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ISSN: 2056-9890

The dipolar cyclo­addition of methyl acrylate to 5,6-di­ethyl-1-methyl-3-oxidopyrazinium

aThe School of Chemistry, The University of Manchester, Manchester M13 9PL, England
*Correspondence e-mail: john.joule@manchester.ac.uk

(Received 26 April 2006; accepted 9 May 2006; online 12 May 2006)

5,6-Diethyl­pyrazin-2-one reacts with iodo­methane to give a quaternary salt, deprotonation of which, in situ, liberates a 3-oxidopyrazinium which undergoes a 1,3-dipolar cyclo­addition with methyl acrylate to form methyl (Z)-5-ethyl-4-ethyl­idene-8-methyl-2-oxo-3,8-diaza­bicyclo­[3.2.1]octane-6-endo-6-carb­oxyl­ate. The crystal structure revealed (i) the existence of the imine product as its enamine tautomer, (ii) the Z geometry of the exocyclic double bond, and (iii) the endo orientation of the ester group. Pairwise hydrogen bonding between the NH H atom and the amide carbonyl group links the molecules into centrosymmetric dimers.

Comment

In our investigations of the 1,3-dipolar cyclo­addition chemistry of 3-oxidopyraziniums (Kiss et al., 1987[Kiss, M., Russell-Maynard, J. & Joule, J. A. (1987). Tetrahedron Lett. 28, 2187-2190.]; Allway et al., 1990[Allway, P. A., Sutherland, J. K. & Joule, J. A. (1990). Tetrahedron Lett. 31, 4781-4783.]; Yates et al., 1995[Yates, N. D., Peters, D. A., Allway, P. A., Beddoes, R. L., Scopes, D. I. C. & Joule, J. A. (1995). Heterocycles, 40, 331-347.]; Helliwell et al., 2006[Helliwell, M., You, Y. & Joule, J. A. (2006). Acta Cryst. E62, o1293-o1294.]), we have demonstrated that these reactions efficiently produce bridged bicyclic systems – 3,8-diaza­bicyclo­[3.2.1]octa­nes – which comprise key structural components of such biologically active natural products as anti­cancer quinocarcin (Takahashi & Tomita, 1983[Takahashi, K. & Tomita, F. (1983). J. Antibiot. 36, 468-470.]; Tomita et al., 1983[Tomita, F., Takahashi, K. & Shimizu, K. (1983). J. Antibiot. 36, 463-467.]; Hirayama & Shirahata, 1983[Hirayama, N. & Shirahata, K. (1983). J. Chem. Soc. Perkin Trans. 2, pp. 1705-1708.]) and anti­biotic lemonomycin (He et al., 2000[He, H., Shen, B. & Carter, G. T. (2000). Tetrahedron Lett. 41, 2067-2071.]).

[Scheme 1]

In a series of benchmark papers by Katritzky and co-workers (for reviews, see Dennis et al., 1976[Dennis, N., Katritzky, A. R. & Takeuchi, Y. (1976). Angew. Chem. Int. Ed. Engl. 15, 1-9.]; Katritzky & Dennis, 1989[Katritzky, A. & Dennis, N. (1989). Chem. Rev. 89, 827-861.]) on the cyclo­additions of 3-oxidopyridiniums, there were no examples of adduct formation using dipoles in which either one or two substituents were located on the 1,3-dipole at the future ring-junction positions. We have shown that one methyl group, so located, is not deleterious to the cyclo­addition process using 1,5,6-trimethyl-3-oxidopyrazinium (Helliwell et al., 2006[Helliwell, M., You, Y. & Joule, J. A. (2006). Acta Cryst. E62, o1293-o1294.]). This report describes our investigation of the reactivity of 5,6-diethyl-1-methyl-3-oxidopyrazinium, (3), in which a larger ethyl group is located at one of the future ring-junction positions and, in addition, this group is adjacent to another relatively bulky ethyl group.

