6-Hy­droxy-5,7,8-trimethyl­chroman-2-one

Goswami, S.K.; Hanton, L.R.; McAdam, C.J.; Moratti, S.C.; Simpson, J.

doi:10.1107/S1600536811019982

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages o1566-o1567

doi:10.1107/S1600536811019982

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6-Hydroxy-5,7,8-trimethylchroman-2-one

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

^aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

(Received 25 May 2011; accepted 26 May 2011; online 4 June 2011)

The title compound, C₁₂H₁₄O₃, consists of a chromanone unit with an –OH substituent at the 4-position and methyl substituents on the remaining C atoms of the aromatic ring. The fused pyranone ring adopts a distorted envelope conformation with the methylene group adjacent to the carbonyl carbon as the flap atom. The crystal structure is stabilized by classical O—H⋯O hydrogen bonds and weak C—H⋯O and C—H⋯π interactions, generating a three-dimensional network.

Related literature

For the synthesis, see: Ong et al. (2008 ). For a related structure, see: Budzianowski & Katrusiak (2002 ). For current applications of this compound, see: Ong et al. (2008); Harada et al. (1987 ); Hernández-Torres et al. (2009 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₄O₃
M_r = 206.23
Monoclinic, P 2₁ /c
a = 4.5339 (6) Å
b = 16.815 (2) Å
c = 13.302 (2) Å
β = 96.495 (8)°
V = 1007.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 89 K
0.38 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2009 ) T_min = 0.809, T_max = 1.00
12531 measured reflections
2021 independent reflections
1535 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.201
S = 1.13
2021 reflections
142 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O9ⁱ	0.85 (2)	2.02 (3)	2.754 (3)	144 (3)
C8—H8B⋯O9ⁱⁱ	0.99	2.58	3.395 (4)	140
C8—H8B⋯O4ⁱⁱⁱ	0.99	2.66	3.440 (4)	136
C7—H7B⋯Cg2^iv	0.99	2.61	3.505 (3)	150
C31—H31C⋯Cg2^v	0.98	2.62	3.512 (3)	151
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+2, -z; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x-1, y, z; (v) x+1, y, z.

Data collection: APEX2 (Bruker 2009); cell refinement: SAINT (Bruker 2009); data reduction: SAINT; program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ) and TITAN2000 (Hunter & Simpson, 1999 ); 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019982/hg5043sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019982/hg5043Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019982/hg5043Isup3.cml

checkCIF report

Comment top

The title compound (I) has been utilized in the synthesis of important members of the Vitamin E family (Harada et al., 1987; Hernández-Torres et al., 2009) and as a redox-trigger in liposome research (Ong et al., 2008). We have utilized (I) in synthesis of redox-active quinone monomers as part of our current interest in electro-mechanical actuators.

The structure of (I), Fig. 1, consists of a chromanone unit with an OH substituent at the 4-position and methyl substituents on C2, C3 and C5. The fused pyranone ring adopts a distorted envelope conformation with the C8 atom as the flap atom. Bond distances (Allen et al., 1987) and angles are normal and similar to those in the closely related compound with two methyl substituents at C7 (4,4-dimethyl-6-hydroxy-5,7,8-trimethylchroman-2-one) (Budzianowski & Katrusiak, 2002).

In the crystal structure classical O4–H4O···O9 hydrogen bonds form zigzag chains down the b axis. Weaker C8–H8B···O4 and C8–H8B···O9 interactions link the chains into sheets in the bc plane (Fig. 2). The structure is further stabilized by C7–H7B···π and C31–H31C···π interactions forming stacks down a, Fig 3.

Related literature top

For the synthesis, see: Ong et al. (2008). For a related structure, see: Budzianowski & Katrusiak (2002). For current applications of this compound, see: Ong et al. (2008); Harada et al. (1987); Hernández-Torres et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared (Ong et al., 2008) by a Friedel-Crafts type addition reaction of trimethylhydroquinone with acrylic acid using methanesulfonic acid as the acid catalyst in dichloroethane at 100°C for 2 h. X-ray quality crystals were grown from aqueous ethanol.

Computing details top

Data collection: APEX2 (Bruker 2009); cell refinement: SAINT (Bruker 2009); data reduction: SAINT (Bruker 2009); program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of (I) showing the atom numbering with ellipsoids drawn at the 50% probability level.
	Fig. 2. bc layer of (I). Dashed lines show O–H···O hydrogen bonds and C–H···O interactions.
	Fig. 3. Crystal packing of (I) showing the three dimensional network structure. Hydrogen bonds are drawn as dashed lines.

