5-Hydr­oxy-2-methyl-4H-pyran-4-one

Shaheen, M.A.; Hartinger, C.G.; Tahir, M.N.; Shafiq, A.A.; Keppler, B.K.

doi:10.1107/S1600536809003158

organic compounds

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doi:10.1107/S1600536809003158

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5-Hydroxy-2-methyl-4H-pyran-4-one

Muhammad Ashraf Shaheen,^a Christian G. Hartinger,^b M. Nawaz Tahir,^c ^* Ahmad Awan Shafiq ^d and Bernhard K. Keppler ^b

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, ^bInstitute of Inorganic Chemistry, University of Vienna, Whaeringer Strasse 42, A-1090 Vienna, Austria, ^cDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^dPAEC, PO Box No. 1114, Islamabad, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 25 January 2009; accepted 26 January 2009; online 31 January 2009)

The title compound, C₆H₆O₃, is a member of the pyrone family. The molecules are planar (r.m.s. deviation of the asymmetric unit is 0.0248 Å, whereas that of the dimer is 0.0360 Å) and they are dimerized due to intermolecular O—H⋯O hydrogen bonds. The dimers are connected to each other through hydrogen bonds involving the CH₃ group and the hydroxy O atom. There are π–π interactions between the centroids of the pyrone rings at a distance of 3.8552 (13) Å. A C—H⋯π interaction also exists between the carbonyl group and the centroid CgA of the pyrone ring, with O⋯CgA = 3.65 (1) Å and C⋯CgA = 4.363 (2) Å.

Related literature

For general background, see: Aytemir et al. (1999 ); Erol & Yulug (1999 ). For studies involving metal complexes of allomaltol, see: Ma et al. (2004 ); Shaheen et al. (2008 , 2008a ). For crystal structures of related compounds, see: Tak et al. (1994 ); Rahman et al. (1997 ).

Experimental

Crystal data

C₆H₆O₃
M_r = 126.11
Triclinic, $[P \overline 1]$
a = 5.4467 (4) Å
b = 7.3301 (5) Å
c = 7.6945 (5) Å
α = 105.354 (3)°
β = 98.416 (4)°
γ = 100.008 (4)°
V = 285.68 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 (2) K
0.22 × 0.20 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.970, T_max = 0.986
6426 measured reflections
1504 independent reflections
713 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.131
S = 1.00
1504 reflections
87 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.87 (3)	2.46 (2)	2.7853 (19)	103.1 (18)
O2—H2⋯O3ⁱ	0.87 (3)	1.83 (3)	2.635 (2)	152 (2)
C6—H6A⋯O2ⁱⁱ	0.96	2.42	3.378 (3)	173
Symmetry codes: (i) -x-1, -y, -z+1; (ii) x, y, z-1; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003158/at2715sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003158/at2715Isup2.hkl

checkCIF report

Comment top

A variety of compounds with a 4(1H)-pyridinone structure have been synthesized and their biological activities studied extensively (Aytemir et al., 1999; Erol & Yulug, 1999). Allomaltol, the title compound (I), (Fig. 1) and its derivatives have been exploited as iron chelators (Ma et al., 2004). Ruthenium and osmium complexes of allomaltol were found to be effective in catalyzing the hydration of chloroacetonitriles (Shaheen et al., 2008, 2008a).

The crystal structures of 3-Hydroxy-4-pyrone (Tak et al., 1994) has been published which have same heterocyclic ring as of title compound. 3-Hydroxy-2-methyl-4H-pyran-4-one (Rahman et al., 1997) has also been published which is chemical isomer of (I) but have different position of CH₃. The title compound has been prepared for various purposes such as complexation and as an intermediate ligand.

The heterocyclic ring is not regular as it has two C—C [1.426 (3), 1.446 (3) Å], two C═C [1.323 (3), 1.334 (3) Å] and two C—O [1.352 (3), 1.358 (3) Å], bonds respectively. Due to intra as well as intermolecular H-bonds (Table 1), the molecules are dimerized with central four-membered [O···H···O···H] ring, (Fig. 2). The dimers are linked to each other through H-bond between CH₃ and hydroxy groups. The molecules may be stabilized due to π–π interaction between the centroids of the ring A (O1/C1–C5). The distance between the centroids of CgA and CgAⁱ [Symmetry code: i = -x, 1 - y, 1 - z] is 3.8552 (13) Å. There exist a C3═O3···π interaction (Table 1), as well.

