N-Formylpiperidine

C₅H₁₀NC(=O)H

Nitrogen

Nuclear Quadrupole Coupling Constants

in N-Formylpiperidine

Nitrogen nqcc's in N-formylpiperidine 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. Structure parameters are given in Table 2, rotational constants in Table 3.

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 = (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. ¹⁴N nqcc's in N-Formylpiperidine (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		1.369		1.392		1.361(2)
X_bb		2.059		2.099		2.119(3)
X_cc	-	3.428	-	3.492	-	3.480(4)
X_ab		0.323		0.314
X_ac		1.614		1.612
X_bc	-	0.646	-	0.630

RMS		0.046 (1.3 %)		0.022 (0.64 %)
RSD		0.030 (1.3 %)		0.030 (1.3 %)

X_xx		1.818		1.835
X_yy		2.186		2.219
X_zz	-	4.004	-	4.054
ETA		0.092		0.095


Table 2. N-Formylpiperidine: B3P86/6-31G(3d,3p) and B3LYP/cc-pVTZ structure parameters (Å and degrees).


	N C,1,B1 C,2,B2,1,A1 C,3,B3,2,A2,1,D1,0 C,4,B4,3,A3,2,D2,0 C,1,B5,2,A4,3,D3,0 H,2,B6,1,A5,6,D4,0 H,2,B7,1,A6,6,D5,0 H,3,B8,2,A7,1,D6,0 H,3,B9,2,A8,1,D7,0 H,4,B10,3,A9,2,D8,0 H,4,B11,3,A10,2,D9,0 H,5,B12,4,A11,3,D10,0 H,5,B13,4,A12,3,D11,0 H,6,B14,1,A13,2,D12,0 H,6,B15,1,A14,2,D13,0 C,1,B16,6,A15,5,D14,0 H,17,B17,1,A16,6,D15,0 O,17,B18,1,A17,6,D16,0

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

	B1=1.45122595 B2=1.52519096 B3=1.52779013 B4=1.52812643 B5=1.4473617 B6=1.09939697 B7=1.09068187 B8=1.09423579 B9=1.09591565 B10=1.09816589 B11=1.09393169 B12=1.09443257 B13=1.09623065 B14=1.09997994 B15=1.09354343 B16=1.35498885 B17=1.1075096 B18=1.21504324 A1=110.55967399 A2=111.04740872 A3=110.85698447 A4=116.56515279 A5=108.90087787 A6=107.04730841 A7=109.30286058 A8=108.91474451 A9=109.32978794 A10=110.50063115 A11=110.7931758 A12=109.73817317 A13=109.33651093 A14=108.36656109 A15=122.4507002 A16=111.69837635 A17=125.71883745 D1=52.6529974 D2=-54.34235218 D3=-54.48366889 D4=66.34664376 D5=-177.06301761 D6=175.03032035 D7=-68.33612186 D8=66.11007999 D9=-177.01380552 D10=175.84227236 D11=-65.96215849 D12=-65.95142239 D13=177.36713157 D14=-124.49609714 D15=-0.06487281 D16=179.8243314	B1=1.45858335 B2=1.52962235 B3=1.53233043 B4=1.5327394 B5=1.45404401 B6=1.09666404 B7=1.08679672 B8=1.09173316 B9=1.09317362 B10=1.09527414 B11=1.09130075 B12=1.09193125 B13=1.09341489 B14=1.09716867 B15=1.09013538 B16=1.35785556 B17=1.10464979 B18=1.21505722 A1=110.7158537 A2=111.28605601 A3=110.98159825 A4=116.4741109 A5=108.89015811 A6=107.26228101 A7=109.23275091 A8=108.87701165 A9=109.30778223 A10=110.41680426 A11=110.68030734 A12=109.66022624 A13=109.34917847 A14=108.47858478 A15=122.38880519 A16=111.8450523 A17=125.89577141 D1=52.34478434 D2=-53.80363988 D3=-54.12958434 D4=66.69554168 D5=-176.68390791 D6=174.71591847 D7=-68.68263491 D8=66.70582387 D9=-176.39662409 D10=175.29404668 D11=-66.61355465 D12=-66.37923651 D13=176.8675324 D14=-125.6437068 D15=0.56443661 D16=-179.6040122


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

		B3P86	B3LYP	Expt. [1]

	A	3932.	3923.	3876.798(12)
	B	1555.	1540.	1557.7934(4)
	C	1233.	1220.	1237.4982(4)

N-Formylmorpholine

N-Formylpyrrolidine

[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 13 Nov 2017