6-Hydroxy-5,7,8-trimethylchroman-2-one top

Crystal data top

C₁₂H₁₄O₃	F(000) = 440
M_r = 206.23	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1569 reflections
a = 4.5339 (6) Å	θ = 2.4–25.9°
b = 16.815 (2) Å	µ = 0.10 mm⁻¹
c = 13.302 (2) Å	T = 89 K
β = 96.495 (8)°	Block, colourless
V = 1007.6 (2) Å³	0.38 × 0.11 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2021 independent reflections
Radiation source: fine-focus sealed tube	1535 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ω scans	θ_max = 26.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker 2009)	h = −5→5
T_min = 0.809, T_max = 1.00	k = −20→20
12531 measured reflections	l = −13→16

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0733P)² + 1.6783P] where P = (F_o² + 2F_c²)/3
2021 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.39 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₁₄O₃	V = 1007.6 (2) Å³
M_r = 206.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.5339 (6) Å	µ = 0.10 mm⁻¹
b = 16.815 (2) Å	T = 89 K
c = 13.302 (2) Å	0.38 × 0.11 × 0.06 mm
β = 96.495 (8)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2021 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2009)	1535 reflections with I > 2σ(I)
T_min = 0.809, T_max = 1.00	R_int = 0.063
12531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	1 restraint
wR(F²) = 0.201	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.39 e Å⁻³
2021 reflections	Δρ_min = −0.27 e Å⁻³
142 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	0.0748 (4)	0.96722 (11)	0.22522 (15)	0.0219 (5)
C1	−0.0405 (6)	0.89510 (16)	0.2597 (2)	0.0194 (6)
C2	−0.2136 (6)	0.90381 (17)	0.3392 (2)	0.0199 (6)
C21	−0.2918 (7)	0.98596 (17)	0.3742 (2)	0.0269 (7)
H21A	−0.4854	0.9843	0.4002	0.040*
H21B	−0.3003	1.0231	0.3171	0.040*
H21C	−0.1402	1.0037	0.4278	0.040*
C3	−0.3075 (6)	0.83491 (17)	0.3848 (2)	0.0207 (6)
C31	−0.4844 (7)	0.83761 (18)	0.4734 (2)	0.0253 (7)
H31A	−0.4523	0.8888	0.5082	0.038*
H31B	−0.4208	0.7944	0.5203	0.038*
H31C	−0.6957	0.8314	0.4496	0.038*
C4	−0.2276 (6)	0.76058 (17)	0.3479 (2)	0.0207 (6)
O4	−0.3260 (5)	0.69559 (12)	0.39722 (16)	0.0261 (5)
H4O	−0.292 (8)	0.6515 (14)	0.369 (2)	0.031*
C5	−0.0575 (6)	0.75268 (17)	0.2672 (2)	0.0210 (6)
C51	0.0261 (7)	0.67095 (17)	0.2340 (2)	0.0258 (7)
H51A	0.1317	0.6425	0.2916	0.039*
H51B	0.1550	0.6756	0.1799	0.039*
H51C	−0.1539	0.6415	0.2090	0.039*
C6	0.0368 (6)	0.82203 (17)	0.2215 (2)	0.0195 (6)
C7	0.2168 (6)	0.82110 (17)	0.1330 (2)	0.0209 (6)
H7A	0.1559	0.7753	0.0886	0.025*
H7B	0.4297	0.8148	0.1578	0.025*
C8	0.1714 (7)	0.89840 (18)	0.0725 (2)	0.0254 (7)
H8A	0.3188	0.9010	0.0231	0.031*
H8B	−0.0288	0.8980	0.0341	0.031*
C9	0.2022 (6)	0.97048 (17)	0.1380 (2)	0.0224 (6)
O9	0.3212 (5)	1.03231 (12)	0.11866 (16)	0.0283 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0275 (11)	0.0175 (10)	0.0222 (11)	−0.0005 (8)	0.0097 (8)	−0.0005 (8)
C1	0.0225 (14)	0.0163 (14)	0.0189 (14)	−0.0006 (11)	0.0010 (11)	0.0019 (11)
C2	0.0190 (14)	0.0215 (14)	0.0195 (14)	0.0027 (11)	0.0043 (11)	−0.0027 (11)
C21	0.0324 (16)	0.0215 (15)	0.0274 (16)	0.0017 (13)	0.0066 (13)	−0.0017 (12)
C3	0.0212 (14)	0.0230 (14)	0.0180 (14)	0.0017 (11)	0.0024 (11)	0.0004 (11)
C31	0.0302 (16)	0.0233 (15)	0.0241 (16)	0.0018 (12)	0.0100 (13)	−0.0006 (12)
C4	0.0200 (14)	0.0205 (14)	0.0211 (14)	−0.0006 (11)	0.0000 (11)	0.0012 (12)
O4	0.0331 (12)	0.0175 (10)	0.0296 (12)	−0.0004 (9)	0.0117 (9)	0.0031 (9)
C5	0.0230 (15)	0.0193 (15)	0.0210 (15)	0.0009 (11)	0.0033 (12)	0.0008 (11)
C51	0.0297 (16)	0.0200 (15)	0.0289 (16)	0.0031 (12)	0.0087 (13)	0.0007 (12)
C6	0.0172 (13)	0.0224 (14)	0.0188 (14)	0.0020 (11)	0.0020 (11)	0.0002 (11)
C7	0.0212 (14)	0.0206 (14)	0.0214 (15)	0.0012 (11)	0.0047 (12)	−0.0007 (12)
C8	0.0317 (17)	0.0247 (15)	0.0207 (15)	−0.0006 (13)	0.0065 (13)	−0.0012 (12)
C9	0.0231 (14)	0.0231 (15)	0.0214 (15)	0.0024 (12)	0.0042 (12)	0.0027 (12)
O9	0.0360 (12)	0.0206 (11)	0.0300 (12)	−0.0021 (9)	0.0111 (10)	0.0025 (9)

