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C(=O)H-NC4H8 |
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Nitrogen |
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Nuclear
Quadrupole Coupling Constants |
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in N-Formylpyrrolidine
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(1-Pyrrolidinecarboxaldehyde) |
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The microwave spectrum of N-Formylpyrrolidine was assigned and analyzed by Lee et al. [1].
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Calculation was made here of
the N nqcc tensor on ropt molecular structures given
by B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ optimization.
These nqcc's are compared with experimental values [1] in Table 1. Structure parameters are
given in Table 2, rotational constants and dipole moments in Table 3. |
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In Table 1,
subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. ETA = (Xxx - Xyy)/Xzz. RMS is the root mean
square difference between calculated and experimental diagonal nqcc's
(percent of average absolute experimental nqcc). RSD is the
calibration residual standard deviation of the B3PW91/6-311+G(df,pd)
model for calculation of nitrogen efg's/nqcc's. |
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Table 1. 14N
nqcc's in N-Formylpyrrolidine
(MHz). Calculation was made on (1) B3P86/6-31G(3d,3p) and (2) B3LYP/cc-pVTZ optimized molecular structures. |
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Calc (1) |
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Calc (2) |
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Expt [1]
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Xaa |
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1.703
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1.721
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1.747(2)
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Xbb |
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2.448
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2.477
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2.500(3)
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Xcc |
- |
4.151
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-
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4.198
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-
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4.247(4)
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Xab |
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0.223
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-
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0.218
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Xac |
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0.329
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0.320
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Xbc |
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0.481
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-
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0.488
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RMS
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0.068 (2.4 %)
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0.034 (1.2 %)
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RSD
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xxx |
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1.647 |
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1.668
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Xyy |
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2.555 |
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2.581
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Xzz |
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4.202 |
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4.249
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ETA |
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0.216 |
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0.215
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| Table 2. N-Formylpyrrolidine. Selected structure parameters (Å
and degrees). ropt(1) = B3P86/6-31G(3d,3p) and ropt(2)
= B3LYP/cc-pVTZ optimized molecular structures.
Complete structures are given here
in Z-matrix format. |
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ropt(1) |
ropt(2) |
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| NC(1) |
1.4584
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1.4646
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| NC(4) |
1.4606
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1.4873
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| NC(14) |
1.3471
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1.3497
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C(1)NC(4)
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112.90
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112.66
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C(1)NC(14)
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125.36
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125.21
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C(4)NC(14)
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121.64
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122.03
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| C(1)NC(14)=O
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178.22
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178.22
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C(4)NC(14)=O
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2.24
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2.22
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| Table 3. N-Formylpyrrolidine.
Rotational constants (MHz) and dipole moments (D). ropt(1)
= B3P86/6-31G(3d,3p) and ropt(2) = B3LYP/cc-pVTZ
optimized molecular structures.
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ropt(1) |
ropt(2) |
Expt [1]
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A |
6154.4
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6135.3
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6097.2012(24)
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B |
1961.4
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1946.8
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1957.5059(4)
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C |
1571.6
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1560.4
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1570.7053(4)
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|µa| |
4.29
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4.48
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4.24(2)
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|µb| |
1.37
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1.43
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1.28(3)
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|µc| |
0.21
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0.21
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0.60(6)
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[1] S.G.Lee, K.W.Hwang, R.K.Bohn, K.W.Hillig II, and R.L.Kuczkowski, Acta Chem. Scand. A 42,603(1988).
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Pyrrolidine |
N-Me-Pyrrolidine |
Nicotine
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Table of Contents |
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Molecules/Nitrogen |
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NCHOPRL.html |
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Last
Modified 20 June 2014 |
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