Dimethyl 4,4-diacetyl­hepta­nedioate

Zhuang, L.; Wang, G.

doi:10.1107/S1600536808043705

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o220

doi:10.1107/S1600536808043705

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Dimethyl 4,4-diacetylheptanedioate

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

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technolgy, Nanjing 210009, People's Republic of China, and ^bDepartment of Light Chemical Engineering, College of Science, Nanjing University of Technolgy, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kingwell2004@sina.com.cn

(Received 20 December 2008; accepted 23 December 2008; online 8 January 2009)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.065
wR(F²) = 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

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
Symmetry codes: (i) -x+2, -y, -z+2; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

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).

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

	Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids.
	Fig. 2. The crystal packing of (I) Intermolecular hydrogen bonds are shown as dashed lines.

Dimethyl 4,4-diacetylheptanedioate top

Crystal data top

C₁₃H₂₀O₆	F(000) = 584
M_r = 272.29	D_x = 1.288 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 11.402 (2) Å	θ = 8–15°
b = 8.6910 (17) Å	µ = 0.10 mm⁻¹
c = 14.845 (3) Å	T = 293 K
β = 107.35 (3)°	Block, colourless
V = 1404.1 (5) Å³	0.30 × 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 tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.970, T_max = 0.990	l = 0→17
2531 measured reflections	3 standard reflections every 200 reflections
2531 independent reflections	intensity decay: 9%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.202	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 1.5P] where P = (F_o² + 2F_c²)/3
2531 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₂₀O₆	V = 1404.1 (5) Å³
M_r = 272.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.402 (2) Å	µ = 0.10 mm⁻¹
b = 8.6910 (17) Å	T = 293 K
c = 14.845 (3) Å	0.30 × 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)	R_int = 0.000
T_min = 0.970, T_max = 0.990	3 standard reflections every 200 reflections
2531 measured reflections	intensity decay: 9%
2531 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.202	H-atom parameters constrained
S = 1.01	Δρ_max = 0.38 e Å⁻³
2531 reflections	Δρ_min = −0.25 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
O1	1.1970 (2)	−0.2798 (3)	0.80271 (19)	0.0587 (7)
O2	1.1274 (2)	−0.0419 (2)	0.80976 (18)	0.0552 (7)
O3	0.5191 (2)	−0.3553 (3)	0.66776 (18)	0.0646 (7)
O4	0.5065 (2)	−0.1212 (3)	0.60519 (17)	0.0585 (7)
O5	0.7976 (2)	0.0496 (2)	0.94983 (17)	0.0506 (6)