Related literature top

For general background, see: Aytemir et al. (1999); Erol & Yulug (1999). For studies involving metal complexes of the title compound, see: Ma et al. (2004); Shaheen et al. (2008, 2008a). For crystal structures of related compounds, see: Tak et al. (1994); Rahman et al. (1997). [Please check amended text]

Experimental top

A mixture of 2-chloromethyl-5-hydroxy-4-pyron (1.0 g, 0.6 mmol) and zinc dust (0.8 g, 12 mmol) in water (20 ml) was stirred for 30 min at 323 K. Concentrated HCl (6 ml) was added dropwise to dissolve the zinc dust completely and the mixture was stirred for 3 h at 353 K. The reaction mixture was transferred to ice–water and extracted with dichloromethane, dried with anhydrous Na₂SO₄ and evaporated to dryness. The crystals of the title compound were obtained by recrystallizing the crude product in isopropanol.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. ORTEP drawing of the title compound, with the atom numbering scheme. The thermal ellipsoids are drawn at the 30% probability level. H atoms are shown by small circles of arbitrary radii.
	Fig. 2. The packing figure (PLATON: Spek, 2003) which shows that the title compound is dimersed and dimers are connected through H-bonds in helical way.

(I) top

Crystal data top

C₆H₆O₃	Z = 2
M_r = 126.11	F(000) = 132
Triclinic, P1	D_x = 1.466 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.4467 (4) Å	Cell parameters from 1504 reflections
b = 7.3301 (5) Å	θ = 2.8–29.1°
c = 7.6945 (5) Å	µ = 0.12 mm⁻¹
α = 105.354 (3)°	T = 296 K
β = 98.416 (4)°	Prismatic, colourless
γ = 100.008 (4)°	0.22 × 0.20 × 0.10 mm
V = 285.68 (4) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1504 independent reflections
Radiation source: fine-focus sealed tube	713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 7.40 pixels mm^-1	θ_max = 29.1°, θ_min = 2.8°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
T_min = 0.970, T_max = 0.986	l = −10→10
6426 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0523P)² + 0.0219P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1504 reflections	Δρ_max = 0.18 e Å⁻³
87 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (14)

Crystal data top

C₆H₆O₃	γ = 100.008 (4)°
M_r = 126.11	V = 285.68 (4) Å³
Triclinic, P1	Z = 2
a = 5.4467 (4) Å	Mo Kα radiation
b = 7.3301 (5) Å	µ = 0.12 mm⁻¹
c = 7.6945 (5) Å	T = 296 K
α = 105.354 (3)°	0.22 × 0.20 × 0.10 mm
β = 98.416 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1504 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	713 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.986	R_int = 0.045
6426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.18 e Å⁻³
1504 reflections	Δρ_min = −0.20 e Å⁻³
87 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.2557 (3)	0.3634 (2)	0.37275 (16)	0.0542 (5)
O2	−0.1534 (3)	0.1916 (2)	0.64758 (18)	0.0641 (6)
O3	−0.4440 (3)	0.0215 (2)	0.29282 (18)	0.0631 (6)
C1	0.1595 (4)	0.3242 (3)	0.5153 (3)	0.0554 (8)
C2	−0.0705 (4)	0.2171 (3)	0.4961 (3)	0.0467 (7)
C3	−0.2315 (4)	0.1292 (3)	0.3153 (3)	0.0455 (7)
C4	−0.1223 (4)	0.1770 (3)	0.1711 (3)	0.0486 (7)
C5	0.1096 (4)	0.2896 (3)	0.2016 (3)	0.0463 (7)
C6	0.2424 (4)	0.3492 (4)	0.0642 (3)	0.0624 (8)
H1	0.26084	0.37532	0.63280	0.0664*
H2	−0.299 (5)	0.111 (4)	0.628 (3)	0.0769*
H4	−0.21633	0.12780	0.05123	0.0584*
H6A	0.13508	0.29403	−0.05590	0.0936*
H6B	0.28060	0.48817	0.09427	0.0936*
H6C	0.39779	0.30418	0.06523	0.0936*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0501 (9)	0.0655 (10)	0.0377 (8)	−0.0005 (7)	−0.0002 (6)	0.0131 (7)
O2	0.0703 (11)	0.0723 (12)	0.0356 (8)	−0.0115 (9)	0.0030 (7)	0.0143 (8)
O3	0.0506 (10)	0.0853 (12)	0.0440 (8)	−0.0041 (9)	0.0051 (7)	0.0182 (8)
C1	0.0612 (15)	0.0605 (15)	0.0346 (10)	0.0001 (12)	−0.0004 (10)	0.0117 (10)
C2	0.0540 (14)	0.0473 (13)	0.0343 (10)	0.0071 (11)	0.0035 (9)	0.0101 (9)
C3	0.0410 (13)	0.0519 (14)	0.0391 (11)	0.0078 (11)	0.0038 (9)	0.0099 (9)
C4	0.0457 (13)	0.0612 (15)	0.0327 (9)	0.0077 (11)	0.0027 (9)	0.0089 (10)
C5	0.0454 (13)	0.0544 (14)	0.0343 (10)	0.0090 (11)	0.0033 (9)	0.0091 (9)
C6	0.0547 (14)	0.0819 (17)	0.0488 (12)	0.0074 (12)	0.0110 (10)	0.0210 (12)

