organic compounds
Dimethyl 2,2-bis(2-cyanoethyl)malonate
aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
*Correspondence e-mail: wjt@njut.edu.cn
The 11H14N2O4, 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.
of the title compound, CRelated literature
For general background, see: Kim et al. (2001); Chetia et al. (2004); Zhang et al. (2004); Ranu & Banerjee (2005). For bond–length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell CAD-4 Software; 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.
Supporting information
10.1107/S1600536808005850/rk2080sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808005850/rk2080Isup2.hkl
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
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).C11H14N2O4 | F(000) = 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 = 10–14° |
b = 8.5060 (17) Å | µ = 0.10 mm−1 |
c = 10.914 (2) Å | T = 293 K |
β = 90.55 (3)° | Block, colourless |
V = 1213.4 (4) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 860 reflections with I > 2σ(I) |
Radiation source: Fine–focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 25.2°, θmin = 2.9° |
ω/2θ scans | h = −15→15 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.961, Tmax = 0.975 | l = 0→12 |
1140 measured reflections | 3 standard reflections every 200 reflections |
1091 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: Direct |
Least-squares matrix: Full | Secondary atom site location: Difmap |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: Geom |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0591P)2 + 3.2284P] where P = (Fo2 + 2Fc2)/3 |
1091 reflections | (Δ/σ)max < 0.001 |
78 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C11H14N2O4 | V = 1213.4 (4) Å3 |
Mr = 238.24 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.071 (3) Å | µ = 0.10 mm−1 |
b = 8.5060 (17) Å | T = 293 K |
c = 10.914 (2) Å | 0.40 × 0.30 × 0.20 mm |
β = 90.55 (3)° |
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 every 200 reflections |
1140 measured reflections | intensity decay: none |
1091 independent reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
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 |
78 parameters |
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 code: (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 code: (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H14N2O4 |
Mr | 238.24 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.071 (3), 8.5060 (17), 10.914 (2) |
β (°) | 90.55 (3) |
V (Å3) | 1213.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.961, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1140, 1091, 860 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.155, 0.99 |
No. of reflections | 1091 |
No. of parameters | 78 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.24 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···N1i | 0.96 | 2.57 | 3.494 (5) | 161 |
Symmetry code: (i) −x, −y+2, −z+1. |
Acknowledgements
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.