N-Nitrosomorpholine

OC₄H₈NN=O

Nitrogen

Nuclear Quadrupole Coupling Constants

in N-Nitrosomorpholine

Nitrogen nqcc's in N-nitrosomorpholine 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-Nitrosomorpholine (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		1.914		1.952		1.930(3)
X_bb		1.454		1.501		1.534(6)
X_cc	-	3.368	-	3.453	-	3.464(7)
X_ab	-	0.260	-	0.280
X_ac	-	1.708	-	1.680
X_bc		0.653		0.618

RMS		0.073 (3.2 %)		0.027 (1.2 %)
RSD		0.030 (1.3 %)		0.030 (1.3 %)

X_xx		1.338		1.370
X_yy		2.591		2.612
X_zz	-	3.929	-	3.982
ETA		0.319		0.312


Table 2. Nitroso ¹⁴N nqcc's in N-Nitrosomorpholine (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		2.060		2.081		2.059(3)
X_bb	-	5.373	-	5.412	-	5.282(6)
X_cc		3.313		3.330		3.223(7)
X_ab		1.041		1.024
X_ac		0.579		0.559
X_bc	-	1.397	-	1.339

RMS		0.074 (2.1 %)		0.098 (2.8 %)
RSD		0.030 (1.3 %)		0.030 (1.3 %)

X_xx		2.105		2.122
X_yy		3.648		3.643
X_zz	-	5.753	-	5.765
ETA		0.268		0.264


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


	N C,1,B1 C,2,B2,1,A1 C,1,B3,2,A2,3,D1,0 C,1,B4,2,A3,3,D2,0 H,2,B5,1,A4,5,D3,0 H,2,B6,1,A5,5,D4,0 H,3,B7,2,A6,1,D5,0 H,3,B8,2,A7,1,D6,0 H,4,B9,1,A8,5,D7,0 H,4,B10,1,A9,5,D8,0 H,5,B11,1,A10,2,D9,0 H,5,B12,1,A11,2,D10,0 N,1,B13,5,A12,4,D11,0 O,14,B15,1,A14,5,D13,0 O,3,B16,2,A15,1,D14,0

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

	B1=1.45010481 B2=1.52264322 B3=2.41699213 B4=1.44515583 B5=1.09623858 B6=1.09156969 B7=1.091499 B8=1.10033347 B9=1.09167403 B10=1.10078074 B11=1.0970199 B12=1.0919059 B13=1.33007251 B15=1.21748966 B16=1.41440148 A1=108.70253913 A2=91.54060605 A3=117.78963247 A4=109.23223707 A5=107.19419588 A6=110.46946793 A7=109.68043031 A8=144.44754229 A9=94.86827502 A10=109.5863715 A11=107.56233032 A12=117.89520643 A14=115.7615631 A15=111.44261024 D1=-21.38975891 D2=-48.00129937 D3=72.31620198 D4=-169.7192788 D5=170.41742333 D6=-69.84511756 D7=13.91258365 D8=-118.48510613 D9=-71.07954336 D10=170.47246842 D11=-128.11117843 D13=178.88472765 D14=52.0825215	B1=1.45800094 B2=1.52660025 B3=2.42830436 B4=1.45133415 B5=1.09381286 B6=1.08758777 B7=1.08871561 B8=1.09731403 B9=1.08886353 B10=1.09773922 B11=1.09453074 B12=1.08870076 B13=1.3329739 B15=1.21846638 B16=1.42148985 A1=108.87515617 A2=91.54404897 A3=117.6072496 A4=109.2148516 A5=107.64509707 A6=110.38963621 A7=109.64298572 A8=144.28655365 A9=95.07139195 A10=109.62062504 A11=107.76660171 A12=117.87885523 A14=116.12699523 A15=111.63140145 D1=-21.49788464 D2=-48.05293222 D3=72.29022907 D4=-169.70710226 D5=170.03926649 D6=-70.27625159 D7=14.35511049 D8=-118.2257979 D9=-71.00099861 D10=170.5625164 D11=-130.01822117 D13=-179.85863397 D14=51.68084618


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

		B3P86	B3LYP	Expt. [1]

	A	4288.	4278.	4265.625(31)
	B	1624.	1604.	1610.5746(9)
	C	1289.	1271.	1277.8064(8)

N-Formylmorpholine

N-Nitrosopyrrolidine

[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 12 Nov 2017