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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o856.
Published online 2008 April 16. doi:  10.1107/S1600536808005850
PMCID: PMC2961140

Dimethyl 2,2-bis­(2-cyano­ethyl)malonate

Abstract

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.

Related literature

For general background, see: Kim et al. (2001 [triangle]); Chetia et al. (2004 [triangle]); Zhang et al. (2004 [triangle]); Ranu & Banerjee (2005 [triangle]). For bond–length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o856-scheme1.jpg

Experimental

Crystal data

  • C11H14N2O4
  • M r = 238.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o856-efi1.jpg
  • a = 13.071 (3) Å
  • b = 8.5060 (17) Å
  • c = 10.914 (2) Å
  • β = 90.55 (3)°
  • V = 1213.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 (2) K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.961, T max = 0.975
  • 1140 measured reflections
  • 1091 independent reflections
  • 860 reflections with I > 2σ(I)
  • R int = 0.048
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.155
  • S = 0.99
  • 1091 reflections
  • 78 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005850/rk2080sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005850/rk2080Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

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.

Figures

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.
Fig. 2.
The 1–D supramolecular structure developed by C—H···N hydrogen bonds (dashed lines) [Symmetry codes: (i) -x, 2 - y, 1 - z].

Crystal data

C11H14N2O4F000 = 504
Mr = 238.24Dx = 1.304 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 13.071 (3) Åθ = 10–14º
b = 8.5060 (17) ŵ = 0.10 mm1
c = 10.914 (2) ÅT = 293 (2) K
β = 90.55 (3)ºBlock, colourless
V = 1213.4 (4) Å30.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.048
Radiation source: Fine–focus sealed tubeθmax = 25.2º
Monochromator: Graphiteθmin = 2.9º
T = 293(2) Kh = −15→15
ω/2θ scansk = 0→10
Absorption correction: ψ scan(North et al., 1968)l = 0→12
Tmin = 0.961, Tmax = 0.9753 standard reflections
1140 measured reflections every 200 reflections
1091 independent reflections intensity decay: none
860 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.065H-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 reflectionsΔρmax = 0.21 e Å3
78 parametersΔρmin = −0.24 e Å3
Primary atom site location: DirectExtinction correction: None

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/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)
O10.15852 (15)1.0070 (2)0.6705 (2)0.0516 (6)
O20.09191 (13)1.1101 (2)0.84034 (16)0.0402 (5)
C2−0.1041 (3)0.7072 (4)0.6228 (3)0.0589 (9)
H2A−0.10560.63110.68900.071*
H2B−0.16280.77600.63120.071*
C3−0.00519 (19)0.8043 (3)0.6315 (2)0.0333 (6)
H3A−0.00130.87370.56120.040*
H3B0.05320.73400.62930.040*
C40.00000.9032 (4)0.75000.0301 (8)
C50.09365 (19)1.0115 (3)0.7444 (2)0.0309 (6)
C60.1753 (2)1.2212 (4)0.8494 (3)0.0481 (8)
H6A0.16671.28530.92090.072*
H6B0.17561.28670.77780.072*
H6C0.23901.16530.85550.072*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0893 (16)0.0651 (16)0.0628 (19)0.0048 (16)−0.0436 (17)−0.0172 (15)
C10.0547 (18)0.0469 (14)0.0532 (17)−0.0015 (14)−0.0192 (13)−0.0050 (14)
O10.0430 (12)0.0432 (12)0.0585 (14)−0.0076 (9)0.0028 (10)−0.0102 (10)
O20.0498 (10)0.0442 (10)0.0465 (11)−0.0111 (8)−0.0098 (8)−0.0088 (8)
C20.0571 (18)0.0484 (17)0.0582 (13)−0.0162 (16)−0.0205 (16)−0.0162 (15)
C30.0404 (14)0.0479 (12)0.0355 (13)0.0018 (11)−0.0067 (10)−0.0007 (10)
C40.0476 (19)0.0472 (16)0.0355 (18)−0.0017 (10)−0.0025 (14)0.0006 (10)
C50.0421 (13)0.0469 (13)0.0344 (13)0.0058 (10)−0.0093 (10)0.0032 (10)
C60.0477 (17)0.0452 (16)0.0549 (18)−0.0162 (14)−0.0138 (13)−0.0046 (13)

Geometric parameters (Å, °)

N1—C11.149 (4)C3—H3A0.9700
C1—C21.476 (4)C3—H3B0.9700
O1—C51.177 (3)C4—C51.534 (3)
O2—C51.341 (3)C4—C5i1.534 (3)
O2—C61.445 (3)C4—C3i1.544 (3)
C2—C31.537 (4)C6—H6A0.9600
C2—H2A0.9700C6—H6B0.9600
C2—H2B0.9700C6—H6C0.9600
C3—C41.544 (3)
N1—C1—C2179.4 (4)C5—C4—C3108.85 (13)
C5—O2—C6116.3 (2)C5i—C4—C3109.39 (13)
C1—C2—C3110.1 (3)C5—C4—C3i109.39 (13)
C1—C2—H2A109.6C5i—C4—C3i108.85 (13)
C3—C2—H2A109.6C3—C4—C3i113.9 (3)
C1—C2—H2B109.6O1—C5—O2125.0 (2)
C3—C2—H2B109.6O1—C5—C4126.0 (2)
H2A—C2—H2B108.1O2—C5—C4108.96 (19)
C2—C3—C4112.0 (2)O2—C6—H6A109.5
C2—C3—H3A109.2O2—C6—H6B109.5
C4—C3—H3A109.2H6A—C6—H6B109.5
C2—C3—H3B109.2O2—C6—H6C109.5
C4—C3—H3B109.2H6A—C6—H6C109.5
H3A—C3—H3B107.9H6B—C6—H6C109.5
C5—C4—C5i106.2 (3)
C1—C2—C3—C4175.4 (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—O1116.0 (3)
C2—C3—C4—C3i64.63 (19)C5i—C4—C5—O255.37 (14)
C6—O2—C5—O12.0 (4)C3—C4—C5—O2173.02 (18)
C6—O2—C5—C4180.0 (2)C3i—C4—C5—O2−61.9 (2)

Symmetry codes: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6B···N1ii0.962.573.494 (5)161

Symmetry codes: (ii) −x, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2080).

References

  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhang, Z., Dong, Y.-W., Wang, G.-W. & Komatsu, K. (2004). Synlett, 1, 61–64.

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