O6	0.8453 (2)	−0.4676 (2)	0.96422 (18)	0.0567 (7)
C1	1.2919 (4)	−0.2184 (5)	0.7683 (3)	0.0710 (12)
H1A	1.3430	−0.3006	0.7586	0.106*
H1B	1.3407	−0.1472	0.8136	0.106*
H1C	1.2556	−0.1660	0.7097	0.106*
C2	1.1177 (3)	−0.1782 (3)	0.8194 (2)	0.0401 (7)
C3	1.0191 (3)	−0.2557 (3)	0.8502 (2)	0.0408 (7)
H3A	1.0564	−0.3225	0.9033	0.049*
H3B	0.9697	−0.3190	0.7991	0.049*
C4	0.9365 (2)	−0.1393 (3)	0.8785 (2)	0.0360 (7)
H4A	0.9057	−0.0673	0.8269	0.043*
H4B	0.9858	−0.0814	0.9324	0.043*
C5	0.4002 (3)	−0.1660 (5)	0.5299 (3)	0.0597 (10)
H5A	0.3724	−0.0805	0.4881	0.089*
H5B	0.3361	−0.1974	0.5557	0.089*
H5C	0.4211	−0.2501	0.4957	0.089*
C6	0.5572 (3)	−0.2265 (4)	0.6703 (2)	0.0430 (7)
C7	0.6632 (3)	−0.1613 (4)	0.7454 (2)	0.0513 (8)
H7A	0.6340	−0.0785	0.7769	0.062*
H7B	0.7214	−0.1179	0.7163	0.062*
C8	0.7290 (3)	−0.2793 (3)	0.8186 (2)	0.0413 (7)
H8A	0.7683	−0.3542	0.7887	0.050*
H8B	0.6686	−0.3333	0.8410	0.050*
C9	0.6618 (3)	−0.1291 (4)	0.9838 (3)	0.0582 (9)
H9A	0.6315	−0.0401	1.0081	0.087*
H9B	0.6907	−0.2033	1.0334	0.087*
H9C	0.5967	−0.1734	0.9338	0.087*
C10	0.7649 (3)	−0.0831 (4)	0.9467 (2)	0.0393 (7)
C11	0.9581 (3)	−0.2844 (4)	1.0738 (2)	0.0539 (9)
H11A	0.9808	−0.3720	1.1146	0.081*
H11B	0.9172	−0.2102	1.1018	0.081*
H11C	1.0305	−0.2389	1.0648	0.081*
C12	0.8733 (3)	−0.3344 (3)	0.9802 (2)	0.0394 (7)
C13	0.8265 (2)	−0.2094 (3)	0.9038 (2)	0.0341 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0587 (14)	0.0424 (13)	0.0902 (18)	0.0057 (11)	0.0453 (14)	0.0031 (12)
O2	0.0663 (15)	0.0377 (13)	0.0743 (16)	−0.0010 (11)	0.0403 (13)	0.0039 (11)
O3	0.0630 (16)	0.0488 (15)	0.0686 (16)	−0.0126 (12)	−0.0008 (13)	0.0054 (12)
O4	0.0587 (15)	0.0523 (14)	0.0544 (14)	−0.0080 (11)	0.0015 (11)	0.0059 (11)
O5	0.0508 (13)	0.0329 (12)	0.0712 (16)	0.0012 (10)	0.0228 (11)	−0.0047 (10)
O6	0.0595 (15)	0.0344 (13)	0.0714 (16)	−0.0049 (10)	0.0123 (12)	0.0102 (11)
C1	0.065 (2)	0.063 (2)	0.105 (3)	−0.0007 (19)	0.055 (2)	−0.006 (2)
C2	0.0444 (17)	0.0383 (17)	0.0393 (16)	−0.0001 (13)	0.0149 (13)	−0.0041 (12)
C3	0.0439 (16)	0.0348 (15)	0.0472 (17)	0.0000 (13)	0.0188 (13)	0.0000 (12)
C4	0.0335 (15)	0.0300 (14)	0.0444 (16)	−0.0032 (12)	0.0114 (12)	−0.0044 (12)
C5	0.0441 (19)	0.075 (3)	0.053 (2)	0.0015 (18)	0.0036 (16)	0.0057 (18)
C6	0.0394 (16)	0.0485 (19)	0.0436 (17)	−0.0009 (14)	0.0163 (14)	−0.0008 (14)
C7	0.0530 (19)	0.0474 (19)	0.0449 (17)	−0.0104 (15)	0.0013 (15)	0.0036 (15)
C8	0.0409 (16)	0.0355 (16)	0.0468 (17)	−0.0046 (13)	0.0122 (14)	−0.0004 (13)
C9	0.050 (2)	0.060 (2)	0.075 (2)	0.0021 (17)	0.0360 (18)	0.0016 (18)
C10	0.0316 (15)	0.0415 (17)	0.0423 (16)	0.0022 (13)	0.0072 (12)	−0.0005 (13)
C11	0.065 (2)	0.0460 (19)	0.0474 (19)	0.0052 (16)	0.0111 (16)	0.0047 (15)
C12	0.0385 (15)	0.0337 (16)	0.0499 (17)	0.0005 (12)	0.0191 (13)	0.0033 (13)
C13	0.0322 (14)	0.0293 (14)	0.0408 (15)	−0.0007 (11)	0.0108 (12)	−0.0010 (11)

