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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2319.
Published online 2010 August 18. doi:  10.1107/S1600536810032149
PMCID: PMC3007919

5-(4-Hy­droxy­benzyl­idene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Abstract

The title compound, C13H12O5, was prepared by the reaction of 2,2-dimethyl-1,3-dioxane-4,6-dione and 4-hy­droxy­benz­alde­hyde in ethanol. The 1,3-dioxane ring is in a distorted boat conformation. In the crystal, inversion dimers linked by pairs of O—H(...)O hydrogen bonds generate R 2 2(20) rings.

Related literature

For a related structure, see: Zeng & Jian (2009 [triangle]).

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Object name is e-66-o2319-scheme1.jpg

Experimental

Crystal data

  • C13H12O5
  • M r = 248.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2319-efi1.jpg
  • a = 13.900 (3) Å
  • b = 10.249 (2) Å
  • c = 8.1357 (16) Å
  • β = 94.47 (3)°
  • V = 1155.5 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 K
  • 0.20 × 0.16 × 0.11 mm

Data collection

  • Bruker SMART CCD diffractometer
  • 10923 measured reflections
  • 2644 independent reflections
  • 2402 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.116
  • S = 1.05
  • 2644 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; 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/S1600536810032149/hb5605sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032149/hb5605Isup2.hkl

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

supplementary crystallographic information

Comment

We have recently reported the crystal structure of 5-(2-fluorobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Zeng & Jian 2009). As part of our search for new Meldrum's acid derivatives, the title compound, (I) (Fig. 1), has been synthesized and its structure is reported here. The crystal structure analysis confirms the title compound with atom C7 bridged by the 1,3-dioxane ring via C7═C6 double bond [1.3580 (16)Å] and the phenyl ring via C7-C8 single bond [1.4513 (15)Å], forming the C6-C7-C8 bond angle of 134.33 (10)°. The crystal structure is stabilized by weak intermolecular O—H···O hydrogen bonds (Table 1).

Experimental

A mixture of malonic acid (6.24 g, 0.06 mol) and acetic anhydride (9 ml) in strong sulfuric acid (0.25 ml) was stirred with water at 303 K, After dissolving, propan-2-one (3.48 g, 0.06 mol) was added dropwise into solution for 1 h. The reaction was allowed to proceed for 2 h. The mixture was cooled and filtered, and then an ethanol solution of 4-hydroxybenzaldehyde (7.32g, 0.06 mol) was added. The solution was then filtered and concentrated. Yellow blocks of (I) were obtained by evaporation of an petroleum ether-acetone (2:1 v/v) solution of the title compound at room temperature over a period of several days.

Refinement

The H atoms were placed in calculated positions (C—H = 0.93–0.97 Å), and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability ellipsoids and spheres of arbritrary size for the H atoms.

Crystal data

C13H12O5F(000) = 520
Mr = 248.23Dx = 1.427 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2644 reflections
a = 13.900 (3) Åθ = 3.2–27.5°
b = 10.249 (2) ŵ = 0.11 mm1
c = 8.1357 (16) ÅT = 293 K
β = 94.47 (3)°Block, yellow
V = 1155.5 (4) Å30.20 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer2402 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
graphiteθmax = 27.5°, θmin = 3.2°
phi and ω scansh = −17→18
10923 measured reflectionsk = −13→13
2644 independent reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0685P)2 + 0.2332P] where P = (Fo2 + 2Fc2)/3
2644 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.28 e Å3

Special details

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)

