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1,3-Dichlorobenzene
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in 1,3-Dichlorobenzene |
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35Cl nqcc's in 1,3-dichlorobenzene were first determined
by Onda and Yamaguchi [1], and revisited by Merke et al. [2]. An
effective molecular structure was reported by Onda et al. [3]. Anderson
et al. [4] report a structure determined by combined analysis of electron
diffraction, rotation constants, and liquid crystal NMR data. |
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Chlorine nqcc's were calculated here on the molecular structures
of Onda et al. and Anderson et al.; and on a structure determined by B3P86/
6-31G(3d,3p) optimization. These calculated nqcc's are compared with
the experimental values of Merke et al. in Tables 1-3. Structure
parameters are compared in Table 4. In Table 5, atomic coordinates
for the optimized structure are given. |
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In Tables 1-3, RMS is the root mean square difference between
calculated and experimental 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 nqcc's. |
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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 plane of the molecule. Ø (degrees) is
the angle between its subscripted parameters. ETA = (Xxx
- Xyy)/Xzz. |
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Table 1. Chlorine
nqcc's in 1,3-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 |
- |
44.07 |
- |
44.174(12) |
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Xbb |
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11.24 |
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10.876(12) |
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Xcc |
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32.83 |
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33.298(12) |
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Xab |
± |
48.72 |
± |
48.181(39) |
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RMS |
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0.35 (1.2 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.60 |
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38.840(41) |
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Xyy |
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32.83 |
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33.298(12) |
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Xzz |
- |
72.44 |
- |
72.138(41) |
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ETA |
- |
0.093 |
- |
0.077 |
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Øz,a |
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30.21 |
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30.13(1) |
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Øa,CCl |
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30.3 |
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30.3 * |
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Øz,CCl |
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0.1 |
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0.2 * |
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37Cl |
Xaa |
- |
34.73 |
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Xbb |
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8.86 |
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Xcc |
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25.87 |
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Xab |
± |
38.40 |
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RSD |
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0.44 (1.1 %) |
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* Calculated here. |
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Table 2. Chlorine
nqcc's in 1,3-Dichlorobenzene (MHz). Calculation was made on the roalpha molecular structure of Anderson et al. [4]. |
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Calc. |
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Expt. [2] |
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35Cl |
Xaa |
- |
44.62 |
- |
44.174(12) |
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Xbb |
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11.64 |
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10.876(12) |
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Xcc |
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32.98 |
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33.298(12) |
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Xab |
± |
48.50 |
± |
48.181(39) |
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RMS |
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0.54 (1.8 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.58 |
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38.840(41) |
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Xyy |
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32.98 |
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33.298(12) |
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Xzz |
- |
72.56 |
- |
72.138(41) |
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ETA |
- |
0.091 |
- |
0.077 |
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Øz,a |
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29.94 |
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30.13(1) |
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Øa,CCl |
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30.14 |
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30.14 * |
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Øz,CCl |
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0.20 |
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0.01 * |
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37Cl |
Xaa |
- |
34.73 |
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Xbb |
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8.86 |
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Xcc |
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25.87 |
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Xab |
± |
38.40 |
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RSD |
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0.44 (1.1 %) |
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* Calculated here. |
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Table 3. Chlorine
nqcc's in 1,3-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 |
- |
44.34 |
- |
44.174(12) |
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Xbb |
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11.33 |
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10.876(12) |
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Xcc |
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33.01 |
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33.298(12) |
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Xab |
± |
48.68 |
± |
48.181(39) |
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RMS |
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0.33 (1.1 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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39.58 |
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38.840(41) |
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Xyy |
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33.01 |
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33.298(12) |
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Xzz |
- |
72.59 |
- |
72.138(41) |
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ETA |
- |
0.091 |
- |
0.077 |
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Øz,a |
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30.12 |
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30.13(1) |
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Øa,CCl |
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30.20 |
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30.20 * |
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Øz,CCl |
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0.09 |
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0.07 * |
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37Cl |
Xaa |
- |
34.95 |
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Xbb |
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8.93 |
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Xcc |
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26.02 |
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Xab |
± |
38.37 |
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RSD |
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0.44 (1.1 %) |
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* Calculated here. |
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The nqcc z-axis makes an angle of 0.09o with the CCl
bond axis. In 1,3-chlorofluorobenzene, this angle is 0.06o.
On the other hand, in 1,2-dichlorobenzene and 1,2-chlorofluorobenzene, this
angle is 1.21o and 1.07o respectively. (Calculated
nqcc's, ropt structures.) |
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| Table 4. Molecular structure parameters (Å and degrees). |
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ro
[3] |
roalpha [4] |
ropt |
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C(1,3)Cl(1,3) |
1.719 |
1.7355 |
1.7328 |
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C(2)C(3) |
1.394 |
1.388 |
1.3894 |
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C(3)C(4) |
1.403 |
1.392 |
1.3895 |
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C(4)C(5) |
1.389 |
1.404 |
1.3893 |
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C(2)H(2) |
1.085 |
1.091 |
1.0820 |
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C(4)H(4) |
1.086 |
1.085 |
1.0827 |
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C(5)H(5) |
1.081 |
1.091 |
1.0845 |
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C(1)C(2)C(3) |
120.0 |
118.1 |
118.23 |
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C(2)C(3)C(4) |
120.1 |
122.3 |
121.58 |
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C(3)C(4)C(5) |
119.4 |
118.1 |
118.80 |
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C(4)C(5)C(6) |
121.0 |
121.1 |
121.01 |
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C(2)C(3)Cl(3) |
119.7 |
118.9 |
118.91 |
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C(3)C(4)H(4) |
118.3 |
121.2 |
120.00 |
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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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C(2) |
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0.0 |
- |
0.671624 |
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C(1,3) |
± |
1.192364 |
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0.041519 |
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C(4,6) |
± |
1.209210 |
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1.430904 |
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C(5) |
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0.0 |
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2.114947 |
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H(2) |
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0.0 |
- |
1.753623 |
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Cl(1,3) |
± |
2.689902 |
- |
0.830275 |
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H(4,6) |
± |
2.153383 |
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1.960849 |
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H(5) |
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0.0 |
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3.199447 |
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[1] M.Onda and I.Yamaguchi, J.Mol.Struct. 36,158(1977). |
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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, Nippon Kagaku Kaishi (Bull.Chem.Soc.Jpn.) 1476,11(1986). |
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[4] D.G.Anderson, S.Cradock, P.B.Liescheski, and D.W.H.Rankin, J.Mol.Struct.
216,181(1990). |
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M.Onda, M.Atsuki, J.Yamaguchi, K.Suga, and I.Yamaguchi, J.Mol.Struct. 295,101(1993): ro structure of 1,3-dichlorobenzene. |
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Chlorobenzene |
1,2-Chlorofluorobenzene |
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1,2-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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13DCB.html |
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Last
Modified 4 June 2003 |
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