5,6-Diethyl­pyrazin-2-one, (1), was prepared by the condensation of hexane-3,4-dione with glycinamide following the established method (Jones, 1949[Jones, R. G. (1949). J. Am. Chem. Soc. 71, 78-81.]; Karmas & Spoerri, 1952[Karmas, G. & Spoerri, P. E. (1952). J. Am. Chem. Soc. 74, 1580-1584.]; Yates et al., 1995[Yates, N. D., Peters, D. A., Allway, P. A., Beddoes, R. L., Scopes, D. I. C. & Joule, J. A. (1995). Heterocycles, 40, 331-347.]). Reaction of (1) with iodo­methane produced the methio­dide (2), treatment of which with triethyl­amine allowed the generation of the zwitterion (3), in situ, and in the presence of methyl acrylate. As in all previous cases, the immediate products of such cyclo­additions [(4) in this case] are not isolated but tautomerize to the more stable enamide structures, (5) in this case. Thus, the presence of even an ethyl group at a future ring-junction position does not prevent cyclo­addition. It is noteworthy that, with increasing bulk, a greater proportion of endo isomer is formed, actually the only stereoisomer isolated in this case. The Z stereochemistry of the exocyclic double bond was established by the crystal structure study. Suitable crystals of the adduct were examined crystallographically, confirming the structure and stereochemistry (Fig. 1[link]). Intermolecular hydrogen bonding between the NH H atom and the amide carbonyl group leads to the formation of centrosymmetric dimers (Table 1[link]).

[Figure 1]
Figure 1
The molecular structure of (5), with displacement ellipsoids drawn at the 50% probability level.

Experimental

To hexane-3,4-dione (4.80 g, 0.04 mol) in water (5 ml) was added sodium metabisulfite (7.60 g, 0.04 mol) and the mixture stirred for 1 h at room temperature. An addition compound was precipitated as a gummy solid on addition of methanol (18 ml) and ethanol (6 ml) and separated by filtration. The solid was dissolved in water (5 ml) and glycinamide hydro­chloride (2.27 g, 0.02 mol) was added. The pH was then adjusted to 8 with 10 M KOH and the mixture maintained at 333–353 K for 2 h. The pH was adjusted to 10 and the mixture kept at 323–333 K for 30 min. The mixture was cooled and adjusted to pH 6 with concentrated HCl, then cooled to 273 K. 5,6-Diethyl­pyrazin-3-one was precipitated as square white crystals (1.34 g, 44%; m.p. 443–445 K), δH (300 MHz, CDCl3) 1.26 (3H, t, J = 7.5 Hz, CH2CH3), 1.34 (3H, t, J = 7.5 Hz, CH2CH3), 2.63 (2H, q, J = 7.5 Hz, CH2CH3), 2.66 (2H, q, J = 7.5 Hz, CH2CH3), 8.07 (1H, s, H-2), 13.32 (1H, s, NH); analysis found: C 62.64, H 7.95, N 16.25%; C8H12N2O requires C, 63.13; H, 7.95; N, 18.41%.

5,6-Diethyl­pyrazin-2-one (500 mg, 3.3 mmol) and iodo­methane (1.2 ml, 16.5 mmol) were heated under reflux in acetonitrile (25 ml) under N2 for 24 h. The solvent was removed under vacuum. The residue was extracted with CH2Cl2 and the solid was filtered off to give the methio­dide as a greenish crystalline solid (548 mg, 57%) which was used in the next step without further purification: Analysis: δH (300 MHz, D2O) 1.20 (3H, t, J = 7.6 Hz, CH2CH3), 1.25 (3H, t, J = 7.6 Hz, CH2CH3), 2.80 (2H, q, J = 7.6 Hz, CH2CH3), 2.90 (2H, q, J = 7.6 Hz, CH2CH3), 4.20 (3H, s, NCH3), 8.15 (1H, s, H-2).

A solution of 1-methyl-5,6-diethyl­pyrazin-3-onium iodide (100 mg, 0.725 mmol) with triethyl­amine (0.22 ml, 1.45 mmol) and methyl acrylate (0.33 ml, 3.63 mmol) in dry acetonitrile (5 ml) was heated at reflux for 1.5 h to give an orange solution. The solvent and excess methyl acrylate were evaporated under vacuum. From the residue a pure sample of methyl 5-ethyl-8-methyl-(Z)-4-ethyl­idene-2-oxo-3,8-diaza­bicyclo­[3.2.1]octane-6-endo-6-carboxyl­ate was obtained by flash chromatography (silica, n-hexa­ne–EtOAc 7:3) as colourless plates (15 mg, 9%). Analysis: δH (300 MHz, CDCl3) 1.01 (3H, t, J = 7 Hz, CH2CH3), 1.56 (3H, d, J = 7 Hz, CHCH3), 1.02 1.66 (1H, m, one of CH2CH3), 2.13 1.03 (1H, m, one of CH2CH3), 2.25 (3H, s, NCH3), 1.04 2.33 (1H, m, H-7), 2.48 (1H, dd, J = 5, 13 Hz, H-7), 1.05 3.21 (1H, dd, J = 5, 11 Hz, H-6), 3.58 (1H, d, J = 8 Hz, H-1), 1.06 3.64 (3H, s, OCH3), 4.53 (1H, q, J = 7 Hz, CHCH3), 1.07 6.95 (1H, s, NH).

