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1,2-Dichlorobenzene
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in 1,2-Dichlorobenzene |
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35Cl nqcc's in 1,2-dichlorobenzene were first determined
by Onda and Yamaguchi [1], and revisited by Merke et al. [2]. An
effective molecular structure was determined by Onda et al. [3]. |
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Chlorine nqcc's were calculated here on the molecular structure
of Onda et al., and on a structure given by B3P86/6-31G(3d,3p) optimization.
These calculated nqcc's are compared with the experimental values in Tables
1 and 2. The structure parameters are compared in Table 3.
In Table 4, atomic coordinates for the optimized structure are given. |
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In Table 1, RMS is the root mean square difference
between calculated and experimental diagonal nqcc's (percentage of the
average of the magnitudes of the experimental nqcc's). RSD is the
calibration residual standard deviation for the B1LYP/TZV(3df,2p) model
for calculation of the chlorine nqcc's. |
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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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Table 1. Chlorine
nqcc's in 1,2-Dichlorobenzene (MHz). Calculation was made on the ro molecular structure of Onda et al. [3]. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
- |
41.49 |
- |
41.1153(35) |
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Xbb |
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8.85 |
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8.3415(96) |
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Xcc |
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32.64 |
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32.7738(61) |
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Xab |
± |
52.24 |
± |
52.41(58) |
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RMS |
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0.37 (1.4 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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41.67 |
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41.57(52) |
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Xyy |
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32.64 |
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32.7738(61) |
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Xzz |
- |
74.31 |
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74.34(52) |
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ETA |
- |
0.122 |
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0.118 |
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Øz,a |
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32.14 |
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32.4 |
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Øa,CCl |
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30.90 |
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30.9 |
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Øz,CCl |
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1.24 |
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1.5 |
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37Cl |
Xaa |
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32.70 |
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Xbb |
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6.98 |
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Xcc |
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25.72 |
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Xab |
± |
41.18 |
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RSD |
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0.44 (1.1 %) |
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Table 2. Chlorine
nqcc's in 1,2-Dichlorobenzene (MHz). Calculation was made on the B3P86/6-31G(3d,3p) ropt structure. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
- |
40.95 |
- |
41.1153(35) |
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Xbb |
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8.41 |
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8.3415(96) |
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Xcc |
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32.54 |
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32.7738(61) |
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Xab |
± |
52.34 |
± |
52.41(58) |
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RMS |
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0.17 (0.63 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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41.60 |
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41.57(52) |
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Xyy |
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32.54 |
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32.7738(61) |
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Xzz |
- |
74.14 |
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74.34(52) |
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ETA |
- |
0.122 |
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0.118 |
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Øz,a |
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32.38 |
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32.4 |
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Øa,CCl |
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31.17 |
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Øz,CCl |
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1.21 |
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37Cl |
Xaa |
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32.27 |
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Xbb |
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6.63 |
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Xcc |
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25.64 |
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Xab |
± |
41.25 |
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RSD |
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0.44 (1.1 %) |
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The nqcc z-axis makes an angle of 1.21o with the CCl
bond axis. In 1,2-chlorofluorobenzene, this angle is 1.07o.
On the other hand, in 1,3-dichlorobenzene and 1,3-chlorofluorobenzene,
this angle is 0.09o and 0.06o respectively.
(Calculated nqcc's, ropt structures.) |
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| Table 3. Molecular structure parameters (Å and degrees). |
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ro
[1] |
ropt |
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C(1,2)Cl(1,2) |
1.729 |
1.7251 |
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C(1)C(2) |
1.398 |
1.3969 |
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C(2)C(3) |
1.393 |
1.3916 |
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C(3)C(4) |
1.397 |
1.3874 |
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C(4)C(5) |
1.394 |
1.3897 |
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C(3)H(3) |
1.083 |
1.0833 |
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C(4)H(4) |
1.080 |
1.0843 |
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C(1)C(2)C(3) |
120.3 |
119.78 |
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C(2)C(3)C(4) |
119.5 |
120.16 |
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C(3)C(4)C(5) |
120.3 |
120.05 |
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C(1)C(2)Cl(2) |
120.9 |
121.17 |
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C(2)C(3)H(3) |
118.7 |
118.78 |
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C(3)C(4)H(4) |
119.5 |
119.56 |
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For comparison with the optimized structure, the B3P86/6-31G(3d,3p)
optimized structure of benzene is CC = 1.3909 Å and CH = 1.0851
Å. |
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| Table 4. Atomic Coordinates, ropt |
| (More figures are shown than are significant.) |
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a (Å) |
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b (Å) |
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Cl(1,2) |
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1.426031 |
± |
1.591375 |
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C(1,2) |
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0.050003 |
± |
0.698460 |
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C(3,6) |
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1.257799 |
± |
1.389658 |
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C(4,5) |
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2.458660 |
± |
0.694872 |
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H(3,6) |
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1.238906 |
± |
2.472784 |
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H(4,5) |
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3.393972 |
± |
1.243330 |
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[1] M.Onda and I.Yamaguchi, J.Mol.Struct. 34,1(1976). |
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[2] I.Merke, Ch.Keussen, H.Dreizler, and M.Onda, Z.Naturforsch.
45a,1273(1990). |
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[3] M.Onda, M.Ueda, M.Atsuki, J.Yamaguchi, and I.Yamaguchi, J.Mol.Struct.
147,77(1986). |
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Chlorobenzene |
1,2-Chlorofluorobenzene |
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1,3-Dichlorobenzene |
1,3-Chlorofluorobenzene |
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1,4-Dichlorobenzene |
1,4-Chlorofluorobenzene |
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cis-2-Chlorophenol |
trans-2-Chlorophenol |
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Table of Contents |
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Molecules/Chlorine |
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12DCB.html |
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Last
Modified 4 June 2003 |
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