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

doi:10.1107/S1600536810032149

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

Wu-Lan Zeng^a^*

^aMicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People’s Republic of China

Correspondence e-mail: wulanzeng/at/163.com

Received August 8, 2010; Accepted August 10, 2010.

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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

An external file that holds a picture, illustration, etc.
Object name is e-66-o2319-scheme1.jpg Object name is e-66-o2319-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₂O₅
M _r = 248.23
Monoclinic,
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
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 1997

); cell refinement: SAINT (Bruker, 1997

); data reduction: SAINT; 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.

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032149/hb5605sup1.cif

Click here to view.^{(15K, cif)}

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

Click here to view.^{(130K, 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.

Figures

Fig. 1.

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

Crystal data

C₁₃H₁₂O₅	F(000) = 520
M_r = 248.23	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2644 reflections
a = 13.900 (3) Å	θ = 3.2–27.5°
b = 10.249 (2) Å	µ = 0.11 mm⁻¹
c = 8.1357 (16) Å	T = 293 K
β = 94.47 (3)°	Block, yellow
V = 1155.5 (4) Å³	0.20 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2402 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
graphite	θ_max = 27.5°, θ_min = 3.2°
phi and ω scans	h = −17→18
10923 measured reflections	k = −13→13
2644 independent reflections	l = −10→10

Refinement

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0685P)² + 0.2332P] where P = (F_o² + 2F_c²)/3
2644 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

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)

	x	y	z	U_iso*/U_eq
O4	0.41524 (6)	0.57554 (9)	0.12495 (11)	0.0401 (2)
O3	0.35540 (6)	0.47383 (10)	0.35423 (10)	0.0409 (2)
O2	0.21646 (6)	0.52747 (11)	0.44151 (11)	0.0468 (3)
O5	−0.22815 (6)	0.59477 (10)	0.25091 (12)	0.0468 (3)
H5A	−0.2323	0.5600	0.3408	0.070*
C7	0.15802 (8)	0.63304 (11)	0.10210 (14)	0.0317 (2)
H7A	0.1617	0.6830	0.0074	0.038*
C11	−0.13455 (8)	0.59747 (11)	0.21578 (14)	0.0316 (2)
C8	0.05963 (8)	0.61437 (10)	0.14540 (13)	0.0288 (2)
C13	0.02894 (8)	0.52087 (11)	0.25578 (14)	0.0313 (2)
H13A	0.0739	0.4638	0.3070	0.038*
C12	−0.06604 (8)	0.51181 (11)	0.28980 (14)	0.0320 (3)
H12A	−0.0848	0.4483	0.3625	0.038*
O1	0.32758 (7)	0.71114 (11)	−0.03290 (14)	0.0580 (3)
C5	0.26819 (8)	0.52924 (12)	0.32898 (14)	0.0337 (3)
C6	0.24587 (8)	0.59391 (11)	0.16895 (14)	0.0318 (2)
C9	−0.01161 (8)	0.69363 (11)	0.06446 (14)	0.0337 (3)
H9A	0.0060	0.7520	−0.0155	0.040*
C10	−0.10703 (8)	0.68732 (11)	0.10023 (15)	0.0355 (3)
H10A	−0.1525	0.7428	0.0474	0.043*
C4	0.32958 (9)	0.63232 (12)	0.07624 (15)	0.0373 (3)
C3	0.41508 (8)	0.45675 (13)	0.21746 (14)	0.0366 (3)
C2	0.51631 (10)	0.43795 (19)	0.29247 (18)	0.0544 (4)
H2A	0.5351	0.5122	0.3594	0.082*
H2B	0.5593	0.4289	0.2064	0.082*
H2C	0.5192	0.3608	0.3595	0.082*
C1	0.37811 (12)	0.34509 (14)	0.11015 (19)	0.0525 (4)
H1A	0.3133	0.3633	0.0669	0.079*
H1B	0.3789	0.2665	0.1744	0.079*
H1C	0.4186	0.3343	0.0207	0.079*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0294 (4)	0.0477 (5)	0.0443 (5)	−0.0016 (3)	0.0091 (3)	0.0076 (4)
O3	0.0317 (4)	0.0625 (6)	0.0287 (4)	0.0045 (4)	0.0036 (3)	0.0062 (4)
O2	0.0318 (4)	0.0783 (7)	0.0309 (4)	−0.0035 (4)	0.0067 (3)	0.0073 (4)
O5	0.0273 (4)	0.0666 (6)	0.0468 (5)	0.0088 (4)	0.0051 (4)	0.0100 (5)
C7	0.0339 (6)	0.0314 (5)	0.0302 (5)	−0.0014 (4)	0.0052 (4)	0.0013 (4)
C11	0.0270 (5)	0.0372 (6)	0.0303 (5)	0.0024 (4)	0.0003 (4)	−0.0045 (4)
C8	0.0290 (5)	0.0293 (5)	0.0281 (5)	−0.0001 (4)	0.0015 (4)	−0.0026 (4)
C13	0.0286 (5)	0.0316 (5)	0.0334 (5)	0.0038 (4)	0.0007 (4)	0.0037 (4)
C12	0.0310 (5)	0.0352 (5)	0.0299 (5)	0.0005 (4)	0.0026 (4)	0.0039 (4)
O1	0.0496 (6)	0.0612 (6)	0.0660 (7)	0.0073 (5)	0.0224 (5)	0.0309 (5)
C5	0.0273 (5)	0.0443 (6)	0.0294 (5)	−0.0052 (4)	0.0025 (4)	0.0005 (4)
C6	0.0298 (5)	0.0360 (5)	0.0301 (5)	−0.0023 (4)	0.0063 (4)	0.0010 (4)
C9	0.0365 (6)	0.0311 (5)	0.0327 (5)	−0.0015 (4)	−0.0015 (4)	0.0038 (4)
C10	0.0334 (6)	0.0347 (6)	0.0373 (6)	0.0052 (4)	−0.0047 (4)	0.0032 (5)
C4	0.0332 (6)	0.0393 (6)	0.0406 (6)	−0.0009 (4)	0.0100 (5)	0.0050 (5)
C3	0.0326 (6)	0.0481 (7)	0.0297 (5)	0.0031 (5)	0.0051 (4)	0.0032 (5)
C2	0.0337 (6)	0.0894 (11)	0.0402 (7)	0.0138 (7)	0.0031 (5)	0.0039 (7)
C1	0.0594 (9)	0.0470 (8)	0.0511 (8)	−0.0002 (6)	0.0036 (7)	−0.0049 (6)