Crystal data
  • C13H20N2O3

  • Mr = 252.31

  • Monoclinic, P 21 /c

  • a = 10.00 (2) Å

  • b = 8.842 (10) Å

  • c = 14.693 (10) Å

  • β = 90.36 (8)°

  • V = 1300 (3) Å3

  • Z = 4

  • Dx = 1.290 Mg m−3

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 (2) K

  • Plate, colourless

  • 0.4 × 0.3 × 0.2 mm

Data collection
  • Rigaku R-AXIS diffractometer

  • φ scans

  • Absorption correction: none

  • 10171 measured reflections

  • 2173 independent reflections

  • 1840 reflections with I > 2σ(I)

  • Rint = 0.042

  • θmax = 25.0°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.126

  • S = 1.06

  • 2173 reflections

  • 171 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.078P)2 + 0.2408P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O3i 0.89 (2) 2.10 (2) 2.975 (3) 170.9 (16)
Symmetry code: (i) -x+1, -y, -z+1.

H atoms bonded to carbon were included in calculated positions using the riding model, with C—H distances of 0.93–0.98 Å and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the other H atoms; H1 was found by difference Fourier methods and refined isotropically.

Data collection: MSC RAXIS11 Control Software (Molecular Structure Corporation, 1992[Molecular Structure Corporation (1992). MSC RAXIS11 Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.]); cell refinement: DENZO (Otwinowski & Minor, 1988[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter & R. M. Sweet, pp. 307-326. London: Academic Press.]); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985[Sheldrick, G. M. (1985). In Crystallographic Computing 3, edited by G. M. Sheldrick, C. Krüger & R. Goddard, pp. 175-189. Oxford University Press.]) and TEXSAN (Molecular Structure Corporation, 1995[Molecular Structure Corporation (1995). TEXSAN. Version 1.7. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL (Bruker, 2001[Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.]).

Supporting information


Comment top

In our investigations of the 1,3-dipolar cycloaddition chemistry of 3-oxidopyraziniums (Kiss et al., 1987; Allway et al., 1990; Yates et al., 1995; Helliwell et al., 2006), we have demonstrated that these reactions efficiently produce bridged bicyclic systems – 3,8-diazabicyclo[3.2.1]octanes – which comprise key structural components of such biologically active natural products as anticancer quinocarcin (Takahashi & Tomita, 1983; Tomita et al., 1983; Hirayama & Shirahata, 1983) and antibiotic lemonomycin (He et al., 2000).

In a series of benchmark papers by Katritzky and co-workers (for reviews, see Dennis et al., 1976; Katritzky & Dennis, 1989) on the cycloadditions of 3-oxidopyridiniums, there were no examples of adduct formation using dipoles in which either one or two substituents were located on the 1,3-dipole at the future ring-junction positions. We have shown that one methyl group, so located, is not deleterious to the cycloaddition process using 1,5,6-trimethyl-3-oxidopyrazinium (Helliwell et al., 2006). This report describes our investigation of the reactivity of 5,6-diethyl-1-methyl-3-oxidopyrazinium, (3), in which a larger ethyl group is located at one of the future ring-junction positions and, in addition, this group is adjacent to another relatively bulky ethyl group.

5,6-Diethylpyrazin-2-one, (1), was prepared by the condensation of hexane-3,4-dione with glycinamide following the established method (Jones, 1949; Karmas & Spoerri, 1952; Yates et al., 1995). Reaction of (1) with iodomethane produced the methiodide (2), treatment of which with triethylamine allowed the generation of the zwitterion (3), in situ, and in the presence of methyl acrylate. As in all previous cases, the immediate products of such cycloadditions [(4) in this case] are not isolated but tautomerize to the more stable enamide structures, (5) in this case. The Z stereochemistry of the exocyclic double bond was established by the crystal structure study. Suitable crystals of the adduct were examined crystallographically, confirming the structure and stereochemistry (Fig. 1). Thus, the presence of even an ethyl group at a future ring-junction position does not prevent cycloaddition. It is noteworthy that, with increasing bulk, a greater proportion of endo isomer is formed, actually the only stereoisomer isolated in this case.