xyzUiso*/Ueq
O40.41524 (6)0.57554 (9)0.12495 (11)0.0401 (2)
O30.35540 (6)0.47383 (10)0.35423 (10)0.0409 (2)
O20.21646 (6)0.52747 (11)0.44151 (11)0.0468 (3)
O5−0.22815 (6)0.59477 (10)0.25091 (12)0.0468 (3)
H5A−0.23230.56000.34080.070*
C70.15802 (8)0.63304 (11)0.10210 (14)0.0317 (2)
H7A0.16170.68300.00740.038*
C11−0.13455 (8)0.59747 (11)0.21578 (14)0.0316 (2)
C80.05963 (8)0.61437 (10)0.14540 (13)0.0288 (2)
C130.02894 (8)0.52087 (11)0.25578 (14)0.0313 (2)
H13A0.07390.46380.30700.038*
C12−0.06604 (8)0.51181 (11)0.28980 (14)0.0320 (3)
H12A−0.08480.44830.36250.038*
O10.32758 (7)0.71114 (11)−0.03290 (14)0.0580 (3)
C50.26819 (8)0.52924 (12)0.32898 (14)0.0337 (3)
C60.24587 (8)0.59391 (11)0.16895 (14)0.0318 (2)
C9−0.01161 (8)0.69363 (11)0.06446 (14)0.0337 (3)
H9A0.00600.7520−0.01550.040*
C10−0.10703 (8)0.68732 (11)0.10023 (15)0.0355 (3)
H10A−0.15250.74280.04740.043*
C40.32958 (9)0.63232 (12)0.07624 (15)0.0373 (3)
C30.41508 (8)0.45675 (13)0.21746 (14)0.0366 (3)
C20.51631 (10)0.43795 (19)0.29247 (18)0.0544 (4)
H2A0.53510.51220.35940.082*
H2B0.55930.42890.20640.082*
H2C0.51920.36080.35950.082*
C10.37811 (12)0.34509 (14)0.11015 (19)0.0525 (4)
H1A0.31330.36330.06690.079*
H1B0.37890.26650.17440.079*
H1C0.41860.33430.02070.079*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O40.0294 (4)0.0477 (5)0.0443 (5)−0.0016 (3)0.0091 (3)0.0076 (4)
O30.0317 (4)0.0625 (6)0.0287 (4)0.0045 (4)0.0036 (3)0.0062 (4)
O20.0318 (4)0.0783 (7)0.0309 (4)−0.0035 (4)0.0067 (3)0.0073 (4)
O50.0273 (4)0.0666 (6)0.0468 (5)0.0088 (4)0.0051 (4)0.0100 (5)
C70.0339 (6)0.0314 (5)0.0302 (5)−0.0014 (4)0.0052 (4)0.0013 (4)
C110.0270 (5)0.0372 (6)0.0303 (5)0.0024 (4)0.0003 (4)−0.0045 (4)
C80.0290 (5)0.0293 (5)0.0281 (5)−0.0001 (4)0.0015 (4)−0.0026 (4)
C130.0286 (5)0.0316 (5)0.0334 (5)0.0038 (4)0.0007 (4)0.0037 (4)
C120.0310 (5)0.0352 (5)0.0299 (5)0.0005 (4)0.0026 (4)0.0039 (4)
O10.0496 (6)0.0612 (6)0.0660 (7)0.0073 (5)0.0224 (5)0.0309 (5)
C50.0273 (5)0.0443 (6)0.0294 (5)−0.0052 (4)0.0025 (4)0.0005 (4)
C60.0298 (5)0.0360 (5)0.0301 (5)−0.0023 (4)0.0063 (4)0.0010 (4)
C90.0365 (6)0.0311 (5)0.0327 (5)−0.0015 (4)−0.0015 (4)0.0038 (4)
C100.0334 (6)0.0347 (6)0.0373 (6)0.0052 (4)−0.0047 (4)0.0032 (5)
C40.0332 (6)0.0393 (6)0.0406 (6)−0.0009 (4)0.0100 (5)0.0050 (5)
C30.0326 (6)0.0481 (7)0.0297 (5)0.0031 (5)0.0051 (4)0.0032 (5)
C20.0337 (6)0.0894 (11)0.0402 (7)0.0138 (7)0.0031 (5)0.0039 (7)
C10.0594 (9)0.0470 (8)0.0511 (8)−0.0002 (6)0.0036 (7)−0.0049 (6)

Geometric parameters (Å, °)

O4—C41.3564 (15)C12—H12A0.9300
O4—C31.4314 (15)O1—C41.1991 (15)
O3—C51.3399 (15)C5—C61.4722 (16)
O3—C31.4493 (14)C6—C41.4882 (16)
O2—C51.2076 (15)C9—C101.3814 (17)
O5—C111.3539 (14)C9—H9A0.9300
O5—H5A0.8200C10—H10A0.9300
C7—C61.3580 (16)C3—C21.5019 (17)
C7—C81.4513 (15)C3—C11.5053 (19)
C7—H7A0.9300C2—H2A0.9600
C11—C101.3907 (17)C2—H2B0.9600
C11—C121.3968 (16)C2—H2C0.9600
C8—C131.4023 (15)C1—H1A0.9600
C8—C91.4044 (15)C1—H1B0.9600
C13—C121.3730 (16)C1—H1C0.9600
C13—H13A0.9300
C4—O4—C3118.76 (9)C8—C9—H9A119.1
C5—O3—C3119.91 (9)C9—C10—C11119.52 (10)
C11—O5—H5A109.5C9—C10—H10A120.2
C6—C7—C8134.33 (10)C11—C10—H10A120.2
C6—C7—H7A112.8O1—C4—O4118.33 (11)
C8—C7—H7A112.8O1—C4—C6125.42 (12)
O5—C11—C10118.41 (10)O4—C4—C6116.21 (10)
O5—C11—C12122.02 (11)O4—C3—O3108.99 (10)
C10—C11—C12119.56 (10)O4—C3—C2106.43 (11)
C13—C8—C9117.19 (10)O3—C3—C2106.12 (10)
C13—C8—C7125.81 (10)O4—C3—C1110.86 (10)
C9—C8—C7116.95 (10)O3—C3—C1110.31 (11)
C12—C13—C8121.38 (10)C2—C3—C1113.88 (13)
C12—C13—H13A119.3C3—C2—H2A109.5
C8—C13—H13A119.3C3—C2—H2B109.5
C13—C12—C11120.30 (10)H2A—C2—H2B109.5
C13—C12—H12A119.9C3—C2—H2C109.5
C11—C12—H12A119.9H2A—C2—H2C109.5
O2—C5—O3117.55 (11)H2B—C2—H2C109.5
O2—C5—C6125.47 (11)C3—C1—H1A109.5
O3—C5—C6116.88 (10)C3—C1—H1B109.5
C7—C6—C5127.45 (10)H1A—C1—H1B109.5
C7—C6—C4115.66 (10)C3—C1—H1C109.5
C5—C6—C4116.62 (10)H1A—C1—H1C109.5
C10—C9—C8121.84 (10)H1B—C1—H1C109.5
C10—C9—H9A119.1

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5A···O2i0.821.982.7919 (14)170

Symmetry codes: (i) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5605).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zeng, W.-L. & Jian, F.-F. (2009). Acta Cryst. E65, o2587. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography