4,7,8-Trimethyl-2H-chromen-2-one

Yang, J.-X.; Tan, X.-M.; Wang, X.-H.; Wang, Y.

doi:10.1107/S1600536812009646

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1014

doi:10.1107/S1600536812009646

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4,7,8-Trimethyl-2H-chromen-2-one

Jian-Xin Yang,^a ^* Xue-Mei Tan,^a Xiang-Hui Wang ^b and Yin Wang ^a

^aInstitute of Materials and Chemical Engineering, Hainan University, Haikou 570228, People's Republic of China, and ^bInstitute of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093, People's Republic of China
^*Correspondence e-mail: yangjxmail@sohu.com

(Received 6 February 2012; accepted 5 March 2012; online 10 March 2012)

The molecule of the title compound, C₁₂H₁₂O₂, is essentially planar, with a maximum deviation from the mean plane of all non-H atoms of 0.038 (1) Å for the methyl C atom in the 8-position. The crystal structure is characterized by antiparallel π–π stacking along the c axis, with centroid–centroid distances as short as 3.866 (1) Å. In the crystal, C—H⋯O hydrogen bonds connect the molecules across the stacks into ribbons in the a-axis direction.

Related literature

For general background to the pharmacological activity of coumarin derivatives, see: Xie et al. (2001 ); Tanitame et al. (2004 ); Shao et al. (1997 ); Rendenbach-Müller et al. (1994 ); Pochet et al. (1996 ). For a related structure, see: Gowda et al. (2010 ).

Experimental

Crystal data

C₁₂H₁₂O₂
M_r = 188.22
Monoclinic, P 2₁ /c
a = 7.276 (3) Å
b = 18.075 (6) Å
c = 7.246 (3) Å
β = 97.055 (5)°
V = 945.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 K
0.44 × 0.31 × 0.26 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
8545 measured reflections
2747 independent reflections
2176 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.112
S = 1.00
2747 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.95	2.56	3.460 (2)	159
C10—H10C⋯O2ⁱⁱ	0.98	2.54	3.493 (2)	164
Symmetry codes: (i) -x+2, -y, -z+2; (ii) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009646/ld2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009646/ld2048Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812009646/ld2048Isup3.cml

checkCIF report

Comment top

Coumarin derivatives exhibit a wide variety of pharmacological activities including anti-HIV (Xie et al., 2001), antibacterial (Tanitame et al., 2004), antioxidant (Shao et al., 1997), antithrombotic (Rendenbach-Müller et al., 1994) and antiinflammatory (Pochet et al., 1996) activities.

The molecular structure is shown in Fig. 1. In the crystal the molecules are linked by C—H···O hydrogen bonds to form ribbon-like motives (Table 1 and Fig. 2).

Related literature top

For general background to thepharmacological activity of coumarin derivatives, see: Xie et al. (2001); Tanitame et al. (2004); Shao et al. (1997); Rendenbach-Müller et al. (1994); Pochet et al. (1996). For a related structure, see: Gowda et al. (2010).

Experimental top

2,3-Dimethyl phenol (10.50 mmol) was slowly added at 278–288 K to a mixture of para-toluenesulfonic acid (0.5 g) and acetylacetic ester (10.50 mmol) while stirring for 30 min. The reaction mixture was stirred continuously for 12 more hours at room temperature and then poured into ice–water mixture (100 ml). The obtained solid was filtered off, washed with cold water and dried at room temperature. Colorless crystals of the title compound suitable for X-ray structure analysis were obtained by slow evaporation of a solution in the mixture of ethanol/ether over a period of two days.

Structure description top

The molecular structure is shown in Fig. 1. In the crystal the molecules are linked by C—H···O hydrogen bonds to form ribbon-like motives (Table 1 and Fig. 2).

For general background to thepharmacological activity of coumarin derivatives, see: Xie et al. (2001); Tanitame et al. (2004); Shao et al. (1997); Rendenbach-Müller et al. (1994); Pochet et al. (1996). For a related structure, see: Gowda et al. (2010).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. H-bonding in the crystals of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.
	Fig. 3. π–π stacking in the crystal of te title compound.

4,7,8-Trimethyl-2H-chromen-2-one top

Crystal data top

C₁₂H₁₂O₂	F(000) = 400
M_r = 188.22	D_x = 1.322 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.276 (3) Å	Cell parameters from 3283 reflections
b = 18.075 (6) Å	θ = 2.3–30.0°
c = 7.246 (3) Å	µ = 0.09 mm⁻¹
β = 97.055 (5)°	T = 153 K
V = 945.8 (6) Å³	Prism, colorless
Z = 4	0.44 × 0.31 × 0.26 mm

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2176 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.028
Graphite monochromator	θ_max = 30.1°, θ_min = 3.1°
Detector resolution: 28.5714 pixels mm^-1	h = −9→10
phi and ω scans	k = −24→25
8545 measured reflections	l = −10→10
2747 independent reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0269P)² + 0.551P] where P = (F_o² + 2F_c²)/3
2747 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₂H₁₂O₂	V = 945.8 (6) Å³
M_r = 188.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.276 (3) Å	µ = 0.09 mm⁻¹
b = 18.075 (6) Å	T = 153 K
c = 7.246 (3) Å	0.44 × 0.31 × 0.26 mm
β = 97.055 (5)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2176 reflections with I > 2σ(I)
8545 measured reflections	R_int = 0.028
2747 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
2747 reflections	Δρ_min = −0.33 e Å⁻³
130 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
H2	0.8364	0.0375	0.9962	0.029*
H5	0.4346	0.2356	0.8389	0.030*
H6	0.4708	0.3629	0.8497	0.030*
H10A	0.5336	0.0381	0.8616	0.035*
H10B	0.4726	0.1097	0.7392	0.035*
H10C	0.4183	0.1026	0.9459	0.035*
H11A	0.6432	0.4698	0.9153	0.037*
H11B	0.8581	0.4625	0.8914	0.037*
H11C	0.7941	0.4634	1.0949	0.037*
H12A	1.1505	0.3139	1.1756	0.036*
H12B	1.0632	0.3953	1.1693	0.036*
H12C	1.1483	0.3633	0.9921	0.036*
C1	1.01364 (18)	0.12436 (7)	1.07922 (18)	0.0243 (3)
C2	0.84235 (18)	0.08992 (7)	1.00252 (18)	0.0244 (3)
C3	0.69054 (18)	0.12937 (7)	0.93951 (18)	0.0224 (3)
C4	0.69972 (17)	0.20939 (7)	0.94548 (17)	0.0207 (2)
C5	0.55137 (18)	0.25623 (7)	0.88512 (19)	0.0248 (3)
C6	0.57298 (19)	0.33200 (7)	0.89207 (19)	0.0251 (3)
C7	0.74262 (18)	0.36425 (7)	0.96038 (18)	0.0234 (3)
C8	0.89411 (18)	0.31925 (7)	1.02295 (18)	0.0221 (3)
C9	0.86750 (17)	0.24271 (7)	1.01382 (17)	0.0206 (2)
C10	0.51347 (19)	0.09170 (8)	0.8651 (2)	0.0296 (3)
C11	0.7611 (2)	0.44726 (7)	0.9660 (2)	0.0305 (3)
C12	1.08022 (19)	0.35066 (8)	1.0964 (2)	0.0299 (3)
O1	1.02050 (12)	0.20031 (5)	1.07807 (13)	0.0240 (2)
O2	1.15405 (14)	0.09227 (6)	1.14331 (15)	0.0338 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0259 (6)	0.0213 (6)	0.0259 (6)	0.0034 (5)	0.0042 (5)	−0.0003 (5)
C2	0.0277 (7)	0.0189 (6)	0.0268 (6)	−0.0011 (5)	0.0041 (5)	−0.0012 (5)
C3	0.0246 (6)	0.0225 (6)	0.0205 (6)	−0.0035 (5)	0.0040 (5)	−0.0007 (5)
C4	0.0213 (6)	0.0211 (6)	0.0200 (6)	−0.0004 (4)	0.0038 (5)	−0.0002 (5)
C5	0.0202 (6)	0.0273 (6)	0.0262 (6)	−0.0003 (5)	0.0001 (5)	0.0003 (5)
C6	0.0238 (6)	0.0258 (6)	0.0254 (6)	0.0048 (5)	0.0014 (5)	0.0024 (5)
C7	0.0276 (6)	0.0204 (6)	0.0223 (6)	0.0014 (5)	0.0039 (5)	0.0018 (5)
C8	0.0223 (6)	0.0222 (6)	0.0220 (6)	−0.0010 (5)	0.0028 (5)	0.0000 (5)
C9	0.0196 (6)	0.0209 (6)	0.0214 (6)	0.0018 (4)	0.0025 (5)	0.0007 (5)
C10	0.0283 (7)	0.0267 (7)	0.0329 (7)	−0.0080 (5)	0.0006 (6)	−0.0005 (6)
C11	0.0366 (8)	0.0209 (6)	0.0335 (8)	0.0024 (5)	0.0016 (6)	0.0023 (5)
C12	0.0265 (7)	0.0257 (7)	0.0359 (7)	−0.0052 (5)	−0.0021 (6)	−0.0010 (6)
O1	0.0205 (4)	0.0212 (4)	0.0296 (5)	0.0020 (3)	−0.0004 (4)	0.0000 (4)
O2	0.0287 (5)	0.0271 (5)	0.0439 (6)	0.0075 (4)	−0.0030 (4)	−0.0006 (4)

Geometric parameters (Å, º) top

C1—C2	1.4421 (19)	C8—C12	1.5042 (18)
C2—H2	0.9500	C10—H10A	0.9800
C2—C3	1.3465 (18)	C10—H10B	0.9800
C3—C4	1.4484 (18)	C10—H10C	0.9800
C3—C10	1.4979 (18)	C11—H11A	0.9800
C4—C5	1.3990 (18)	C11—H11B	0.9800
C4—C9	1.3964 (17)	C11—H11C	0.9800
C5—H5	0.9500	C12—H12A	0.9800
C5—C6	1.3788 (19)	C12—H12B	0.9800
C6—H6	0.9500	C12—H12C	0.9800
C6—C7	1.3994 (19)	O1—C1	1.3739 (16)
C7—C8	1.3998 (18)	O1—C9	1.3842 (15)
C7—C11	1.5067 (19)	O2—C1	1.2163 (16)
C8—C9	1.3973 (18)

O1—C1—C2	117.34 (11)	C9—C8—C12	120.26 (12)
O2—C1—C2	125.95 (13)	C4—C9—C8	123.63 (11)
O2—C1—O1	116.71 (12)	O1—C9—C4	120.83 (11)
C1—C2—H2	118.8	O1—C9—C8	115.54 (11)
C3—C2—H2	118.8	H10A—C10—H10B	109.5
C3—C2—C1	122.43 (12)	H10A—C10—H10C	109.5
C2—C3—C4	119.07 (12)	H10B—C10—H10C	109.5
C2—C3—C10	120.99 (12)	C3—C10—H10A	109.5
C4—C3—C10	119.94 (12)	C3—C10—H10B	109.5
C5—C4—C3	124.33 (12)	C3—C10—H10C	109.5
C9—C4—C3	118.45 (11)	H11A—C11—H11B	109.5
C9—C4—C5	117.21 (12)	H11A—C11—H11C	109.5
C4—C5—H5	119.7	H11B—C11—H11C	109.5
C6—C5—H5	119.7	C7—C11—H11A	109.5
C6—C5—C4	120.63 (12)	C7—C11—H11B	109.5
C5—C6—H6	119.4	C7—C11—H11C	109.5
C5—C6—C7	121.22 (12)	H12A—C12—H12B	109.5
C7—C6—H6	119.4	H12A—C12—H12C	109.5
C6—C7—C8	119.86 (12)	H12B—C12—H12C	109.5
C6—C7—C11	119.76 (12)	C8—C12—H12A	109.5
C8—C7—C11	120.39 (12)	C8—C12—H12B	109.5
C7—C8—C12	122.29 (12)	C8—C12—H12C	109.5
C9—C8—C7	117.45 (12)	C1—O1—C9	121.80 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.56	3.460 (2)	159
C10—H10C···O2ⁱⁱ	0.98	2.54	3.493 (2)	164

Symmetry codes: (i) −x+2, −y, −z+2; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₂
M_r	188.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	7.276 (3), 18.075 (6), 7.246 (3)
β (°)	97.055 (5)
V (Å³)	945.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.44 × 0.31 × 0.26

Data collection
Diffractometer	Rigaku AFC10/Saturn724+
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8545, 2747, 2176
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.112, 1.00
No. of reflections	2747
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.33

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.56	3.460 (2)	159
C10—H10C···O2ⁱⁱ	0.98	2.54	3.493 (2)	164

Symmetry codes: (i) −x+2, −y, −z+2; (ii) x−1, y, z.

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (No. 20962007) and the Creative Talents Plan of the Hainan University 211 Project.

References

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