Experimental top

To hexane-3,4-dione (4.80 g, 0.04 mol) in water (5 ml) was added sodium metabisulfite (7.60 g, 0.04 mol) and the mixture stirred for 1 h at room temperature. An addition compound was precipitated as a gummy solid on addition of methanol (18 ml) and ethanol (6 ml) and separated by filtration. The solid was dissolved in water (5 ml) and glycinamide hydrochloride (2.27 g, 0.02 mol) was added. The pH was then adjusted to 8 with 10 M KOH and the mixture maintained at 333–353 K for 2 h. The pH was adjusted to 10 and the mixture kept at 323–333 K for 30 min. The mixture was cooled and adjusted to pH 6 with concentrated HCl, then cooled to 273 K. 5,6-Diethylpyrazin-3-one was precipitated as square white crystals (1.34 g, 44%; m.p. 443–445 K), δH (300 MHz, CDCl3) 1.26 (3H, t, J = 7.5 Hz, CH2CH3), 1.34 (3H, t, J = 7.5 Hz, CH2CH3), 2.63 (2H,q, J = 7.5 Hz, CH2CH3), 2.66 (2H, q, J = 7.5 Hz, CH2CH3), 8.07 (1H, s, H-2), 13.32 (1H, s, NH); analysis found: C 62.64, H 7.95, N 16.25%; C8H12N2O requires C, 63.13; H, 7.95; N, 18.41%

5,6-Diethylpyrazin-2-one (500 mg, 3.3 mmol) and iodomethane (1.2 ml, 16.5 mmol) were heated under reflux in acetonitrile (25 ml) under N2 for 24 h. The solvent was removed under vacuum. The residue was extracted with CH2Cl2 and the solid was filtered off to give the methiodide as a greenish crystalline solid (548 mg, 57%) which was used in the next step without further purification: Analysis: δH (300 MHz, D2O) 1.20 (3H,t, J = 7.6 Hz, CH2CH3), 1.25 (3H, t, J = 7.6 Hz, CH2CH3), 2.80 (2H, q, J = 7.6 Hz, CH2CH3), 2.90 (2H, q, J = 7.6 Hz, CH2CH3), 4.20 (3H, s, NCH3), 8.15 (1H, s, H-2).

A solution of 1-methyl-5,6-diethylpyrazine-3-onium iodide (100 mg, 0.725 mmol) with triethylamine (0.22 ml, 1.45 mmol) and methyl acrylate (0.33 ml, 3.63 mmol) in dry acetonitrile (5 ml) was heated at reflux for 1.5 h to give an orange solution. The solvent and excess methyl acrylate were evaporated under vacuum. From the residue a pure sample of methyl 5-ethyl-8-methyl-(Z)-4-ethylidene-2-oxo-3,8-diazabicyclo[3.2.1]octane-6-endo- 6-carboxylate was obtained by flash chromatography (silica, n-hexane–EtOAc 7:3) as colourless plates (15 mg, 9%). Analysis: δH (300 MHz, CDCl3) 1.01 (3H, t, J = 7 Hz, CH2CH3), 1.56 (3H, d, J = 7 Hz, CHCH3), 1.02 1.66 (1H, m, one of CH2CH3), 2.13 1.03 (1H, m, one of CH2CH3), 2.25 (3H, s, NCH3), 1.04 2.33 (1H, m, H-7), 2.48 (1H, dd, J = 5, 13 Hz, H-7), 1.05 3.21 (1H, dd, J = 5, 11 Hz, H-6), 3.58 (1H, d, J = 8 Hz, H-1), 1.06 3.64 (3H, s, OCH3), 4.53 (1H, q, J = 7 Hz, CHCH3), 1.07 6.95 (1H, s, NH).

Refinement top

H atoms bonded to carbon were included in calculated positions using the riding model, with C—H distances of 0.93–0.98 Å and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the other H atoms; H1 was found by difference Fourier methods and refined isotropically.

