Dimethyl 4,4-diacetyl­hepta­nedioate

Ling-hua Zhuang; Guo-wei Wang

doi:10.1107/S1600536808043705

. 2009 Jan 8;65(Pt 2):o220. doi: 10.1107/S1600536808043705

Dimethyl 4,4-diacetylheptanedioate

Ling-hua Zhuang ^a, Guo-wei Wang ^b,^*

PMCID: PMC2968235 PMID: 21581838

Abstract

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.

Related literature

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

Crystal data

C₁₃H₂₀O₆
M _r = 272.29
Monoclinic,
a = 11.402 (2) Å
b = 8.6910 (17) Å
c = 14.845 (3) Å
β = 107.35 (3)°
V = 1404.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.970, T _max = 0.990
2531 measured reflections
2531 independent reflections
1783 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.202
S = 1.01
2531 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043705/sj2570sup1.cif

e-65-0o220-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043705/sj2570Isup2.hkl

e-65-0o220-Isup2.hkl^{(124.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O5ⁱ	0.97	2.58	3.418 (4)	145
C3—H3B⋯O2ⁱⁱ	0.97	2.55	3.500 (4)	165

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Symmetry codes: (i) Inline graphic ; (ii) .

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 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.

Experimental

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).