Geometric parameters (Å, º) top

O1—C9	1.354 (3)	C4—C5	1.398 (4)
O1—C1	1.417 (3)	O4—H4O	0.854 (18)
C1—C6	1.390 (4)	C5—C6	1.404 (4)
C1—C2	1.394 (4)	C5—C51	1.505 (4)
C2—C3	1.397 (4)	C51—H51A	0.9800
C2—C21	1.512 (4)	C51—H51B	0.9800
C21—H21A	0.9800	C51—H51C	0.9800
C21—H21B	0.9800	C6—C7	1.506 (4)
C21—H21C	0.9800	C7—C8	1.530 (4)
C3—C4	1.405 (4)	C7—H7A	0.9900
C3—C31	1.500 (4)	C7—H7B	0.9900
C31—H31A	0.9800	C8—C9	1.490 (4)
C31—H31B	0.9800	C8—H8A	0.9900
C31—H31C	0.9800	C8—H8B	0.9900
C4—O4	1.374 (3)	C9—O9	1.212 (4)

C9—O1—C1	121.4 (2)	C4—C5—C51	119.4 (3)
C6—C1—C2	123.9 (3)	C6—C5—C51	122.2 (3)
C6—C1—O1	121.3 (2)	C5—C51—H51A	109.5
C2—C1—O1	114.6 (2)	C5—C51—H51B	109.5
C1—C2—C3	117.9 (3)	H51A—C51—H51B	109.5
C1—C2—C21	120.1 (3)	C5—C51—H51C	109.5
C3—C2—C21	122.0 (3)	H51A—C51—H51C	109.5
C2—C21—H21A	109.5	H51B—C51—H51C	109.5
C2—C21—H21B	109.5	C1—C6—C5	118.3 (3)
H21A—C21—H21B	109.5	C1—C6—C7	118.5 (3)
C2—C21—H21C	109.5	C5—C6—C7	123.3 (2)
H21A—C21—H21C	109.5	C6—C7—C8	110.5 (2)
H21B—C21—H21C	109.5	C6—C7—H7A	109.6
C2—C3—C4	118.9 (3)	C8—C7—H7A	109.6
C2—C3—C31	122.2 (3)	C6—C7—H7B	109.6
C4—C3—C31	118.9 (3)	C8—C7—H7B	109.6
C3—C31—H31A	109.5	H7A—C7—H7B	108.1
C3—C31—H31B	109.5	C9—C8—C7	112.6 (2)
H31A—C31—H31B	109.5	C9—C8—H8A	109.1
C3—C31—H31C	109.5	C7—C8—H8A	109.1
H31A—C31—H31C	109.5	C9—C8—H8B	109.1
H31B—C31—H31C	109.5	C7—C8—H8B	109.1
O4—C4—C5	121.9 (2)	H8A—C8—H8B	107.8
O4—C4—C3	115.5 (2)	O9—C9—O1	117.4 (3)
C5—C4—C3	122.6 (3)	O9—C9—C8	126.0 (3)
C4—O4—H4O	113 (2)	O1—C9—C8	116.6 (2)
C4—C5—C6	118.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O9ⁱ	0.85 (2)	2.02 (3)	2.754 (3)	144 (3)
C8—H8B···O9ⁱⁱ	0.99	2.58	3.395 (4)	140
C8—H8B···O4ⁱⁱⁱ	0.99	2.66	3.440 (4)	136
C7—H7B···Cg2^iv	0.99	2.61	3.505 (3)	150
C31—H31C···Cg2^v	0.98	2.62	3.512 (3)	151

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₃
M_r	206.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	89
a, b, c (Å)	4.5339 (6), 16.815 (2), 13.302 (2)
β (°)	96.495 (8)
V (Å³)	1007.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.11 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2009)
T_min, T_max	0.809, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	12531, 2021, 1535
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.201, 1.13
No. of reflections	2021
No. of parameters	142
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.27

Computer programs: APEX2 (Bruker 2009), SAINT (Bruker 2009), OLEX2 (Dolomanov et al., 2009), SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O9ⁱ	0.854 (18)	2.02 (3)	2.754 (3)	144 (3)
C8—H8B···O9ⁱⁱ	0.99	2.58	3.395 (4)	140
C8—H8B···O4ⁱⁱⁱ	0.99	2.66	3.440 (4)	136
C7—H7B···Cg2^iv	0.99	2.61	3.505 (3)	150
C31—H31C···Cg2^v	0.98	2.62	3.512 (3)	151

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

Acknowledgements

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.

References

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages o1566-o1567

doi:10.1107/S1600536811019982

Open

access