Computing details top

Data collection: MSC RAXIS11 Control Software (Molecular Structure Corporation, 1992); cell refinement: DENZO (Otwinowski, 1988); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985) and TEXSAN (Molecular Structure Corporation, 1995); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. Plot of (5), with displacement ellipsoids drawn at the 50% probability level.
methyl (Z)-5-ethyl-4-ethylidene-8-methyl-2-oxo-3,8-diazabicyclo[3.2.1]octane-6-endo- 6-carboxylate top
Crystal data top
C13H20N2O3F(000) = 544
Mr = 252.31Dx = 1.290 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 10171 reflections
a = 10.00 (2) Åθ = 2.0–25.0°
b = 8.842 (10) ŵ = 0.09 mm1
c = 14.693 (10) ÅT = 293 K
β = 90.36 (8)°Plate, colourless
V = 1300 (3) Å30.4 × 0.3 × 0.2 mm
Z = 4
Data collection top
Rigaku R-AXIS
diffractometer
1840 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.042
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
40 x 5° ϕ scansh = 011
10171 measured reflectionsk = 010
2173 independent reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.078P)2 + 0.2408P]
where P = (Fo2 + 2Fc2)/3
2173 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C13H20N2O3V = 1300 (3) Å3
Mr = 252.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.00 (2) ŵ = 0.09 mm1
b = 8.842 (10) ÅT = 293 K
c = 14.693 (10) Å0.4 × 0.3 × 0.2 mm
β = 90.36 (8)°
Data collection top
Rigaku R-AXIS
diffractometer
1840 reflections with I > 2σ(I)
10171 measured reflectionsRint = 0.042
2173 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.18 e Å3
2173 reflectionsΔρmin = 0.18 e Å3
171 parameters
Special details top

