|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
C7H13N |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Nitrogen |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in
1-Asabicyclo[2.2.2.]octane
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
The nitrogen nqcc in
1-asabicyclo[2.2.2.]octane (aka quinuclidine) was measured by Vormann
and Dreizler [1].
A heavy atom substitution structure was determined by Consalvo
and Stahl [2]. Calculation of the nqcc was made here on this
structure complemented here with MP2/6-31G(d,p) optimization for
the C-H geometry, and on several ab
initioand
HF-DFT optimized structures. These are compared with the
experimental nqcc in Table 1. Parameters for the substitution and
B3P86/6-31G(3d,3p) optimized structures are given in Table 2.
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
Table 1.
Nitrogen
nqcc's in 1-Asabicyclo[2.2.2.]octane, and Rotational Constant B.
Calculation was made on the substitution structure [2], and on
structures given by Method/Basis
optimization (column 1). |
|
|
|
|
|
|
|
| |
|
|
eQq (MHz) |
B (MHz)
|
|
| |
|
|
|
|
|
|
Experimental [1] |
- |
5.1915(36) |
2425.56577(33) |
|
|
|
|
|
|
|
|
Substitution Structure |
- |
5.174 |
2440.5 |
|
|
|
|
|
|
|
| |
Method/6-31G(d,p) |
|
Calc. |
Calc. |
|
|
|
|
|
|
|
|
HF |
- |
5.293 |
2443.9 |
|
|
B3LYP |
- |
5.217 |
2533.9 |
|
|
B1LYP |
- |
5.227 |
2535.5 |
|
|
B3P86 |
- |
5.205 |
2559.3 |
|
|
B3PW91 |
- |
5.209 |
2552.6 |
|
| |
mPW1PW91 |
-
|
5.208
|
2561.8
|
|
|
PBE1PBE |
- |
5.204 |
2563.3 |
|
|
MP2 |
- |
5.121 |
2563.4 |
|
|
|
|
|
|
|
|
Method/6-31G(3d,3p) |
|
|
|
|
|
|
|
|
|
|
|
HF |
- |
5.278 |
2445.9 |
|
|
B3LYP |
- |
5.244 |
2417.1 |
|
|
B1LYP |
- |
5.248 |
2418.4 |
|
|
B3P86 |
- |
5.200 |
2563.4 |
|
|
B3PW91 |
- |
5.223 |
2556.6 |
|
|
mPW1PW91 |
- |
5.219 |
2565.8 |
|
|
PBE1PBE |
- |
5.214 |
2567.2 |
|
|
|
|
|
|
|
|
Method/6-311G(3d,3p) |
|
|
|
|
|
|
|
|
|
|
|
HF |
- |
5.275 |
2448.6 |
|
|
B3P86 |
- |
5.214 |
2444.3 |
|
|
mPW1PW91 |
- |
5.207 |
2447.1 |
|
|
PBE1PBE |
- |
5.201 |
2448.2 |
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Several optimization models give
structures - most importantly, NC bond lengths and CNC angles - on
which
good agreement is obtained between calculated and experimental nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
| Table 2.
1-Asabicyclo[2.2.2.]octane. Substitution, rs and
B3P86/6-31G(3d,3p) optimized, ropt
structures. Heavy atom parameters (Å and degrees).
Complete structures are given here
in Z-matrix format. |
|
|
|
|
|
|
|
|
|
|
rs [2] |
ropt |
|
|
|
|
|
|
|
|
NC(2) |
1.466(7) |
1.4619 |
|
C(2)C(5) |
1.552(14) |
1.5534 |
|
C(5)C(8) |
1.529(7) |
1.5326 |
|
N - - - C(8) |
2.5798 * |
2.5692 |
|
C(2)NC(3) |
109.11 * |
109.40 |
|
NC(2)C(5) |
111.85(53) |
111.80 |
| |
C(2)C(5)C(8) |
108.32(55) |
107.90 |
|
|
|
|
|
|
|
|
|
|
* Derived here. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] K.Vormann and H.Dreizler,
J.Mol.Struct. 190,489(1988). |
|
|
[2] D.Consalvo and W.Stahl,
J.Mol.Struct. 447,119(1998). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
(CH3)3N |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
C7H13N.html |
|
|
|
|
|
|
Last
Modified 25 March 2006 |
|
|
|
|
|
|
|
|
|
|
