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4-Cl-C5H4N
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in 4-Chloropyridine |
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Nitrogen and chlorine nqcc's
in 4-chloropyridine were first determined by Caminati and Forti [1],
and revisited by Heineking and Dreizler [2]. |
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Calculation was made here of the nitrogen
and chlorine nqcc's on the molecular structure given by B3P86/6-31G(3d,3p)
optimization. These are compared with the experimental values in
Table 1 and 2. Structure parameters are given in Table 3, atomic
coordinates in Table 4, and rotational constants in Table 5. |
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In Tables 1 and 2, RMS is the root mean square differene between calculated and
experimental nqcc's (percent of average experimental nqcc). 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 4-35Chloropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [2] |
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14N |
Xaa |
- |
4.839 |
- |
4.81(1) |
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Xbb |
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1.517 |
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1.64(4) |
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Xcc |
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3.322 |
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3.17(4) |
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ETA * |
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0.373 |
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RMS |
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0.11 (3.6 %) |
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RSD |
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0.030 (1.3 %) |
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* ETA = (Xbb
- Xcc)/Xaa = (Xxx - Xyy)/Xzz. |
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Table 2. Chlorine nqcc's in 4-Chloropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
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72.08 |
- |
71.65(2) |
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Xbb |
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40.24 |
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39.25(11) |
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Xcc |
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31.84 |
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32.40(11) |
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ETA * |
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0.116 |
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RMS |
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0.70 (1.5 %) |
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RSD |
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0.49 (1.1 %) |
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37Cl |
Xaa |
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56.81 |
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56.4(1) |
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Xbb |
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31.72 |
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30.8(3) |
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Xcc |
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25.09 |
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25.6(3) |
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RMS |
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0.6 (1.7 %) |
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RSD |
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0.44 (1.1 %) |
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* ETA = (Xbb
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| Table 3. 4-Chloropyridine and Pyridine. Molecular structure parameters, ropt (Å
and degrees). |
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4-Cl-Pyridine |
Pyridine |
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N(1)C(2) |
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1.3327 |
1.3336 |
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C(2)C(3) |
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1.3901 |
1.3904 |
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C(3)C(4) |
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1.3873 |
1.3885 |
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C(4)Cl(4) |
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1.7297 |
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C(2)H(2) |
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1.0875 |
1.0880 |
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C(3)H(3) |
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1.0830 |
1.0845 |
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C(6)N(1)C(2) |
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116.86 |
117.03 |
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N(1)C(2)C(3) |
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124.22 |
123.80 |
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C(2)C(3)C(4) |
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117.50 |
118.44 |
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C(3)C(4)C(5) |
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119.70 |
118.50 |
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N(1)C(2)H(2) |
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116.17 |
115.94 |
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C(4)C(3)H(3) |
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121.22 |
121.35 |
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| Table 4. 4-Chloropyridine. 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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2.3319 |
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0.0 |
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C(2,6) |
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1.6342 |
± |
1.1354 |
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C(3.5) |
- |
0.2456 |
± |
1.1996 |
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C(4) |
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0.4512 |
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0.0 |
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Cl(4) |
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2.1810 |
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0.0 |
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H(2,6) |
- |
2.2145 |
± |
2.0550 |
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H(3,5) |
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0.2733 |
± |
2.1503 |
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| Table 5. 4-Chloropyridine. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt. [2] |
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A |
6066.0 |
6019.0(4) |
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B |
1576.8 |
1572.631(2) |
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C |
1251.5 |
1246.748(2) |
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[1] W.Caminati and P.Forti, Chem.Phys.Lett. 38,222(1976). |
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[2] N.Heineking and H.Dreizler, Z.Naturforsch. 41a,1297(1986). |
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Pyridine |
2-Chloropyridine |
3-Chloropyridine
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2-Fluoropyridine |
3-Fluoropyridine |
4-Fluoropyridine |
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2-Bromopyridine |
3-Bromopyridine |
4-Bromopyridine |
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Table of Contents
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Molecules/Nitrogen |
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Molecules/Chlorine |
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4MCP.html |
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Last
Modified 6 Dec 2003 |
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