Acta Cryst. (2008). E64, o856 [ doi:10.1107/S1600536808005850 ]
The asymmetric unit of the title compound, C11H14N2O4, contains one half-molecule; a twofold rotation axis passes through the central C atom. Intermolecular C-H
N hydrogen bonds link the molecules into a one-dimensional supramolecular structure.
Dimethyl malonate (50 mmol) was dissolves in n–hexane (20 ml), then anhydrous potassium carbonate (100 mmol) and tetrabutylammonium bromide (1 g) was added. Finally acrylonitrile (100 mmol) was slowly dropped to the solution above. The resulting mixture was refluxed for 12 h, and 100 ml water was added to the mixture and the organic layer was dried with magnesium sulfate and vacuumed to removed the solvent. Then the crude compound I was obtained. It was crystallized from ethyl acetate (15 ml). Crystals of I suitable for X–ray diffraction were obtained by slow evaporation of an alcohol solution. 1H NMR (CDCl3, δ, p.p.m.) 3.83 (s, 6H), 2.47 (t, 4H), 2.26 (t, 4H).
All H atoms were positioned geometrically, with C—H = 0.96 and 0.97Å for methyl and methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for methylene H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./rk2080fig1thm.gif)
| Fig. 1. A view of the molecular structure of I showing the atom–numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a spheres of arbitrary radius. |
![[Figure 2]](./rk2080fig2thm.gif)
| Fig. 2. The 1–D supramolecular structure developed by C—H···N hydrogen bonds (dashed lines) [Symmetry codes: (i) -x, 2 - y, 1 - z]. |
| C11H14N2O4 | F000 = 504 |
| Mr = 238.24 | Dx = 1.304 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 25 reflections |
| a = 13.071 (3) Å | θ = 10–14º |
| b = 8.5060 (17) Å | µ = 0.10 mm−1 |
| c = 10.914 (2) Å | T = 293 (2) K |
| β = 90.55 (3)º | Block, colourless |
| V = 1213.4 (4) Å3 | 0.40 × 0.30 × 0.20 mm |
| Z = 4 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.048 |
| Radiation source: Fine–focus sealed tube | θmax = 25.2º |
| Monochromator: Graphite | θmin = 2.9º |
| T = 293(2) K | h = −15→15 |
| ω/2θ scans | k = 0→10 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→12 |
| Tmin = 0.961, Tmax = 0.975 | 3 standard reflections |
| 1140 measured reflections | every 200 reflections |
| 1091 independent reflections | intensity decay: none |
| 860 reflections with I > 2σ(I) |
| Refinement on F2 | Secondary atom site location: Difmap |
| Least-squares matrix: Full | Hydrogen site location: Geom |
| R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
| wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.0591P)2 + 3.2284P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.99 | (Δ/σ)max < 0.001 |
| 1091 reflections | Δρmax = 0.21 e Å−3 |
| 78 parameters | Δρmin = −0.24 e Å−3 |
| Primary atom site location: Direct | Extinction correction: None |
| C11H14N2O4 | V = 1213.4 (4) Å3 |
| Mr = 238.24 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 13.071 (3) Å | µ = 0.10 mm−1 |
