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3-Cl-C5H4N
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in 3-Chloropyridine |
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Chlorine and nitrogen nqcc's in 3-chloropyridine were measured
by Heineking and Dreizler [1]. Earlier measurements were reported
by Brown and J.Matouskova [2], Sharma and S.Doraiswany [3], and Chatterjee
and Ghosh [4]. |
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Calculation of the nitrogen and
chlorine nqcc's were made here on the B3P86/6-31G(3d,3p) optimized
molecular structure. These are compared with the experimental
values in Tables 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, 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.
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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 3-35Chloropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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0.006 |
- |
0.009(13) |
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Xbb |
- |
3.476 |
- |
3.473(10) |
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Xcc |
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3.470 |
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3.482(16) |
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|Xab| |
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2.677 |
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RMS |
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0.011 (0.5 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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1.458 |
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1.447 * |
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Xyy |
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3.470 |
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3.482 |
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Xzz |
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4.928 |
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4.929 |
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ETA |
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0.408 |
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0.413 |
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Øz,a |
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61.52 |
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61.45 |
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Øa,bi |
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60.43 |
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60.43 |
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Øz,bi ** |
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1.09 |
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1.02 |
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* Calculated
here from the experimental diagonal nqcc's and the calculated off-diagonal
nqcc. |
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** The z-axis makes an angle of 1.09o
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-Chloropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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72.68 |
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72.255(19) |
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Xbb |
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39.17 |
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38.500(13) |
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Xcc |
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33.50 |
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33.755(23) |
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|Xab| |
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2.23 |
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RMS |
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0.48 (1.0 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.22 |
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38.54 * |
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Xyy |
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33.50 |
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33.755 |
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Xzz |
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72.72 |
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72.30 |
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ETA |
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0.079 |
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0.066 |
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Øz,a |
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1.14 |
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1.15 |
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Øa,CCl |
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1.33 |
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1.33 |
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Øz,CCl |
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0.19 |
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0.18 |
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37Cl |
Xaa |
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57.28 |
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Xbb |
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30.87 |
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Xcc |
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26.40 |
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|Xab| |
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1.74 |
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RSD |
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0.44 (1.1 %) |
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* Calculated
here from the experimental diagonal nqcc's and the calculated off-diagonal
nqcc. |
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| Table 3. 3-Chloropyridine and Pyridine. Molecular structure parameters, ropt (Å
and degrees). |
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3-Cl-Pyridine |
Pyridine |
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C(3)Cl(3) |
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1.7307 |
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N(1)C(2) |
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1.3291 |
1.3336 |
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C(2)C(3) |
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1.3926 |
1.3904 |
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C(3)C(4) |
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1.3868 |
1.3885 |
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C(4)C(5) |
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1.3883 |
1.3885 |
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C(5)C(6) |
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1.3893 |
1.3904 |
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C(6)N(1) |
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1.3336 |
1.3336 |
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C(2)H(2) |
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1.0866 |
1.0880 |
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C(4)H(4) |
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1.0835 |
1.0851 |
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C(5)H(5) |
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1.0842 |
1.0845 |
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C(6)H(6) |
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1.0871 |
1.0880 |
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C(6)N(1)C(2) |
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117.83 |
117.03 |
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N(1)C(2)C(3) |
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122.61 |
123.80 |
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C(2)C(3)C(4) |
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119.61 |
118.44 |
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C(3)C(4)C(5) |
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117.68 |
118.50 |
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C(4)C(5)C(6) |
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118.82 |
118.44 |
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C(5)C(6)N(1) |
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123.45 |
123.80 |
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N(1)C(2)H(2) |
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117.36 |
115.94 |
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C(2)C(3)Cl(3) |
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119.76 |
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C(3)C(4)H(4) |
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120.54 |
120.75 |
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C(4)C(5)H(5) |
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120.66 |
121.35 |
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C(5)C(6)H(6) |
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120.53 |
120.26 |
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| Table 4. 3-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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1.6144 |
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1.1998 |
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C(2) |
- |
0.2859 |
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1.1646 |
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C(3) |
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0.4333 |
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0.0280 |
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C(4) |
- |
0.2452 |
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1.2374 |
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C(5) |
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1.6330 |
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1.1983 |
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C(6) |
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2.2681 |
- |
0.0374 |
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H(2) |
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0.2390 |
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2.1160 |
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Cl(3) |
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2.1636 |
- |
0.0123 |
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H(4) |
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0.2992 |
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2.1742 |
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H(5) |
- |
2.2120 |
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2.1149 |
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H(6) |
- |
3.3534 |
- |
0.1004 |
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| Table 5. 3-Chloropyridine. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt. [1] |
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A |
5885.7 |
5839.5330(12) |
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B |
1608.0 |
1604.1875(6) |
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C |
1262.9 |
1258.3121(5) |
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[1] N.Heineking and H.Dreizler, Z.Naturforsch. 43a,657(1988). |
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[2] R.D.Brown and J.Matouskova, J.Mol.Struct. 29,33(1975). |
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[3] S.D.Sharma and S.Doraiswany, J.Mol.Spectrosc. 57,377(1975). |
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[4] A.Chatterjee and D.K.Ghosh, Indian J.Phys. 48,958(1974). |
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Pyridine |
2-Chloropyridine |
4-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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3MCP.html |
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Last
Modified 6 Dec 2003 |
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