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C6H5F-d1
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Deuterium |
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Nuclear
Quadrupole Coupling Constants |
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in Fluorobenzene-d1 |
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Deuterium nqcc's in monodeuterated fluorobenzene (2-,
3-, and 4-d1) were measured by Jans-Bürli, M.Oldani, and A.Bauder [1].
Doraiswamy and Sharma [2] determined for fluorobenzene an ro
molecular structure. |
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Calculation was made here of the deuterium
nqcc's on the molecular structure of Doraiswamy and Sharma, and on a structure
given by B3P86/6-31G(3d,3p) optimization. In Tables 1 and 2, the calculated
nqcc's are compared with the experimental values. In Table 3, the
principal values of the nqcc tensors calculated on the optimized structure
are collected for easy comparison. The structure parameters are compared
in Table 4. In Table 5, atomic coordinates for the optimized structure
are given. |
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In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor,
the 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 plane of the molecule. Ø (degrees) is the angle between
its subscripted parameters. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the overall root mean square
difference between calculated and experimental inertia axes nqcc's (percentage
of the average of the magnitudes of the experimental nqcc's). RSD
is the calibration residual standard deviation for the B3LYP/6-31G(df,3p)
model for calculation of the nqcc's. |
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Table 1. Deuterium
nqcc's in Fluorobenzene-d1 (kHz). Calculation was made on
the ro structure [2].
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Calc. |
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Expt. [1] |
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2H(4) |
Xaa |
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194.8 |
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187.7(15) |
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Xbb |
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- 91.3 |
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- 89.0(30) |
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Xcc |
- |
103.6 |
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- 98.7(25) |
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ETA |
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0.063 |
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2H(3) |
Xaa |
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- 12.8 |
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- 9.6(33) |
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Xbb |
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113.4 |
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112.6(32) |
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Xcc |
- |
100.5 |
- |
103.0(26) |
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|Xab| |
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125.4 |
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Xxx |
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- 90.1 |
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- 88.0 * |
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Xyy |
- |
100.5 |
- |
103.0 |
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Xzz |
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190.7 |
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191.0 |
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ETA |
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0.054 |
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0.078 |
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Øz,a |
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60.36 |
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58.00 |
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Øa,CD |
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60.43 |
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60.43 |
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Øz,CD |
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0.07 |
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2.44 |
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2H(2) |
Xaa |
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- 9.7 |
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- 18.0(26) |
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Xbb |
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112.0 |
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115.7(27) |
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Xcc |
- |
102.3 |
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- 97.7(22) |
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|Xab| |
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128.1 |
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Xxx |
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- 90.7 |
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- 95.6 * |
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Xyy |
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102.3 |
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- 97.7 |
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Xzz |
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193.0 |
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193.3 |
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ETA |
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0.060 |
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0.011 |
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Øz,a |
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58.61 |
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58.78 |
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Øa,CD |
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58.33 |
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58.33 |
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Øz,CD |
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0.28 |
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0.45 |
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RMS |
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4.7 (5.1 %) |
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RSD |
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1.1 (0.9 %) |
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* Calculated here from the experimental diagonal
nqcc's and the calculated value of Xab. |
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Table 2. Deuterium
nqcc's in Fluorobenzene-d1 (kHz). 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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2H(4) |
Xaa |
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190.0 |
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187.7(15) |
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Xbb |
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- 88.8 |
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- 89.0(30) |
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Xcc |
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101.1 |
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- 98.7(25) |
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ETA |
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0.065 |
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2H(3) |
Xaa |
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- 11.6 |
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- 9.6(33) |
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Xbb |
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111.2 |
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112.6(32) |
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Xcc |
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- 99.6 |
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103.0(26) |
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|Xab| |
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124.6 |
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Xxx |
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- 89.2 |
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- 87.3 * |
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Xyy |
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- 99.6 |
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103.0 |
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Xzz |
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188.7 |
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190.3 |
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ETA |
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0.055 |
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0.082 |
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Øz,a |
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60.13 |
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58.06 |
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Øa,CD |
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60.17 |
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60.17 |
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Øz,CD |
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0.03 |
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2.11 |
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2H(2) |
Xaa |
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- 9.6 |
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- 18.0(26) |
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Xbb |
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110.4 |
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115.7(27) |
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Xcc |
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100.8 |
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- 97.7(22) |
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|Xab| |
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126.0 |
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Xxx |
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- 89.2 |
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- 93.8 * |
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Xyy |
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100.8 |
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- 97.7 |
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Xzz |
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190.0 |
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191.5 |
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ETA |
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0.061 |
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0.020 |
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Øz,a |
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58.63 |
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58.97 |
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Øa,CD |
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58.34 |
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58.34 |
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Øz,CD |
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0.29 |
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0.63 |
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RMS |
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3.9 (4.2 %) |
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RSD |
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1.1 (0.9 %) |
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* Calculated here from the experimental diagonal
nqcc's and the calculated value of Xab. |
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Table 3. Principal
values of the deuterium nqcc tensor calculated on the B3P86/6-31G(3d,3p)
optimized structures of phenylacetylene (PhA), fluorobenzene (FB), and benzene.