Experimental. δC (75 MHz, CDCl3) 158.5, 144.5, 138.3, 135.84, 25.0, 23.4, 13.9, 13.7; m/z (CI) 153 (MH+, 100%), 154 (15), 109 (12), 82 (12)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two least-squares planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving least-squares planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.00713 (12)0.37042 (15)0.64648 (8)0.0435 (4)
O20.91004 (14)0.32829 (17)0.51163 (8)0.0529 (4)
O30.43880 (12)0.18148 (13)0.51024 (8)0.0426 (4)
N10.62102 (13)0.10340 (15)0.58974 (9)0.0292 (3)
H10.6108 (18)0.014 (2)0.5634 (12)0.042 (5)*
N20.58051 (13)0.33475 (14)0.71113 (8)0.0284 (3)
C10.72468 (15)0.12658 (17)0.65483 (10)0.0254 (4)
C20.71966 (15)0.28016 (17)0.70353 (9)0.0259 (4)
C30.77540 (15)0.40708 (17)0.63903 (10)0.0292 (4)
H30.79450.49650.67630.035*
C40.65738 (16)0.44507 (18)0.57582 (11)0.0341 (4)
H4A0.67520.41290.51400.041*
H4B0.63910.55280.57590.041*
C50.53965 (16)0.35593 (17)0.61632 (11)0.0295 (4)
H50.45630.41390.61210.035*
C60.52718 (15)0.20660 (18)0.56728 (10)0.0291 (4)
C70.81900 (16)0.02317 (18)0.66776 (11)0.0329 (4)
H70.88130.04350.71340.040*
C80.83674 (19)0.1226 (2)0.61733 (14)0.0474 (5)
H8A0.75910.14180.58040.071*
H8B0.84840.20370.66010.071*
H8C0.91410.11590.57920.071*
C90.78835 (17)0.27527 (19)0.79723 (10)0.0336 (4)
H9A0.75090.19210.83180.040*
H9B0.88260.25420.78860.040*
C100.7754 (2)0.4189 (2)0.85282 (13)0.0527 (6)
H10A0.81710.50110.82110.079*
H10B0.81820.40520.91090.079*
H10C0.68250.44150.86170.079*
C110.90159 (17)0.36412 (18)0.59040 (11)0.0330 (4)
C121.13479 (19)0.3331 (3)0.60806 (15)0.0539 (5)
H12A1.13160.23270.58330.081*
H12B1.20240.33800.65460.081*
H12C1.15560.40380.56060.081*
C130.49022 (18)0.2418 (2)0.76527 (12)0.0412 (4)
H13A0.40120.28180.76090.062*
H13B0.51900.24270.82770.062*
H13C0.49110.13990.74280.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0292 (7)0.0591 (8)0.0422 (7)0.0029 (6)0.0038 (5)0.0015 (6)
O20.0510 (8)0.0719 (10)0.0358 (7)0.0004 (7)0.0024 (6)0.0108 (6)
O30.0444 (7)0.0371 (7)0.0460 (7)0.0040 (5)0.0255 (6)0.0061 (5)
N10.0332 (8)0.0249 (7)0.0294 (7)0.0039 (6)0.0106 (6)0.0051 (6)
N20.0282 (7)0.0297 (7)0.0272 (7)0.0019 (5)0.0028 (5)0.0010 (5)
C10.0257 (8)0.0274 (8)0.0231 (7)0.0013 (6)0.0039 (6)0.0004 (6)
C20.0271 (8)0.0264 (8)0.0240 (8)0.0015 (6)0.0054 (6)0.0010 (6)
C30.0325 (9)0.0247 (8)0.0304 (8)0.0041 (6)0.0036 (7)0.0012 (6)
C40.0399 (10)0.0278 (8)0.0344 (9)0.0010 (7)0.0061 (7)0.0072 (7)
C50.0293 (9)0.0266 (8)0.0324 (8)0.0053 (6)0.0091 (7)0.0007 (6)
C60.0290 (9)0.0307 (8)0.0274 (8)0.0005 (7)0.0064 (6)0.0014 (6)
C70.0300 (9)0.0315 (9)0.0372 (9)0.0038 (7)0.0093 (7)0.0035 (7)
C80.0379 (10)0.0421 (10)0.0620 (13)0.0112 (8)0.0104 (9)0.0155 (9)
C90.0397 (10)0.0355 (9)0.0256 (8)0.0025 (7)0.0101 (7)0.0026 (7)
C100.0722 (14)0.0507 (12)0.0352 (10)0.0086 (10)0.0186 (10)0.0141 (9)
C110.0363 (10)0.0293 (8)0.0335 (9)0.0051 (7)0.0018 (7)0.0017 (7)
C120.0353 (11)0.0666 (13)0.0598 (13)0.0065 (9)0.0047 (9)0.0047 (10)
C130.0376 (10)0.0489 (11)0.0371 (9)0.0018 (8)0.0068 (7)0.0000 (8)
Geometric parameters (Å, º) top
O1—C111.336 (3)C5—C61.509 (3)
O1—C121.438 (3)C5—H50.9800
O2—C111.204 (2)C7—C81.498 (3)
O3—C61.234 (2)C7—H70.9300
N1—C61.349 (3)C8—H8A0.9600
N1—C11.421 (3)C8—H8B0.9600
N1—H10.89 (2)C8—H8C0.9600
N2—C131.460 (3)C9—C101.516 (3)
N2—C51.461 (2)C9—H9A0.9700
N2—C21.478 (3)C9—H9B0.9700
C1—C71.327 (3)C10—H10A0.9600
C1—C21.536 (2)C10—H10B0.9600
C2—C91.535 (2)C10—H10C0.9600
C2—C31.573 (2)C12—H12A0.9600
C3—C111.503 (3)C12—H12B0.9600
