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OC2H3CH2Cl |
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Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in (Chloromethyl)oxirane
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Complete nqcc tensors were determined by Heineking et al. [1] for both 35Cl and 37Cl in the two conformers of (chloromethyl)oxirane shown below: |
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CMO gauche I |
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CMO gauche II |
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Calculation of the
nqcc's was made here on molecular structures obtained by
MP2/6-311+G(d,p)
optimization.
These are compared with the experimental nqcc's 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. Øz,CCl (degrees) is the angle between the principal z-axis of the nqcc tensor and the CCl bond axis. ETA = (Xxx - Xyy)/Xzz. |
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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 of
the B1LYP/TZV(3df,2p) model for calculation of the nqcc's. |
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Table 1. Chlorine
nqcc's in CMO, gauche I (MHz). Calculation was made on the MP2/6-311+G(d,p) optimized structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
- |
37.13 |
- |
38.193(3) |
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Xbb |
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2.65 |
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4.0835 |
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Xcc |
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34.48 |
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34.1095 |
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Xab * |
- |
50.82 |
- |
49.79(9) |
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Xac * |
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11.72 |
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12.13(90) |
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Xbc * |
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9.08 |
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8.87(29) |
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RMS |
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1.05 (4.1 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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35.94 |
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35.81(78) |
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Xyy |
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37.90 |
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37.43(66) |
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Xzz |
- |
73.84 |
- |
73.24(34) |
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ETA |
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0.027 |
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Øz,CCl |
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0.45 |
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37Cl |
Xaa |
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29.50 |
- |
30.326(3) |
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Xbb |
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2.32 |
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3.431 |
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Xcc |
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27.18 |
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26.895 |
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Xab * |
- |
39.96 |
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39.13(4) |
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Xac * |
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9.24 |
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9.04(48) |
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Xbc * |
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7.12 |
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7.12(33) |
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RMS |
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0.81 (4.0 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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28.32 |
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27.77(56) |
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Xyy |
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29.87 |
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29.84(51) |
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Xzz |
- |
58.19 |
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57.62(19) |
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ETA |
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0.027 |
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Øz,CCl |
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0.45 |
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* The algebraic signs of the
off-diagonal components depend on the orientation of the molecule
with respect to the positive/negative sense of the a,b,c axes. Here, the algebraic signs correspond
to the atomic a,b,c coordinates given in Table 4. |
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Table 2. Chlorine
nqcc's in CMO, gauche II (MHz). Calculation was made on the MP2/6-311+G(d,p) optimized structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
- |
41.39 |
- |
41.0538(13) |
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Xbb |
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8.20 |
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8.0246 |
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Xcc |
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33.19 |
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33.0292 |
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Xab * |
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47.26 |
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46.91(4) |
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Xac * |
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15.58 |
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15.17(24) |
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Xbc * |
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10.39 |
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10.07(10) |
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RMS |
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0.24 (0.87 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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35.80 |
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35.53(25) |
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Xyy |
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37.46 |
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37.05(20) |
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Xzz |
- |
73.26 |
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72.59(12) |
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ETA |
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0.023 |
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Øz,CCl |
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0.30 |
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37Cl |
Xaa |
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32.84 |
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32.5791(23) |
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Xbb |
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6.66 |
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6.53155 |
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Xcc |
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26.18 |
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26.04755 |
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Xab * |
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37.15 |
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36.85(2) |
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Xac * |
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12.26 |
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12.13(32) |
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Xbc * |
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8.13 |
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7.77(20) |
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RMS |
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0.18 (0.85 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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28.21 |
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27.13(40) |
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Xyy |
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29.52 |
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31.19(36) |
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Xzz |
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57.74 |
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58.32(19) |
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ETA |
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0.023 |
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Øz,CCl |
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0.30 |
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| Table 3. Heavy atom structure parameters, MP2/6-311+G(d,p) ropt (Å
and degrees). Complete molecular structure parameters are given here in Z-matrix format. |
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| CMO gauche I |
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C(1)C(2) |
1.4699 |
| C(2)O |
1.4301 |
| OC(1) |
1.4377 |
| C(2)C(7) |
1.4966 |
| C(7)Cl |
1.7843 |
| OC(2)C(1) |
59.42 |
| C(2)C(1)O |
58.91 |
| C(1)OC(2) |
61.67 |
| C(1)C(2)C(7) |
120.41 |
| C(2)C(7)Cl |
110.42 |
| H(6)C(2)C(7)Cl |
57.79 |
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| CMO gauche II |
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C(1)C(2) |
1.4652 |
| C(2)O |
1.4343 |
| OC(1) |
1.4420 |
| C(2)C(7) |
1.5005 |
| C(7)Cl |
1.7845 |
| OC(2)C(1) |
59.64 |
| C(2)C(1)O |
59.12 |
| C(1)OC(2) |
61.25 |
| C(1)C(2)C(7) |
120.66 |
| C(2)C(7)Cl |
109.54 |
| H(6)C(2)C(7)Cl |
60.55 |
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| Table 4. (Chloromethyl)oxirane. Heavy atom coordinates, ropt. 35Cl species. |
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| CMO gauche I |
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a (Å) |
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b (Å) |
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c (Å) |
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C(1) |
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2.2098 |
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0.3499 |
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0.0501 |
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C(2) |
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0.8494 |
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0.1964 |
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0.4848 |
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O |
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1.4918 |
- |
0.8877 |
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0.1914 |
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C(7) |
- |
0.3164 |
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0.8158 |
- |
0.2204 |
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Cl |
- |
1.7821 |
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0.1751 |
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0.0111 |
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| CMO gauche II |
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C(1) |
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1.6734 |
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0.9014 |
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0.2028 |
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C(2) |
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0.8158 |
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0.0850 |
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0.4591 |
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O |
- |
2.1228 |
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0.4539 |
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0.0020 |
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C(7) |
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0.3175 |
- |
0.7328 |
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0.2810 |
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Cl |
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1.8252 |
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0.1707 |
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0.0266 |
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| Table 5. (Chloromethyl)oxirane. Rotational constants (MHz). 35Cl species. |
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Calc., ropt |
Expt. [1] |
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CMO gauche I |
A |
13 258.0 |
13 372.7536(16) |
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B |
2 101.5 |
2 080.4258(5) |
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C |
1 947.3 |
1 932.4577(4) |
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CMO gauche II |
A |
13 202.5 |
13 143.9390(6) |
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B |
2 029.0 |
2 031.06521(17) |
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C |
1 889.4 |
1 889.75326(9) |
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[1] N.Heineking, J.-U.Grabow, and I.Merke, J.Mol.Struct. 612,231(2002). |
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M.A.Mohammadi and W.V.F.Brooks, J.Mol.Spectrosc. 78,89(1979).
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(Chloromethyl)cyclopropane |
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Table of Contents |
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Molecules/Chlorine |
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cycOC2H3CH2Cl.html |
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Last
Modified 22 Jan 2006 |
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