Geometric parameters (Å, º) top

O1—C1	1.358 (3)	C4—C5	1.334 (3)
O1—C5	1.352 (3)	C5—C6	1.480 (3)
O2—C2	1.356 (3)	C1—H1	0.9300
O3—C3	1.243 (3)	C4—H4	0.9300
O2—H2	0.87 (3)	C6—H6A	0.9600
C1—C2	1.323 (3)	C6—H6B	0.9600
C2—C3	1.446 (3)	C6—H6C	0.9600
C3—C4	1.426 (3)

O1···O3ⁱ	3.200 (2)	C2···O1ⁱⁱⁱ	3.350 (3)
O1···O1ⁱⁱ	3.078 (2)	C2···O2^vi	3.405 (3)
O1···C2ⁱⁱⁱ	3.350 (3)	C2···C1ⁱⁱⁱ	3.501 (3)
O2···O3	2.7853 (19)	C2···C2^vi	3.415 (3)
O2···C6^iv	3.378 (3)	C6···O2^ix	3.378 (3)
O2···O3^v	2.635 (2)	C3···H2^v	3.00 (3)
O2···C2^vi	3.405 (3)	C4···H6C^vii	3.0000
O3···O2^v	2.635 (2)	H2···O3	2.46 (2)
O3···O1^vii	3.200 (2)	H2···O3^v	1.83 (3)
O3···O2	2.7853 (19)	H2···C3^v	3.00 (3)
O2···H6Bⁱⁱⁱ	2.9000	H4···H6A	2.4500
O2···H6A^iv	2.4200	H4···O3^viii	2.8200
O3···H2	2.46 (2)	H6A···O2^ix	2.4200
O3···H2^v	1.83 (3)	H6A···H4	2.4500
O3···H4^viii	2.8200	H6B···O2ⁱⁱⁱ	2.9000
C1···C1ⁱⁱⁱ	3.387 (3)	H6C···C4ⁱ	3.0000
C1···C2ⁱⁱⁱ	3.501 (3)

C1—O1—C5	118.57 (18)	O1—C5—C4	121.3 (2)
C2—O2—H2	116.2 (15)	O1—C1—H1	118.00
O1—C1—C2	123.6 (2)	C2—C1—H1	118.00
O2—C2—C3	120.55 (19)	C3—C4—H4	119.00
C1—C2—C3	120.2 (2)	C5—C4—H4	119.00
O2—C2—C1	119.3 (2)	C5—C6—H6A	109.00
O3—C3—C4	124.7 (2)	C5—C6—H6B	109.00
C2—C3—C4	113.9 (2)	C5—C6—H6C	109.00
O3—C3—C2	121.4 (2)	H6A—C6—H6B	109.00
C3—C4—C5	122.5 (2)	H6A—C6—H6C	109.00
O1—C5—C6	111.28 (19)	H6B—C6—H6C	109.00
C4—C5—C6	127.5 (2)

C5—O1—C1—C2	0.0 (3)	C1—C2—C3—O3	177.0 (2)
C1—O1—C5—C4	−1.4 (3)	C1—C2—C3—C4	−2.6 (3)
C1—O1—C5—C6	179.1 (2)	O3—C3—C4—C5	−178.3 (2)
O1—C1—C2—O2	−177.69 (19)	C2—C3—C4—C5	1.3 (3)
O1—C1—C2—C3	2.0 (4)	C3—C4—C5—O1	0.7 (4)
O2—C2—C3—O3	−3.3 (3)	C3—C4—C5—C6	−179.9 (2)
O2—C2—C3—C4	177.2 (2)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y, z+1; (v) −x−1, −y, −z+1; (vi) −x, −y, −z+1; (vii) x−1, y, z; (viii) −x−1, −y, −z; (ix) x, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.87 (3)	2.46 (2)	2.7853 (19)	103.1 (18)
O2—H2···O3^v	0.87 (3)	1.83 (3)	2.635 (2)	152 (2)
C6—H6A···O2^ix	0.9600	2.4200	3.378 (3)	173.00
C3—O3···CgA^vii	1.24 (1)	3.65 (1)	4.363 (2)	118 (1)

Symmetry codes: (v) −x−1, −y, −z+1; (vii) x−1, y, z; (ix) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₆H₆O₃
M_r	126.11
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.4467 (4), 7.3301 (5), 7.6945 (5)
α, β, γ (°)	105.354 (3), 98.416 (4), 100.008 (4)
V (Å³)	285.68 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.22 × 0.20 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.970, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	6426, 1504, 713
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.131, 1.00
No. of reflections	1504
No. of parameters	87
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.87 (3)	2.46 (2)	2.7853 (19)	103.1 (18)
O2—H2···O3ⁱ	0.87 (3)	1.83 (3)	2.635 (2)	152 (2)
C6—H6A···O2ⁱⁱ	0.9600	2.4200	3.378 (3)	173.00
C3—O3···CgAⁱⁱⁱ	1.243 (3)	3.6465 (19)	4.363 (2)	117.56 (13)

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

References

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doi:10.1107/S1600536809003158

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