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CH2CH2CH2CHCl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in Cyclobutyl Chloride
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Calculation of the
chlorine nqcc's in equatorial cyclobutyl chloride was made on the
effective structure of Kim and Gwinn [1], and on
a structure obtained by B3P86/6-31G(3d,3p) optimization (with and
without correction of the C-Cl bond length - see below). These
are compared with the experimental nqcc's [1,2] in Tables 1 - 3.
Structure parameters are compared in Table 4. |
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In Tables 1 - 3, subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. Ø (degrees) is the angle between its subscripted parameters. 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 chlorine nqcc's. |
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Table 1. 35Cl
nqcc's in Cyclobutyl Chloride (MHz). Calculation was made on the ro
structure [1]. |
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Calc.
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Expt. [1] |
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Expt. [2] |
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Xaa |
- |
58.20 |
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56.58(10) |
- |
56.052(3) |
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Xbb |
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34.94 |
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32.98 |
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32.667 |
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Xcc |
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23.26 |
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23.60(10) |
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23.385 |
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|Xac| |
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33.85 |
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32.0(6) |
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RMS |
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1.48 (3.9 %) |
1.81 (4.8 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Table 2. 35Cl
nqcc's in Cyclobutyl Chloride (MHz). 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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Expt. [2] |
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Xaa |
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57.74 |
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56.58(10) |
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56.052(3) |
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Xbb |
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33.39 |
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32.98 |
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32.667 |
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Xcc |
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24.35 |
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23.60(10) |
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23.385 |
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|Xac| |
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31.81 |
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32.0(6) |
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RMS |
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0.83 (2.2 %) |
1.20 (3.2 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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That the calculated
nqcc's are uniformly greater (in magnitude) than the experimental
values suggests that the optimized CCl bond length 1.7872 Å is too long. Thus,
the structure was optimized at the MP2/6-311+G(2d,p) level of theory
and the CCl bond length corrected according to the method of Merke et
al. [3]. This corrected CCl bond length is 1.7746 Å.
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Table 3. 35Cl
nqcc's in Cyclobutyl Chloride (MHz). Calculation was made on the B3P86/6-31G(3d,3p) ropt
structure but with CCl = 1.7746 Å. |
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Calc.
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Expt. [1] |
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Expt. [2] |
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Xaa |
- |
57.37 |
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56.58(10) |
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56.052(3) |
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Xbb |
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33.18 |
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32.98 |
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32.667 |
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Xcc |
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24.18 |
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23.60(10) |
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23.385 |
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|Xac| |
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31.77 |
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32.0(6) |
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RMS |
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0.58 (1.5 %) |
0.94 (2.5 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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35.10 |
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Xyy |
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33.18 |
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Xzz |
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68.28 |
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ETA |
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0.028 |
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Øz,a |
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18.96 |
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Øa,CCl |
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17.99 |
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Øz,CCl |
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0.97 |
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| Table 4. Cyclobutyl Chloride. Heavy atom structure parameters (Å
and degrees). ropt
is B3P86/6-31G(3d,3p). Complete ropt structure is given here in Z-matrix format. |
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ro [1] |
ropt |
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ClC(2) |
1.775(5) |
1.7872 |
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1.7746 * |
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C(2)C(3) |
1.525(5) |
1.5331 |
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C(2)C(5) |
1.550(5) |
1.5473 |
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Cl-C(3)C(2)C(4) |
135(1) |
131.93 |
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C(3)C(2)C(4) |
90.8(5) |
89.53 |
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"pucker" |
20(1) |
29.35 |
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Pucker is the angle between the C(3)C(2)C(4) and C(3)C(5)C(4) planes. |
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* Corrected MP2/6-311+G(2d,p) CCl bond length. |
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[1] H.Kim and W.D.Gwinn, J.Chem.Phys. 44,865(1966). |
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[2] R.Subramanian, J.M.Szarko, W.C.Pringle, and S.E.Novick, J.Mol.Struct. 742,165(2005). |
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[3] I.Merke, L.Poteau, G.Wlodarczak,
A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996). |
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Table of Contents |
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Molecules/Chlorine |
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CH23CHCl.html |
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Last
Modified 2 Aug 2007 |
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