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Acta Cryst. (2009). E65, o220    [ doi:10.1107/S1600536808043705 ]

Dimethyl 4,4-diacetylheptanedioate

L. Zhuang and G. Wang

Abstract top

The molecule of the title dicarbonyl compound, C13H20O6, possesses approximate local twofold symmetry. In the crystal, intermolecular C-H...O hydrogen bonds link the molecules, generating a chain structure.

Comment top

Dicarbonyl compounds represent an important class of starting materials used 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 diethyl malonate as the starting mateiral, but only a few Michael Addition diadducts have been synthesized under normal condition (Ranu & Banerjee, 2005; Wang et al., 2008). We are focusing our synthetic and structural studies on new products of Michael Addition diadducts from dicarbonyl compounds. We report here the crystal structure of the title dicarbonyl compound (I), Fig 1.

All bond lengths in the compound are within normal ranges (Allen et al., 1987). The central C13 atom lies on a lies on a non-crystallographic pseudo twofold rotation axis. Intermolecular C—H···O hydrogen bond (Table 1, Fig.2) help to establish the one-dimensional supramolecular structure.

Related literature top

For general background, see: Kim et al. (2001); Chetia et al. (2004); Ranu & Banerjee (2005); Wang et al. (2008). For bond-length data, see: Allen et al. (1987).

Experimental top

Acetylacetone (50 mmol), anhydrous potassium carbonate (100 mmol), tetrabutylammonium bromide (1 g) were dissolved in toluene (20 ml) and methyl acrylate (100 mmol) was slowly dropped to the mixture which was stirred for 24 h at 303–333 K, then 100 ml water was added. The organic layer was dried with magnesium sulfate and the solvent removed under vacuum to obtain the crude product, (I). Crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution. 1H NMR (CDCl3, δ, p.p.m.) 3.62(s, 6H), 2.23(m, 4H), 2.144 (m, 10H).