Geometric parameters (Å, º) top

O1—C2	1.339 (4)	C5—H5B	0.9600
O1—C1	1.430 (4)	C5—H5C	0.9600
O2—C2	1.202 (4)	C6—C7	1.491 (4)
O3—C6	1.197 (4)	C7—C8	1.519 (4)
O4—C6	1.331 (4)	C7—H7A	0.9700
O4—C5	1.436 (4)	C7—H7B	0.9700
O5—C10	1.209 (4)	C8—C13	1.538 (4)
O6—C12	1.206 (4)	C8—H8A	0.9700
C1—H1A	0.9600	C8—H8B	0.9700
C1—H1B	0.9600	C9—C10	1.494 (4)
C1—H1C	0.9600	C9—H9A	0.9600
C2—C3	1.495 (4)	C9—H9B	0.9600
C3—C4	1.524 (4)	C9—H9C	0.9600
C3—H3A	0.9700	C10—C13	1.540 (4)
C3—H3B	0.9700	C11—C12	1.501 (5)
C4—C13	1.539 (4)	C11—H11A	0.9600
C4—H4A	0.9700	C11—H11B	0.9600
C4—H4B	0.9700	C11—H11C	0.9600
C5—H5A	0.9600	C12—C13	1.546 (4)

C2—O1—C1	116.4 (3)	C8—C7—H7A	108.9
C6—O4—C5	117.5 (3)	C6—C7—H7B	108.9
O1—C1—H1A	109.5	C8—C7—H7B	108.9
O1—C1—H1B	109.5	H7A—C7—H7B	107.7
H1A—C1—H1B	109.5	C7—C8—C13	113.8 (2)
O1—C1—H1C	109.5	C7—C8—H8A	108.8
H1A—C1—H1C	109.5	C13—C8—H8A	108.8
H1B—C1—H1C	109.5	C7—C8—H8B	108.8
O2—C2—O1	122.5 (3)	C13—C8—H8B	108.8
O2—C2—C3	125.8 (3)	H8A—C8—H8B	107.7
O1—C2—C3	111.8 (3)	C10—C9—H9A	109.5
C2—C3—C4	111.6 (2)	C10—C9—H9B	109.5
C2—C3—H3A	109.3	H9A—C9—H9B	109.5
C4—C3—H3A	109.3	C10—C9—H9C	109.5
C2—C3—H3B	109.3	H9A—C9—H9C	109.5
C4—C3—H3B	109.3	H9B—C9—H9C	109.5
H3A—C3—H3B	108.0	O5—C10—C9	120.6 (3)
C3—C4—C13	114.8 (2)	O5—C10—C13	121.5 (3)
C3—C4—H4A	108.6	C9—C10—C13	117.9 (3)
C13—C4—H4A	108.6	C12—C11—H11A	109.5
C3—C4—H4B	108.6	C12—C11—H11B	109.5
C13—C4—H4B	108.6	H11A—C11—H11B	109.5
H4A—C4—H4B	107.5	C12—C11—H11C	109.5
O4—C5—H5A	109.5	H11A—C11—H11C	109.5
O4—C5—H5B	109.5	H11B—C11—H11C	109.5
H5A—C5—H5B	109.5	O6—C12—C11	121.3 (3)
O4—C5—H5C	109.5	O6—C12—C13	121.1 (3)
H5A—C5—H5C	109.5	C11—C12—C13	117.5 (3)
H5B—C5—H5C	109.5	C8—C13—C4	113.4 (2)
O3—C6—O4	123.0 (3)	C8—C13—C10	108.4 (2)
O3—C6—C7	125.7 (3)	C4—C13—C10	108.9 (2)
O4—C6—C7	111.2 (3)	C8—C13—C12	109.4 (2)
C6—C7—C8	113.3 (3)	C4—C13—C12	109.2 (2)
C6—C7—H7A	108.9	C10—C13—C12	107.3 (2)

C1—O1—C2—O2	−2.7 (5)	C3—C4—C13—C10	170.5 (2)
C1—O1—C2—C3	177.0 (3)	C3—C4—C13—C12	53.6 (3)
O2—C2—C3—C4	−5.9 (4)	O5—C10—C13—C8	−118.2 (3)
O1—C2—C3—C4	174.3 (3)	C9—C10—C13—C8	61.1 (3)
C2—C3—C4—C13	175.5 (2)	O5—C10—C13—C4	5.6 (4)
C5—O4—C6—O3	0.9 (5)	C9—C10—C13—C4	−175.1 (3)
C5—O4—C6—C7	−177.8 (3)	O5—C10—C13—C12	123.7 (3)
O3—C6—C7—C8	4.6 (5)	C9—C10—C13—C12	−57.0 (3)
O4—C6—C7—C8	−176.7 (3)	O6—C12—C13—C8	9.0 (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—C10	54.8 (3)	C11—C12—C13—C4	62.4 (3)
C7—C8—C13—C12	171.5 (3)	O6—C12—C13—C10	126.4 (3)
C3—C4—C13—C8	−68.8 (3)	C11—C12—C13—C10	−55.5 (3)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₀O₆
M_r	272.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.402 (2), 8.6910 (17), 14.845 (3)
β (°)	107.35 (3)
V (Å³)	1404.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.970, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2531, 2531, 1783
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.202, 1.01
No. of reflections	2531
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O5ⁱ	0.97	2.58	3.418 (4)	144.7
C3—H3B···O2ⁱⁱ	0.97	2.55	3.500 (4)	165.1

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y−1/2, −z+3/2.

Acknowledgements

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

References

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