Geometric parameters (Å, °)

O4—C4	1.3564 (15)	C12—H12A	0.9300
O4—C3	1.4314 (15)	O1—C4	1.1991 (15)
O3—C5	1.3399 (15)	C5—C6	1.4722 (16)
O3—C3	1.4493 (14)	C6—C4	1.4882 (16)
O2—C5	1.2076 (15)	C9—C10	1.3814 (17)
O5—C11	1.3539 (14)	C9—H9A	0.9300
O5—H5A	0.8200	C10—H10A	0.9300
C7—C6	1.3580 (16)	C3—C2	1.5019 (17)
C7—C8	1.4513 (15)	C3—C1	1.5053 (19)
C7—H7A	0.9300	C2—H2A	0.9600
C11—C10	1.3907 (17)	C2—H2B	0.9600
C11—C12	1.3968 (16)	C2—H2C	0.9600
C8—C13	1.4023 (15)	C1—H1A	0.9600
C8—C9	1.4044 (15)	C1—H1B	0.9600
C13—C12	1.3730 (16)	C1—H1C	0.9600
C13—H13A	0.9300

C4—O4—C3	118.76 (9)	C8—C9—H9A	119.1
C5—O3—C3	119.91 (9)	C9—C10—C11	119.52 (10)
C11—O5—H5A	109.5	C9—C10—H10A	120.2
C6—C7—C8	134.33 (10)	C11—C10—H10A	120.2
C6—C7—H7A	112.8	O1—C4—O4	118.33 (11)
C8—C7—H7A	112.8	O1—C4—C6	125.42 (12)
O5—C11—C10	118.41 (10)	O4—C4—C6	116.21 (10)
O5—C11—C12	122.02 (11)	O4—C3—O3	108.99 (10)
C10—C11—C12	119.56 (10)	O4—C3—C2	106.43 (11)
C13—C8—C9	117.19 (10)	O3—C3—C2	106.12 (10)
C13—C8—C7	125.81 (10)	O4—C3—C1	110.86 (10)
C9—C8—C7	116.95 (10)	O3—C3—C1	110.31 (11)
C12—C13—C8	121.38 (10)	C2—C3—C1	113.88 (13)
C12—C13—H13A	119.3	C3—C2—H2A	109.5
C8—C13—H13A	119.3	C3—C2—H2B	109.5
C13—C12—C11	120.30 (10)	H2A—C2—H2B	109.5
C13—C12—H12A	119.9	C3—C2—H2C	109.5
C11—C12—H12A	119.9	H2A—C2—H2C	109.5
O2—C5—O3	117.55 (11)	H2B—C2—H2C	109.5
O2—C5—C6	125.47 (11)	C3—C1—H1A	109.5
O3—C5—C6	116.88 (10)	C3—C1—H1B	109.5
C7—C6—C5	127.45 (10)	H1A—C1—H1B	109.5
C7—C6—C4	115.66 (10)	C3—C1—H1C	109.5
C5—C6—C4	116.62 (10)	H1A—C1—H1C	109.5
C10—C9—C8	121.84 (10)	H1B—C1—H1C	109.5
C10—C9—H9A	119.1

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2ⁱ	0.82	1.98	2.7919 (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]

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