N-Nitrosopyrrolidine

C₄H₈NN=O

Nitrogen

Nuclear Quadrupole Coupling Constants

in N-Nitrosopyrrolidine

Nitrogen nqcc's in N-nitrosopyrrolidine were determined by Lou et al. [1].

Calculation of the nqcc's was made here on molecular structures derived by B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ optimization. Calculated and experimental nqcc's are compared in Tables 1 and 2. Structure parameters are given in Table 3, rotational constants in Table 4.

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. ETA = (X_xx - X_yy)/X_zz.

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 B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.


Table 1. Amino ¹⁴N nqcc's in N-Nitrosopyrrolidine (MHz). Calculation was made on r_opt structures given by (1) B3P86/6-31G(3d,3p) and (2) B3LYP/cc-pVTZ optimization.

		Calc. (1)		Calc. (2)		Expt. [1]

X_aa		2.113		2.128		2.136(7)
X_bb		1.785		1.808		1.863(21)
X_cc	-	3.899	-	3.936	-	3.999(22)
X_ab		0.391		0.395
X_ac	-	0.429	-	0.411
X_bc		0.299		0.300

RMS		0.074 (2.8 %)		0.049 (1.8 %)
RSD		0.030 (1.3 %)		0.030 (1.3 %)

X_xx		1.566		1.583
X_yy		2.380		2.399
X_zz	-	3.946	-	3.982
ETA		0.206		0.205


Table 2. Nitroso ¹⁴N nqcc's in N-Nitrosopyrrolidine (MHz). Calculation was made on r_opt structures given by (1) B3P86/6-31G(3d,3p) and (2) B3LYP/cc-pVTZ optimization.

		Calc. (1)		Calc. (2)		Expt. [1]

X_aa		1.791		1.821		1.787(8)
X_bb	-	5.438	-	5.470	-	5.362(27)
X_cc		3.647		3.649		3.575(28)
X_ab	-	1.580	-	1.542
X_ac		0.024		0.014
X_bc	-	0.273	-	0.301

RMS		0.060 (1.7 %)		0.078 (2.2 %)
RSD		0.030 (1.3 %)		0.030 (1.3 %)

X_xx		2.117		2.130
X_yy		3.658		3.661
X_zz	-	5.775	-	5.791
ETA		0.267		0.264


Table 3. N-Nitrosopyrrolidine: B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ structure parameters (Å and degrees).


	C C,1,B1 C,2,B2,1,A1 C,3,B3,2,A2,1,D1,0 N,4,B4,3,A3,2,D2,0 H,1,B5,5,A4,4,D3,0 H,1,B6,5,A5,4,D4,0 H,2,B7,1,A6,5,D5,0 H,2,B8,1,A7,5,D6,0 H,3,B9,2,A8,1,D7,0 H,3,B10,2,A9,1,D8,0 H,4,B11,3,A10,2,D9,0 H,4,B12,3,A11,2,D10,0 N,5,B13,4,A12,3,D11,0 O,14,B14,5,A13,4,D12,0

	B3P86/6-31G(3d,3p)	B3LYP/cc-pVTZ

	B1=1.52718159 B2=1.53440146 B3=1.53038059 B4=1.46023311 B5=1.09039999 B6=1.09650368 B7=1.09398598 B8=1.09110012 B9=1.09091076 B10=1.09382614 B11=1.09547821 B12=1.09232148 B13=1.3128116 B14=1.22486024 A1=103.13787238 A2=104.21643995 A3=102.63384421 A4=109.99166285 A5=110.4031736 A6=109.79612134 A7=112.52196493 A8=112.95805706 A9=109.95884988 A10=113.46444344 A11=114.34316511 A12=124.09005096 A13=114.17440901 D1=37.16192961 D2=-25.74457099 D3=140.28331426 D4=-100.11910919 D5=84.27775113 D6=-155.45087139 D7=159.22859957 D8=-80.63239091 D9=91.63520867 D10=-145.25942193 D11=177.74213399 D12=3.95350957	B1=1.53095524 B2=1.53885646 B3=1.53403549 B4=1.46741313 B5=1.08746798 B6=1.09384432 B7=1.09137059 B8=1.08842586 B9=1.08834569 B10=1.09128455 B11=1.0923893 B12=1.089176 B13=1.31458424 B14=1.22634295 A1=103.22132511 A2=104.23657086 A3=102.75138828 A4=110.07321268 A5=110.41498735 A6=109.79836927 A7=112.51570035 A8=112.9214374 A9=109.93081578 A10=113.2128364 A11=114.13593131 A12=124.51118684 A13=114.68105052 D1=36.99430834 D2=-25.85862908 D3=139.71098571 D4=-100.67213572 D5=84.58852078 D6=-155.13400627 D7=159.0306784 D8=-80.81866889 D9=91.60831124 D10=-145.46043942 D11=178.15846181 D12=4.00859468


Table 4. N-Nitrosopyrrolidine: Rotational Constants (MHz); B3P86/6-31G(3d,3p), B3LYP/cc-pVTZ, and Experimental.

		B3P86	B3LYP	Expt. [1]

	A	6143.	6126.	6061.41(20)
	B	2082.	2063.	2077.557(5)
	C	1650.	1636.	1650.531(5)

N-Formylpyrrolidine

N-Nitrosomorpholine

[1] Q.Lou, K.W.Hwang, X.Z.Liu, C.Sahi, R.K.Bohn, and C.W.Bock, J.Mol.Struct. 445,117(1998).

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Last Modified 11 Nov 2017