Refinement top

All H atoms were positioned geometrically, with C—H = 0.96 and 0.97 Å 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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids.
[Figure 2] Fig. 2. The crystal packing of (I) Intermolecular hydrogen bonds are shown as dashed lines.
Dimethyl 4,4-diacetylheptanedioate top
Crystal data top
C13H20O6F(000) = 584
Mr = 272.29Dx = 1.288 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 27 reflections
a = 11.402 (2) Åθ = 8–15°
b = 8.6910 (17) ŵ = 0.10 mm−1
c = 14.845 (3) ÅT = 293 K
β = 107.35 (3)°Block, colourless
V = 1404.1 (5) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1783 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 25.3°, θmin = 1.9°
ω/2θ scansh = −13→13
Absorption correction: ψ scan
(North et al., 1968)		k = 0→10
Tmin = 0.970, Tmax = 0.990l = 0→17
2531 measured reflections3 standard reflections every 200 reflections
2531 independent reflections intensity decay: 9%
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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.202H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1P)2 + 1.5P]
where P = (Fo2 + 2Fc2)/3
2531 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C13H20O6V = 1404.1 (5) Å3
Mr = 272.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.402 (2) ŵ = 0.10 mm−1
b = 8.6910 (17) ÅT = 293 K
c = 14.845 (3) Å0.30 × 0.20 × 0.10 mm
β = 107.35 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1783 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.970, Tmax = 0.990θmax = 25.3°
2531 measured reflections3 standard reflections every 200 reflections
2531 independent reflections intensity decay: 9%
Refinement top
R[F2 > 2σ(F2)] = 0.065H-atom parameters constrained
wR(F2) = 0.202Δρmax = 0.38 e Å−3
S = 1.00Δρmin = −0.25 e Å−3
2531 reflectionsAbsolute structure: ?
172 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. 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 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 > σ(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 R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.1970 (2)−0.2798 (3)0.80271 (19)0.0587 (7)
O21.1274 (2)−0.0419 (2)0.80976 (18)0.0552 (7)
O30.5191 (2)−0.3553 (3)0.66776 (18)0.0646 (7)
O40.5065 (2)−0.1212 (3)0.60519 (17)0.0585 (7)
O50.7976 (2)0.0496 (2)0.94983 (17)0.0506 (6)
O60.8453 (2)−0.4676 (2)0.96422 (18)0.0567 (7)
C11.2919 (4)−0.2184 (5)0.7683 (3)0.0710 (12)
H1A1.3430−0.30060.75860.106*
H1B1.3407−0.14720.81360.106*
H1C1.2556−0.16600.70970.106*
C21.1177 (3)−0.1782 (3)0.8194 (2)0.0401 (7)
C31.0191 (3)−0.2557 (3)0.8502 (2)0.0408 (7)
H3A1.0564−0.32250.90330.049*
H3B0.9697−0.31900.79910.049*
C40.9365 (2)−0.1393 (3)0.8785 (2)0.0360 (7)
H4A0.9057−0.06730.82690.043*
H4B0.9858−0.08140.93240.043*
C50.4002 (3)−0.1660 (5)0.5299 (3)0.0597 (10)
H5A0.3724−0.08050.48810.089*
H5B0.3361−0.19740.55570.089*
H5C0.4211−0.25010.49570.089*
C60.5572 (3)−0.2265 (4)0.6703 (2)0.0430 (7)
C70.6632 (3)−0.1613 (4)0.7454 (2)0.0513 (8)
H7A0.6340−0.07850.77690.062*
H7B0.7214−0.11790.71630.062*
C80.7290 (3)−0.2793 (3)0.8186 (2)0.0413 (7)
H8A0.7683−0.35420.78870.050*
H8B0.6686−0.33330.84100.050*
C90.6618 (3)−0.1291 (4)0.9838 (3)0.0582 (9)
H9A0.6315−0.04011.00810.087*
H9B0.6907−0.20331.03340.087*
H9C0.5967−0.17340.93380.087*
C100.7649 (3)−0.0831 (4)0.9467 (2)0.0393 (7)
C110.9581 (3)−0.2844 (4)1.0738 (2)0.0539 (9)
H11A0.9808−0.37201.11460.081*
H11B0.9172−0.21021.10180.081*
H11C1.0305−0.23891.06480.081*
C120.8733 (3)−0.3344 (3)0.9802 (2)0.0394 (7)
C130.8265 (2)−0.2094 (3)0.9038 (2)0.0341 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0587 (14)0.0424 (13)0.0902 (18)0.0057 (11)0.0453 (14)0.0031 (12)
O20.0663 (15)0.0377 (13)0.0743 (16)−0.0010 (11)0.0403 (13)0.0039 (11)
O30.0630 (16)0.0488 (15)0.0686 (16)−0.0126 (12)−0.0008 (13)0.0054 (12)
O40.0587 (15)0.0523 (14)0.0544 (14)−0.0080 (11)0.0015 (11)0.0059 (11)
