 |
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ETA |
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0.329 |
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Øz,a |
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55.29 |
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Øa,bi |
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54.29 |
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Øz,bi * |
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1.00 |
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* The
z-axis makes an angle of 1.00o with the external bisector
( 'bi' ) of the C(6)N(1)C(2) angle, and tilts toward C(2). |
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Table 2. Chlorine nqcc's in 3-35Cl-4-Fluoropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. |
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35Cl |
Xaa |
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73.69 |
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Xbb |
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39.34 |
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Xcc |
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34.35 |
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|Xab| |
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15.17 |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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41.34 |
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Xyy |
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34.35 |
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Xzz |
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75.69 |
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ETA |
- |
0.092 |
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Øz,a |
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7.51 |
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Øa,CCl |
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6.68 |
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Øz,CCl |
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0.84 |
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Table 3. Nitrogen and Chlorine nqcc's in 3-37Cl-4-Fluoropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. |
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14N |
Xaa |
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0.380 |
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Xbb |
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2.792 |
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Xcc |
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3.172 |
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|Xab| |
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2.949 |
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RSD |
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0.030 (1.3 %) |
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37Cl |
Xaa |
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58.40 |
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Xbb |
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31.33 |
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Xcc |
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27.07 |
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|Xab| |
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10.67 |
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RSD |
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0.44 (1.1 %) |
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| Table 4. 3-Chloro-4-Fluoropyridine. Molecular structure parameters, ropt (Å
and degrees). |
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N(1)C(2) |
1.3287 |
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C(2)C(3) |
1.3933 |
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C(3)C(4) |
1.3894 |
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C(4)C(5) |
1.3831 |
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C(5)C(6) |
1.3888 |
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C(6)N(1) |
1.3332 |
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C(2)H(2) |
1.0867 |
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C(3)Cl(3) |
1.7176 |
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C(4)F(4) |
1.3284 |
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C(5)H(5) |
1.0831 |
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C(6)H(6) |
1.0866 |
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C(6)N(1)C(2) |
117.66 |
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N(1)C(2)C(3) |
123.53 |
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C(2)C(3)C(4) |
117.58 |
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C(3)C(4)C(5) |
119.85 |
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C(4)C(5)C(6) |
117.56 |
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C(5)C(6)N(1) |
123.83 |
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N(1)C(2)H(2) |
117.41 |
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C(2)C(3)Cl(3) |
121.39 |
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C(3)C(4)F(4) |
120.18 |
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C(4)C(5)H(5) |
120.16 |
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C(5)C(6)H(6) |
119.93 |
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| Table 5. 3-35Cl-4-Fluoropyridine. Atomic coordinates, ropt. Normal species. |
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a (Å) |
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b (Å) |
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N(1) |
-
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1.8255 |
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1.3424 |
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C(2) |
- |
0.5010 |
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1.4475 |
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C(3) |
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0.3581 |
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0.3506 |
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C(4) |
- |
0.2148 |
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0.9152 |
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C(5) |
- |
1.5915 |
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1.0477 |
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C(6) |
- |
2.3490 |
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0.1163 |
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H(2) |
- |
0.0786 |
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2.4488 |
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Cl(3) |
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2.0640 |
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0.5504 |
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F(4) |
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0.5560 |
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1.9970 |
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H(5) |
- |
2.0433 |
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2.0321 |
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H(6) |
- |
3.4339 |
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0.0571 |
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| Table 6. 3-35Cl-4-Fluoropyridine. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt. |
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A |
2941.5 |
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B |
1582.6 |
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C |
1029.0 |
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Pyridine |
3-Chloropyridine |
3,4-Dichloropyridine
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3-Chloro-5-Fluoropyridine |
2-Fluoro-3-Chloropyridine |
3,5-Dichloropyridine |
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Table of Contents
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Molecules/Nitrogen |
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Molecules/Chlorine |
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34CFP.html |
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Last
Modified 15 Nov 2003 |
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