| b = 8.5060 (17) Å | T = 293 (2) K |
| c = 10.914 (2) Å | 0.40 × 0.30 × 0.20 mm |
| β = 90.55 (3)º |
| Enraf–Nonius CAD-4 diffractometer | 860 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.048 |
| Tmin = 0.961, Tmax = 0.975 | 3 standard reflections |
| 1140 measured reflections | every 200 reflections |
| 1091 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.065 | 78 parameters |
| wR(F2) = 0.155 | H-atom parameters constrained |
| S = 0.99 | Δρmax = 0.21 e Å−3 |
| 1091 reflections | Δρmin = −0.24 e Å−3 |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F2, conventional R–factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F2 are statistically about twice as large as those based on F, and RR–factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| N1 | −0.1143 (3) | 0.5595 (3) | 0.4119 (3) | 0.0730 (10) | |
| C1 | −0.1098 (2) | 0.6248 (3) | 0.5039 (3) | 0.0471 (7) | |
| O1 | 0.15852 (15) | 1.0070 (2) | 0.6705 (2) | 0.0516 (6) | |
| O2 | 0.09191 (13) | 1.1101 (2) | 0.84034 (16) | 0.0402 (5) | |
| C2 | −0.1041 (3) | 0.7072 (4) | 0.6228 (3) | 0.0589 (9) | |
| H2A | −0.1056 | 0.6311 | 0.6890 | 0.071* | |
| H2B | −0.1628 | 0.7760 | 0.6312 | 0.071* | |
| C3 | −0.00519 (19) | 0.8043 (3) | 0.6315 (2) | 0.0333 (6) | |
| H3A | −0.0013 | 0.8737 | 0.5612 | 0.040* | |
| H3B | 0.0532 | 0.7340 | 0.6293 | 0.040* | |
| C4 | 0.0000 | 0.9032 (4) | 0.7500 | 0.0301 (8) | |
| C5 | 0.09365 (19) | 1.0115 (3) | 0.7444 (2) | 0.0309 (6) | |
| C6 | 0.1753 (2) | 1.2212 (4) | 0.8494 (3) | 0.0481 (8) | |
| H6A | 0.1667 | 1.2853 | 0.9209 | 0.072* | |
| H6B | 0.1756 | 1.2867 | 0.7778 | 0.072* | |
| H6C | 0.2390 | 1.1653 | 0.8555 | 0.072* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0893 (16) | 0.0651 (16) | 0.0628 (19) | 0.0048 (16) | −0.0436 (17) | −0.0172 (15) |
| C1 | 0.0547 (18) | 0.0469 (14) | 0.0532 (17) | −0.0015 (14) | −0.0192 (13) | −0.0050 (14) |
| O1 | 0.0430 (12) | 0.0432 (12) | 0.0585 (14) | −0.0076 (9) | 0.0028 (10) | −0.0102 (10) |
| O2 | 0.0498 (10) | 0.0442 (10) | 0.0465 (11) | −0.0111 (8) | −0.0098 (8) | −0.0088 (8) |
| C2 | 0.0571 (18) | 0.0484 (17) | 0.0582 (13) | −0.0162 (16) | −0.0205 (16) | −0.0162 (15) |
| C3 | 0.0404 (14) | 0.0479 (12) | 0.0355 (13) | 0.0018 (11) | −0.0067 (10) | −0.0007 (10) |
| C4 | 0.0476 (19) | 0.0472 (16) | 0.0355 (18) | −0.0017 (10) | −0.0025 (14) | 0.0006 (10) |
| C5 | 0.0421 (13) | 0.0469 (13) | 0.0344 (13) | 0.0058 (10) | −0.0093 (10) | 0.0032 (10) |
| C6 | 0.0477 (17) | 0.0452 (16) | 0.0549 (18) | −0.0162 (14) | −0.0138 (13) | −0.0046 (13) |
| N1—C1 | 1.149 (4) | C3—H3A | 0.9700 |
| C1—C2 | 1.476 (4) | C3—H3B | 0.9700 |
| O1—C5 | 1.177 (3) | C4—C5 | 1.534 (3) |
| O2—C5 | 1.341 (3) | C4—C5i | 1.534 (3) |
| O2—C6 | 1.445 (3) | C4—C3i | 1.544 (3) |
| C2—C3 | 1.537 (4) | C6—H6A | 0.9600 |
| C2—H2A | 0.9700 | C6—H6B | 0.9600 |
| C2—H2B | 0.9700 | C6—H6C | 0.9600 |
| C3—C4 | 1.544 (3) | ||
| N1—C1—C2 | 179.4 (4) | C5—C4—C3 | 108.85 (13) |