C3—C41.535 (3)C12—H12C0.9600
C3—H30.9800C13—H13A0.9600
C4—C51.540 (3)C13—H13B0.9600
C4—H4A0.9700C13—H13C0.9600
C4—H4B0.9700
C11—O1—C12116.64 (17)C1—C7—C8127.49 (16)
C6—N1—C1124.81 (15)C1—C7—H7116.3
C6—N1—H1114.7 (12)C8—C7—H7116.3
C1—N1—H1120.3 (12)C7—C8—H8A109.5
C13—N2—C5114.90 (15)C7—C8—H8B109.5
C13—N2—C2116.32 (16)H8A—C8—H8B109.5
C5—N2—C2103.16 (14)C7—C8—H8C109.5
C7—C1—N1120.81 (16)H8A—C8—H8C109.5
C7—C1—C2124.61 (15)H8B—C8—H8C109.5
N1—C1—C2114.53 (13)C10—C9—C2114.83 (14)
N2—C2—C9110.96 (15)C10—C9—H9A108.6
N2—C2—C1110.95 (13)C2—C9—H9A108.6
C9—C2—C1112.15 (12)C10—C9—H9B108.6
N2—C2—C398.63 (14)C2—C9—H9B108.6
C9—C2—C3113.70 (14)H9A—C9—H9B107.5
C1—C2—C3109.71 (14)C9—C10—H10A109.5
C11—C3—C4114.38 (17)C9—C10—H10B109.5
C11—C3—C2114.08 (14)H10A—C10—H10B109.5
C4—C3—C2104.27 (15)C9—C10—H10C109.5
C11—C3—H3107.9H10A—C10—H10C109.5
C4—C3—H3107.9H10B—C10—H10C109.5
C2—C3—H3107.9O2—C11—O1122.95 (18)
C3—C4—C5103.97 (16)O2—C11—C3126.01 (17)
C3—C4—H4A111.0O1—C11—C3111.03 (17)
C5—C4—H4A111.0O1—C12—H12A109.5
C3—C4—H4B111.0O1—C12—H12B109.5
C5—C4—H4B111.0H12A—C12—H12B109.5
H4A—C4—H4B109.0O1—C12—H12C109.5
N2—C5—C6111.40 (13)H12A—C12—H12C109.5
N2—C5—C4102.95 (15)H12B—C12—H12C109.5
C6—C5—C4108.93 (14)N2—C13—H13A109.5
N2—C5—H5111.1N2—C13—H13B109.5
C6—C5—H5111.1H13A—C13—H13B109.5
C4—C5—H5111.1N2—C13—H13C109.5
O3—C6—N1122.59 (17)H13A—C13—H13C109.5
O3—C6—C5122.57 (14)H13B—C13—H13C109.5
N1—C6—C5114.83 (15)
C6—N1—C1—C7174.78 (15)C2—N2—C5—C668.66 (15)
C6—N1—C1—C22.8 (2)C13—N2—C5—C4175.55 (13)
C13—N2—C2—C962.39 (17)C2—N2—C5—C447.93 (17)
C5—N2—C2—C9170.88 (12)C3—C4—C5—N223.33 (15)
C13—N2—C2—C163.00 (17)C3—C4—C5—C695.00 (15)
C5—N2—C2—C163.73 (15)C1—N1—C6—O3179.98 (15)
C13—N2—C2—C3178.04 (12)C1—N1—C6—C50.8 (2)
C5—N2—C2—C351.31 (13)N2—C5—C6—O3142.49 (16)
C7—C1—C2—N2152.27 (16)C4—C5—C6—O3104.6 (2)
N1—C1—C2—N230.24 (18)N2—C5—C6—N138.29 (19)
C7—C1—C2—C927.6 (2)C4—C5—C6—N174.6 (2)
N1—C1—C2—C9154.96 (14)N1—C1—C7—C82.9 (3)
C7—C1—C2—C399.8 (2)C2—C1—C7—C8174.41 (17)
N1—C1—C2—C377.69 (19)N2—C2—C9—C1049.66 (19)
N2—C2—C3—C11160.56 (12)C1—C2—C9—C10174.36 (15)
C9—C2—C3—C1181.93 (19)C3—C2—C9—C1060.4 (2)
C1—C2—C3—C1144.55 (17)C12—O1—C11—O20.5 (2)
N2—C2—C3—C435.10 (15)C12—O1—C11—C3179.45 (15)
C9—C2—C3—C4152.61 (13)C4—C3—C11—O215.9 (2)
C1—C2—C3—C480.91 (16)C2—C3—C11—O2104.03 (19)
C11—C3—C4—C5132.86 (15)C4—C3—C11—O1164.10 (13)
C2—C3—C4—C57.59 (15)C2—C3—C11—O175.98 (17)
C13—N2—C5—C658.97 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.89 (2)2.10 (2)2.975 (3)170.9 (16)
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC13H20N2O3
Mr252.31
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)10.00 (2), 8.842 (10), 14.693 (10)
β (°) 90.36 (8)
V3)1300 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerRigaku R-AXIS
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10171, 2173, 1840
Rint0.042
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.126, 1.06
No. of reflections2173
No. of parameters171
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.18

Computer programs: MSC RAXIS11 Control Software (Molecular Structure Corporation, 1992), DENZO (Otwinowski, 1988), DENZO, SHELXS86 (Sheldrick, 1985) and TEXSAN (Molecular Structure Corporation, 1995), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.89 (2)2.10 (2)2.975 (3)170.9 (16)
Symmetry code: (i) x+1, y, z+1.
 

Acknowledgements

YY gratefully acknowledges a studentship from The University of Manchester.

References

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