O50.0508 (13)0.0329 (12)0.0712 (16)0.0012 (10)0.0228 (11)−0.0047 (10)
O60.0595 (15)0.0344 (13)0.0714 (16)−0.0049 (10)0.0123 (12)0.0102 (11)
C10.065 (2)0.063 (2)0.105 (3)−0.0007 (19)0.055 (2)−0.006 (2)
C20.0444 (17)0.0383 (17)0.0393 (16)−0.0001 (13)0.0149 (13)−0.0041 (12)
C30.0439 (16)0.0348 (15)0.0472 (17)0.0000 (13)0.0188 (13)0.0000 (12)
C40.0335 (15)0.0300 (14)0.0444 (16)−0.0032 (12)0.0114 (12)−0.0044 (12)
C50.0441 (19)0.075 (3)0.053 (2)0.0015 (18)0.0036 (16)0.0057 (18)
C60.0394 (16)0.0485 (19)0.0436 (17)−0.0009 (14)0.0163 (14)−0.0008 (14)
C70.0530 (19)0.0474 (19)0.0449 (17)−0.0104 (15)0.0013 (15)0.0036 (15)
C80.0409 (16)0.0355 (16)0.0468 (17)−0.0046 (13)0.0122 (14)−0.0004 (13)
C90.050 (2)0.060 (2)0.075 (2)0.0021 (17)0.0360 (18)0.0016 (18)
C100.0316 (15)0.0415 (17)0.0423 (16)0.0022 (13)0.0072 (12)−0.0005 (13)
C110.065 (2)0.0460 (19)0.0474 (19)0.0052 (16)0.0111 (16)0.0047 (15)
C120.0385 (15)0.0337 (16)0.0499 (17)0.0005 (12)0.0191 (13)0.0033 (13)
C130.0322 (14)0.0293 (14)0.0408 (15)−0.0007 (11)0.0108 (12)−0.0010 (11)
Geometric parameters (Å, °) top
O1—C21.339 (4)C5—H5B0.9600
O1—C11.430 (4)C5—H5C0.9600
O2—C21.202 (4)C6—C71.491 (4)
O3—C61.197 (4)C7—C81.519 (4)
O4—C61.331 (4)C7—H7A0.9700
O4—C51.436 (4)C7—H7B0.9700
O5—C101.209 (4)C8—C131.538 (4)
O6—C121.206 (4)C8—H8A0.9700
C1—H1A0.9600C8—H8B0.9700
C1—H1B0.9600C9—C101.494 (4)
C1—H1C0.9600C9—H9A0.9600
C2—C31.495 (4)C9—H9B0.9600
C3—C41.524 (4)C9—H9C0.9600
C3—H3A0.9700C10—C131.540 (4)
C3—H3B0.9700C11—C121.501 (5)
C4—C131.539 (4)C11—H11A0.9600
C4—H4A0.9700C11—H11B0.9600
C4—H4B0.9700C11—H11C0.9600
C5—H5A0.9600C12—C131.546 (4)
C2—O1—C1116.4 (3)C8—C7—H7A108.9
C6—O4—C5117.5 (3)C6—C7—H7B108.9
O1—C1—H1A109.5C8—C7—H7B108.9
O1—C1—H1B109.5H7A—C7—H7B107.7
H1A—C1—H1B109.5C7—C8—C13113.8 (2)
O1—C1—H1C109.5C7—C8—H8A108.8
H1A—C1—H1C109.5C13—C8—H8A108.8
H1B—C1—H1C109.5C7—C8—H8B108.8
O2—C2—O1122.5 (3)C13—C8—H8B108.8
O2—C2—C3125.8 (3)H8A—C8—H8B107.7
O1—C2—C3111.8 (3)C10—C9—H9A109.5
C2—C3—C4111.6 (2)C10—C9—H9B109.5
C2—C3—H3A109.3H9A—C9—H9B109.5
C4—C3—H3A109.3C10—C9—H9C109.5
C2—C3—H3B109.3H9A—C9—H9C109.5
C4—C3—H3B109.3H9B—C9—H9C109.5
H3A—C3—H3B108.0O5—C10—C9120.6 (3)
C3—C4—C13114.8 (2)O5—C10—C13121.5 (3)
C3—C4—H4A108.6C9—C10—C13117.9 (3)
C13—C4—H4A108.6C12—C11—H11A109.5
C3—C4—H4B108.6C12—C11—H11B109.5
C13—C4—H4B108.6H11A—C11—H11B109.5
H4A—C4—H4B107.5C12—C11—H11C109.5
O4—C5—H5A109.5H11A—C11—H11C109.5
O4—C5—H5B109.5H11B—C11—H11C109.5
H5A—C5—H5B109.5O6—C12—C11121.3 (3)
O4—C5—H5C109.5O6—C12—C13121.1 (3)
H5A—C5—H5C109.5C11—C12—C13117.5 (3)
H5B—C5—H5C109.5C8—C13—C4113.4 (2)
O3—C6—O4123.0 (3)C8—C13—C10108.4 (2)
O3—C6—C7125.7 (3)C4—C13—C10108.9 (2)
O4—C6—C7111.2 (3)C8—C13—C12109.4 (2)
C6—C7—C8113.3 (3)C4—C13—C12109.2 (2)
C6—C7—H7A108.9C10—C13—C12107.3 (2)
C1—O1—C2—O2−2.7 (5)C3—C4—C13—C10170.5 (2)
C1—O1—C2—C3177.0 (3)C3—C4—C13—C1253.6 (3)
O2—C2—C3—C4−5.9 (4)O5—C10—C13—C8−118.2 (3)
O1—C2—C3—C4174.3 (3)C9—C10—C13—C861.1 (3)
C2—C3—C4—C13175.5 (2)O5—C10—C13—C45.6 (4)
C5—O4—C6—O30.9 (5)C9—C10—C13—C4−175.1 (3)
C5—O4—C6—C7−177.8 (3)O5—C10—C13—C12123.7 (3)
O3—C6—C7—C84.6 (5)C9—C10—C13—C12−57.0 (3)
O4—C6—C7—C8−176.7 (3)O6—C12—C13—C89.0 (4)
C6—C7—C8—C13−171.8 (3)C11—C12—C13—C8−172.9 (3)
C7—C8—C13—C4−66.3 (3)O6—C12—C13—C4−115.7 (3)
C7—C8—C13—C1054.8 (3)C11—C12—C13—C462.4 (3)
C7—C8—C13—C12171.5 (3)O6—C12—C13—C10126.4 (3)
C3—C4—C13—C8−68.8 (3)C11—C12—C13—C10−55.5 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4B···O5i0.972.583.418 (4)145
C3—H3B···O2ii0.972.553.500 (4)165
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4B···O5i0.972.583.418 (4)145
C3—H3B···O2ii0.972.553.500 (4)165
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y−1/2, −z+3/2.
Acknowledgements top

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

references
References top

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.

Wang, G.-W., Zhuang, L.-H., Wu, W.-Y. & Wang, J.-T. (2008). Acta Cryst. E64, o856.