| C5—O2—C6 | 116.3 (2) | C5i—C4—C3 | 109.39 (13) |
| C1—C2—C3 | 110.1 (3) | C5—C4—C3i | 109.39 (13) |
| C1—C2—H2A | 109.6 | C5i—C4—C3i | 108.85 (13) |
| C3—C2—H2A | 109.6 | C3—C4—C3i | 113.9 (3) |
| C1—C2—H2B | 109.6 | O1—C5—O2 | 125.0 (2) |
| C3—C2—H2B | 109.6 | O1—C5—C4 | 126.0 (2) |
| H2A—C2—H2B | 108.1 | O2—C5—C4 | 108.96 (19) |
| C2—C3—C4 | 112.0 (2) | O2—C6—H6A | 109.5 |
| C2—C3—H3A | 109.2 | O2—C6—H6B | 109.5 |
| C4—C3—H3A | 109.2 | H6A—C6—H6B | 109.5 |
| C2—C3—H3B | 109.2 | O2—C6—H6C | 109.5 |
| C4—C3—H3B | 109.2 | H6A—C6—H6C | 109.5 |
| H3A—C3—H3B | 107.9 | H6B—C6—H6C | 109.5 |
| C5—C4—C5i | 106.2 (3) | ||
| C1—C2—C3—C4 | 175.4 (2) | C5i—C4—C5—O1 | −126.7 (3) |
| C2—C3—C4—C5 | −173.0 (2) | C3—C4—C5—O1 | −9.0 (3) |
| C2—C3—C4—C5i | −57.4 (3) | C3i—C4—C5—O1 | 116.0 (3) |
| C2—C3—C4—C3i | 64.63 (19) | C5i—C4—C5—O2 | 55.37 (14) |
| C6—O2—C5—O1 | 2.0 (4) | C3—C4—C5—O2 | 173.02 (18) |
| C6—O2—C5—C4 | 180.0 (2) | C3i—C4—C5—O2 | −61.9 (2) |
| Symmetry codes: (i) −x, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6B···N1ii | 0.96 | 2.57 | 3.494 (5) | 161 |
| Symmetry codes: (ii) −x, −y+2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6B···N1i | 0.96 | 2.57 | 3.494 (5) | 161 |
| Symmetry codes: (i) −x, −y+2, −z+1. |
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Chetia, A., Saikia, C. J., Lekhok, K. C. & Boruah, R. C. (2004). Tetrahedron Lett. 45, 2649–2651.
Enraf–Nonius (1989). CAD–4 Software.Enraf–Nonius, Delft, The Netherlands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Kim, D. Y., Huh, S. C. & Kim, S. M. (2001). Tetrahedron Lett. 42, 6299–6301.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Ranu, B. C. & Banerjee, S. (2005). Org. Lett. 7, 3049–3052.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhang, Z., Dong, Y.-W., Wang, G.-W. & Komatsu, K. (2004). Synlett, 1, 61–64.
Dicarbonyl compounds represent an important class of starting materials to increase the carbon number of organic compounds (Kim et al., 2001). Some dicarbonyl compounds are useful for the synthesis of enantiomerically pure alcohols (Chetia et al., 2004).
Many dicarbonyl compounds have been synthesized with "Michael Addition" method using diethy malonate as starting compound, but only a few "Michael Addition" diadducts were synthesized under normal condition (Zhang et al., 2004; Ranu & Banerjee, 2005). We are focusing our synthetic and structure studies on new products of "Michael Addition" diadducts from dicarbonyl compounds. We here report the crystal structure of the title compound (I).
The atom–numbering scheme of I is shown in Fig. 1, and all bond lengths and angles are within normal ranges (Allen et al., 1987). The asymmetric unit contains one half–molecule, and C4 lies on the twofold rotation axis vertical to ac plane, which generates the other half–molecule. An intermolecular C—H···N hydrogen bond (table and Fig. 2) helps to establish the 1–D supramolecular structure.