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2-Cl-C5H4N
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in 2-Chloropyridine |
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Chlorine and nitrogen nqcc's in 2-chloropyridine were determined
by Meyer, Andersen, and Dreizler [1]. Previous measurements of the
chlorine nqcc's had been reported by Walden and Cook [2], Scappini and
Guarnieri [3], and Doraiswany and Sharma [4]. |
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Calculation was made here of the
nitrogen and chlorine nqcc's 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 2-Chloropyridine (MHz). Calculation
was made on the B3P86/6-31G(3d,3p) ropt structure. |
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[a] 35Cl species, and [b] 37Cl species. |
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Calc. |
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Expt. [1] |
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14N [a] |
Xaa |
- |
0.094 |
- |
0.09(2) |
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Xbb |
- |
2.917 |
- |
2.94(2) |
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Xcc |
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3.012 |
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3.03(3) |
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|Xab| |
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2.897 |
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RMS |
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0.02 (0.8 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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1.716 |
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1.71 * |
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Xyy |
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3.012 |
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3.03 |
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Xzz |
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4.728 |
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4.74 |
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ETA |
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0.274 |
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0.278 |
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Øz,a |
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57.99 |
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58.1 |
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Øa,bi |
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57.81 |
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57.81 |
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Øz,bi ** |
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0.17 |
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0.3 |
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14N [b] |
Xaa |
- |
0.093 |
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0.07(4) |
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Xbb |
- |
2.918 |
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2.99(6) |
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Xcc |
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3.012 |
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3.06(7) |
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|Xab| |
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2.896 |
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RMS |
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0.05 (2.5 %) |
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RSD |
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0.030 (1.3 %) |
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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 0.17o with the external bisector ( 'bi' ) of the C(6)N(1)C(2)
angle, and tilts toward C(6). |
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Table 2. Chlorine nqcc's in 2-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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70.85 |
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70.42(4) |
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Xbb |
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40.60 |
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39.69(2) |
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Xcc |
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30.25 |
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30.73(4) |
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|Xab| |
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0.14 |
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RMS |
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0.64 (1.4 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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40.60 |
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39.69 * |
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Xyy |
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30.25 |
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30.73 |
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Xzz |
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70.85 |
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70.42 |
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ETA |
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0.146 |
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0.127 |
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Øz,a |
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0.07 |
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0.07 |
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Øa,CCl |
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0.26 |
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0.26 |
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Øz,CCl |
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0.19 |
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0.19 |
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37Cl |
Xaa |
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55.84 |
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55.47(5)
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Xbb |
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31.99 |
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31.23(8) |
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Xcc |
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23.84 |
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24.24(9) |
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|Xab| |
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0.09 |
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RMS |
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0.54 (1.5 %) |
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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. 2-Chloropyridine and Pyridine. Molecular structure parameters, ropt (Å
and degrees). |
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2-Cl-Pyridine |
Pyridine |
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C(2)Cl |
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1.7401 |
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N(1)C(2) |
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1.3168 |
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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1.3859 |
1.3885 |
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C(4)C(5) |
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1.3907 |
1.3885 |
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C(5)C(6) |
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1.3874 |
1.3904 |
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C(6)N(1) |
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1.3357 |
1.3336 |
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C(3)H(3) |
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1.0826 |
1.0845 |
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C(4)H(4) |
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1.0848 |
1.0851 |
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C(5)H(5) |
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1.0835 |
1.0845 |
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C(6)H(6) |
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1.0869 |
1.0880 |
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C(6)N(1)C(2) |
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116.98 |
117.03 |
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N(1)C(2)C(3) |
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124.96 |
123.80 |
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C(2)C(3)C(4) |
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117.18 |
118.44 |
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C(3)C(4)C(5) |
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119.17 |
118.50 |
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C(4)C(5)C(6) |
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118.18 |
118.44 |
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C(5)C(6)N(1) |
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123.54 |
123.80 |
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N(1)C(2)Cl(2) |
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116.57 |
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C(2)C(3)H(3) |
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120.58 |
120.21 |
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C(3)C(4)H(4) |
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120.06 |
120.75 |
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C(4)C(5)H(5) |
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121.39 |
121.35 |
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C(5)C(6)H(6) |
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120.80 |
120.26 |
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| Table 4. 2-Chloropyridine. Atomic coordinates, ropt. Normal species. |
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a (Å) |
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b (Å) |
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Cl(2) |
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2.1331 |
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0.0113 |
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N(1) |
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0.1906 |
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1.1772 |
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C(2) |
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0.3930 |
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0.0033 |
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C(3) |
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0.2766 |
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1.2243 |
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C(4) |
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1.6619 |
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1.1866 |
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C(5) |
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2.3064 |
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0.0458 |
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C(6) |
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1.5262 |
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1.1930 |
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H(3) |
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0.2758 |
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2.1554 |
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H(4) |
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2.2307 |
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2.1103 |
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H(5) |
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3.3875 |
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0.1172 |
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H(6) |
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1.9851 |
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2.1783 |
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| Table 5. 2-Chloropyridine. Rotational Constants
(MHz). Normal species. |
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Calc ropt |
Expt. [1] |
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A |
5920.1 |
5872.0279(6) |
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B |
1641.1 |
1637.8348(1) |
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C |
1284.9 |
1280.5136(1) |
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[1] M.Meyer, U.Andersen, and H.Dreizler, Z.Naturforsch. 42a,197
(1987). |
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[2] R.T.Walden and R.L.Cook, J.Mol.Spectrosc. 52,244(1974). |
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[3] F.Scappini and A.Guarnieri, Z.Naturforsch. 27a,1011(1972). |
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[4] S.Doraiswany and D.Sharma, CurrentSci. 42,511(1972). |
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Pyridine |
3-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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2MCP.html |
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Last
Modified 15 Nov 2003 |
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