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3-Cl-C6H4CN
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in 3-Chlorobenzonitrile
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Chlorine and nitrogen nqcc tensors in 3-chlorobenzonitrile were determined
by Varadwaj, et al. [1]. |
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Calculation was made here of the
nitrogen and chlorine nqcc tensors on a molecular structure given by
B3P86/6-31G(3d,3p) optimization. These are compared with the
experimental
values 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; subscripts 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 difference between calculated and
experimental diagonal nqcc's (percent of the average of the magnitudes of the experimental nqcc's). 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-Benzonitrile (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 |
- |
2.668 |
- |
2.6687(18) |
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Xbb |
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0.687 |
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0.6849(21) |
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Xcc |
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1.980 |
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1.9838(21) |
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Xab |
- |
2.834 |
- |
2.924(58) |
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RMS |
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0.003 (0.14 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.303 |
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2.379(50) |
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Xyy |
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1.980 |
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1.9838(21) |
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Xzz |
- |
4.284 |
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4.363(50) |
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ETA |
- |
0.075 |
- |
0.091(12) |
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Øz,a |
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29.69 |
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30.08(25) |
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Øa,CN |
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29.69 |
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Øz,CN |
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0.00 |
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Table 2. Chlorine nqcc's in 3-35Cl-Benzonitrile (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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44.56 |
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44.1848(19) |
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Xbb |
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11.31 |
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10.6890(22) |
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Xcc |
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33.25 |
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33.4958(22) |
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Xab |
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49.29 |
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48.759(32) |
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RMS |
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0.44 (1.5 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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40.03 |
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39.200(28) |
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Xyy |
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33.25 |
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33.4958(22) |
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Xzz |
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73.28 |
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72.695(28) |
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ETA |
- |
0.0925 |
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0.0785(4) |
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Øz,a |
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30.23 |
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30.316(8) |
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Øa,CCl |
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30.31 |
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Øz,CCl |
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0.08 |
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Table 3. Nitrogen and Chlorine nqcc's in 3-37Cl-Benzonitrile (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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2.605 |
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2.6095 * |
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Xbb |
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0.624 |
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0.6232 |
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Xcc |
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1.980 |
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1.9864 |
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Xab |
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2.871 |
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RMS |
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0.004 (0.25 %) |
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RSD |
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0.030 (1.3 %) |
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37Cl |
Xaa |
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35.97 |
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35.633 ** |
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Xbb |
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9.76 |
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9.235 |
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Xcc |
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26.20 |
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26.398 |
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Xab |
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38.35 |
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RMS |
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0.38 (1.6 %) |
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RSD |
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0.44 (1.1 %) |
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* Calculated
here from (3/2)Xaa = -3.9143(98) MHz and (Xbb - Xcc)/4 = -0.3408(15) MHz [1]. |
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** Calculated
here from (3/2)Xaa = -53.450(42) MHz and (Xbb - Xcc)/4 = -4.2909(54) MHz [1]. |
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| Table 4. 3-Chlorobenzonitrile. Molecular structure parameters, ropt (Å
and degrees). Z-Matrix. |
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C(1)C(2) |
1.3980 |
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C(2)C(3) |
1.3869 |
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C(3)C(4) |
1.3909 |
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C(4)C(5) |
1.3897 |
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C(5)C(6) |
1.3870 |
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C(6)C(1) |
1.3981 |
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C(6)C(1)C(2) |
120.62 |
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C(1)C(2)C(3) |
118.81 |
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C(2)C(3)C(4) |
121.19 |
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C(3)C(4)C(5) |
119.35 |
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C(4)C(5)C(6) |
120.65 |
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C(5)C(6)C(1) |
119.37 |
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C(1)C(11) |
1.4294 |
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C(11)N |
1.1579 |
| N tilts away from Cl |
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C(1)C(11)N |
179.88 |
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C(3)Cl |
1.7299 |
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C(2)C(3)Cl |
119.27 |
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C(2)H |
1.0824 |
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C(1)C(2)H |
120.55 |
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C(4)H |
1.0832 |
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C(3)C(4)H |
119.69 |
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C(5)H |
1.0841 |
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C(4)C(5)H |
119.48 |
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C(6)H |
1.0830 |
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C(5)C(6)H |
120.98 |
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| Table 5. 3-Chlorobenzonitrile. Atomic coordinates, ropt. Normal species. |
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a (Å) |
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b (Å) |
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C(1) |
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1.3240 |
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0.0202 |
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C(2) |
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0.1227 |
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0.6950 |
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C(3) |
- |
1.0732 |
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0.0072 |
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C(4) |
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1.0920 |
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1.3980 |
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C(5) |
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0.1100 |
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2.0955 |
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C(6) |
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1.3204 |
- |
1.4184 |
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H(7) |
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0.1268 |
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1.7774 |
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H(8) |
- |
2.0401 |
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1.9219 |
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H(9) |
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0.0978 |
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3.1796 |
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H(10) |
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2.2603 |
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1.9566 |
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C(11) |
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2.5643 |
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0.6903 |
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N(12) |
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3.5702 |
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1.2638 |
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Cl(13) |
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2.5668 |
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0.8657 |
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| Table 6. 3-Chlorobenzonitrile. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt. [1] |
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A |
2786.9 |
2774.187266(49) |
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B |
890.4 |
887.656955(55) |
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C |
674.8 |
672.342238(52) |
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[1] P.R.Varadwaj, A.I.Jaman, Z.Kisiel, L.Pszczółkowski, J.Mol.Spectrosc. 239,88(2006). |
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Benzonitrile |
1,3-Chlorofluorobenzene |
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Chlorobenzene |
1,3-Dichlorobenzene |
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meta-Tolunitrile |
meta-Fluorobenzonitrile |
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2-Chlorobenzonitrile |
4-Chlorobenzonitrile |
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Table of Contents
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Molecules/Nitrogen |
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Molecules/Chlorine |
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3ClC6H4CN.html |
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Last
Modified 20 June 2006 |
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