6-Hy­droxy-7,8-dimethyl­chroman-2-one

Shailesh K Goswami; Lyall R Hanton; C John McAdam; Stephen C Moratti; Jim Simpson

doi:10.1107/S1600536812029704

. 2012 Jul 4;68(Pt 8):o2332–o2333. doi: 10.1107/S1600536812029704

6-Hydroxy-7,8-dimethylchroman-2-one

Shailesh K Goswami ^a, Lyall R Hanton ^a, C John McAdam ^a, Stephen C Moratti ^a, Jim Simpson ^a,^*

PMCID: PMC3414271 PMID: 22904804

Abstract

The title compound, C₁₁H₁₂O₃, is essentially planar, with an r.m.s. deviation of 0.179 Å from the mean plane through the 14 non-H atoms in the molecule. The benzene ring and the pyranone mean plane are inclined at 13.12 (6)° to one another and the pyranone ring adopts a flattened chair conformation. In the crystal, O—H⋯O hydrogen bonds and C—H⋯O contacts form R ₁ ²(6) rings and link molecules into chains along b. Additional C—H⋯O contacts generate inversion dimers, with R ₂ ²(8) ring motifs, and form sheets parallel to (-102) which are linked by C—H⋯π interactions.

Related literature

For the synthesis, see: Lecea et al. (2010 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶) and for related structures, see: Cameron et al. (2011 ▶); Goswami et al. (2011 ▶, 2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₁₂O₃
M _r = 192.21
Triclinic,
a = 6.2808 (14) Å
b = 8.630 (2) Å
c = 9.389 (2) Å
α = 88.603 (6)°
β = 83.638 (5)°
γ = 69.088 (5)°
V = 472.40 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 92 K
0.34 × 0.32 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ▶) T _min = 0.656, T _max = 0.747
9073 measured reflections
3963 independent reflections
3368 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.188
S = 1.11
3963 reflections
132 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: APEX2 (Bruker, 2011 ▶) and SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029704/lh5497sup1.cif

e-68-o2332-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029704/lh5497Isup2.hkl

e-68-o2332-Isup2.hkl^{(194.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812029704/lh5497Isup3.cml

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

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

Cg is the centroid of the C4–C9 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8O⋯O1ⁱ	0.89 (2)	1.89 (2)	2.7788 (15)	175 (2)
C9—H9⋯O1ⁱ	0.95	2.63	3.3371 (16)	132
C2—H2A⋯O1ⁱⁱ	0.99	2.52	3.4626 (16)	159
C3—H3B⋯Cg ⁱⁱⁱ	0.99	2.54	3.4771 (15)	157
C61—H61C⋯Cg ^iv	0.98	2.79	3.6956 (16)	153

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

Acknowledgments

We thank the New Economy Research Fund (grant No. UOO-X0808) for support of this work and the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Our current research is focused on the preparation of quinone/hydroquinone based monomers for utilization in redox-active polymer gels. Synthesis of such systems is a multi-step process and often passes through a hydropyranone intermediate (Lecea et al., 2010; Cameron et al., 2011; Goswami et al., 2011). The title compound illustrates one such intermediate and was isolated during the synthesis of a trifluoromethyl substituted hydroquinone.

The title compound (I), Fig 1, is almost planar with an r.m.s. deviation of 0.179 Å from the best fit plane through the 14 non-hydrogen atoms in the molecule. The maximum deviation from this plane is 0.5437 (11) Å for C2. This is in keeping with the fact that the pyranone ring adopts a flattened chair conformation with the C2 atom displaced by 0.6004 (17) Å from the plane through C1/O2/C5/C4/C3 which, in turn, has an r.m.s. deviation of 0.076 Å. This is in contrast to the closely related 5,6-dimethyl-1,2,9,10- tetrahydropyrano[3,2-f]chromene-3,8-dione (Goswami et al., 2012), where both the C2 and O2 atoms of the pyranone rings were displaced significantly from the molecular plane in opposite directions. A search of the Cambridge Structural Database (Allen, 2002) revealed only two additional tetrahydropyrano derivatives (Goswami et al., 2011, Cameron et al., 2011). However, removing the restraint on substitution at the 3 and 4 positions of the pyranone ring, reveals the structures of more than 190 chromanone derivatives. The bond distances (Allen et al., 1987) and angles in the molecule are normal and, despite the variation in the pyranone ring conformations, similar to those found in related structures (Goswami et al., 2011, 2012; Cameron et al., 2011).

In the crystal structure, O8—H8O···O1 hydrogen bonds, augmented by non-classical C9—H9···O1 contacts, form R²₁(6) rings (Bernstein et al., 1995) and link molecules into rows along b, Fig 2. C2—H2A···O1 hydrogen bonds form inversion dimers generating R²₂(8) rings, Fig 3, which further connect the molecules into sheets approximately parallel to the (-1, 0, 2) plane, Fig 4. C—H···π contacts are also present linking adjacent molecules above and below the plane of the C4···C9 benzene ring and forming columns approximately orthogonal to the (-1, 0, 2) plane and resulting in a series of stacked layers, Fig 5.

Experimental

The title compound was prepared according to the literature (Lecea et al., 2010) by a Friedel-Crafts type reaction of 2,3-dimethylhydroquinone with acrylic acid. X-ray quality crystals of (I) were grown from CDCl₃.