(kHz and degrees) |
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Xzz |
Xyy |
Xxx |
ETA |
Øz,CD |
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C6H5D |
189.0 |
-99.9 |
-89.1 |
0.057 |
0 |
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PhA D(4) |
188.9 |
-99.7 |
-89.1 |
0.056 |
0 |
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FB D(4) |
190.0 |
-101.1 |
-88.8 |
0.065 |
0 |
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PhA D(3) |
188.8 |
-99.7 |
-89.0 |
0.057 |
0.01 |
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FB D(3) |
188.7 |
-99.6 |
-89.2 |
0.055 |
0.03 |
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PhA D(2) |
188.3 |
-99.8 |
-88.6 |
0.059 |
0.20 |
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FB D(2) |
190.0 |
-100.8 |
-89.2 |
0.061 |
0.29 |
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The "bond bending" seen in D(2) compared with D(3) recalls that seen
in chlorofluorobenzene (CFB). In 1,3-CFB, Øz,CCl
is 0.06o. In 1,2-CFB, it is 1.07o. Otherwise,
the fluorine substituent has little - if any - effect on the deuterium coupling. |
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| Table 4. Fluorobenzene. Molecular structure parameters (Å
and degrees). |
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ro [2] |
ropt |
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C(1)F |
1.354 |
1.3443 |
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C(1)C(2) |
1.385 |
1.3846 |
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C(2)C(3) |
1.396 |
1.3904 |
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C(3)C(4) |
1.398 |
1.3909 |
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C(2)H(2) |
1.081 |
1.0837 |
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C(3)H(3) |
1.083 |
1.0847 |
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C(4)H(4) |
1.080 |
1.0842 |
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C(6)C(1)C(2) |
123.2 |
122.47 |
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C(1)C(2)C(3) |
118.1 |
118.35 |
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C(2)C(3)C(4) |
120.5 |
120.48 |
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C(3)C(4)C(5) |
119.7 |
119.87 |
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C(1)C(2)H(2) |
119.9 |
119.57 |
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C(2)C(3)H(3) |
119.2 |
119.42 |
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| Table 5. Fluorobenzene. Atomic coordinates,
ropt |
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a (Å) |
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b (Å) |
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F |
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2.1997 |
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0 |
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C(1) |
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0.8554 |
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0 |
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C(2,6) |
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0.1891 |
± |
1.2137 |
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C(3,5) |
- |
1.2013 |
± |
1.2038 |
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C(4) |
- |
1.8981 |
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0 |
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H(2,6) |
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0.7579 |
± |
2.1361 |
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H(3,5) |
- |
1.7409 |
± |
2.1447 |
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H(4) |
- |
2.9823 |
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0 |
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[1] S.Jans-Bürli, M.Oldani, and A.Bauder, Mol.Phys. 68,1111(1989). |
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[2] S.Doraiswamy and S.D.Sharma, J.Mol.Struct. 102,81(1983). |
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Benzene-d1 |
Phenylacetylene-d1 |
Pyridine-4D |
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1,2-Chlorofluorobenzene |
1,3-Chlorofluorobenzene |
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Table of Contents |
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Molecules/Deuterium |
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C6H5F.html |
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Last
Modified 2 June 2003 |
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