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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 |
- |
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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Z.Kisiel, E.Białkowska-Jaworska,
L.Pszczółkowski, J.Mol.Spectrosc. 232,47(2005): ro
and
rm(1L) structures. |
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L.Nygaard, I.Bojesen, T.Pedersen, and
J.Rastrup-Andersen, J.Mol.Struct. 2,209(1968): rs
structure. |
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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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