3-Acetyl-4-hy-droxy-6,7-dimethyl-2H-chromen-2-one.

In the title coumarin derivative, C(13)H(12)O(4), the 2H-chromene ring system is essentially planar [maximum deviation = 0.047 (1) Å]. An intra-molecular hydrogen bond is observed between the hy-droxy and the ketonic O atoms. In the crystal, pairs of inter-molecular C-H⋯O hydrogen bonds link inversion-related mol-ecules into dimers. Additional inter-molecular C-H⋯O hydrogen bonds further inter-connect these dimers into two-dimensional arrays incorporating R(2) (2)(9) ring motifs.

Related literature

For general background to and applications of coumarin derivatives, see: Eisenhauer & Link (1953 ▶); Franz et al. (1981 ▶); Frontiera et al. (2009 ▶); Maurer & Arlt (1998 ▶). Tamura et al. (1982 ▶); Wang et al. (2007 ▶). For graph-set theory of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related coumaric structure, see: Mechi et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C13H12O4

M = 232.23

Monoclinic,

a = 3.9491 (4) Å

b = 12.1359 (11) Å

c = 22.101 (2) Å

β = 90.563 (1)°

V = 1059.16 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.32 × 0.19 × 0.13 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.966, T max = 0.986

13172 measured reflections

3139 independent reflections

2539 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.148

S = 1.05

3139 reflections

161 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045010/rz2512sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045010/rz2512Isup2.hkl

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

C13H12O4	F(000) = 488
Mr = 232.23	Dx = 1.456 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5636 reflections
a = 3.9491 (4) Å	θ = 3.2–30.2°
b = 12.1359 (11) Å	µ = 0.11 mm−1
c = 22.101 (2) Å	T = 100 K
β = 90.563 (1)°	Block, brown
V = 1059.16 (17) Å3	0.32 × 0.19 × 0.13 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	3139 independent reflections
Radiation source: fine-focus sealed tube	2539 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 30.2°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
Tmin = 0.966, Tmax = 0.986	k = −17→17
13172 measured reflections	l = −29→31

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0758P)2 + 0.5033P] where P = (Fo2 + 2Fc2)/3
3139 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
O1	0.2856 (2)	0.47223 (7)	0.06747 (4)	0.0226 (2)
O2	0.8349 (3)	0.53534 (8)	0.22188 (4)	0.0257 (2)
O3	0.8887 (3)	0.33852 (8)	0.23973 (5)	0.0279 (2)
O4	0.2728 (3)	0.29458 (8)	0.08591 (5)	0.0282 (2)
C1	0.3765 (3)	0.38338 (10)	0.10303 (6)	0.0207 (2)
C2	0.3684 (3)	0.57902 (10)	0.08348 (6)	0.0194 (2)
C3	0.2653 (3)	0.66119 (10)	0.04395 (6)	0.0203 (2)
H3A	0.1509	0.6432	0.0083	0.024*
C4	0.3335 (3)	0.77060 (10)	0.05780 (6)	0.0193 (2)
C5	0.5009 (3)	0.79852 (10)	0.11250 (6)	0.0198 (2)
C6	0.6079 (3)	0.71492 (10)	0.15068 (6)	0.0203 (2)
H6A	0.7232	0.7324	0.1863	0.024*
C7	0.5447 (3)	0.60395 (10)	0.13639 (6)	0.0192 (2)
C8	0.6577 (3)	0.51334 (10)	0.17322 (5)	0.0193 (2)
C9	0.5807 (3)	0.40436 (10)	0.15620 (5)	0.0184 (2)
C10	0.7117 (3)	0.31530 (11)	0.19379 (6)	0.0218 (3)
C11	0.6506 (4)	0.19714 (11)	0.18029 (7)	0.0259 (3)
H11B	0.7690	0.1525	0.2094	0.039*
H11C	0.7309	0.1805	0.1405	0.039*
H11D	0.4124	0.1820	0.1822	0.039*
C12	0.2309 (3)	0.85786 (11)	0.01304 (6)	0.0249 (3)
H12A	0.0781	0.8268	−0.0164	0.037*
H12B	0.4284	0.8854	−0.0069	0.037*
H12C	0.1207	0.9171	0.0338	0.037*
C13	0.5604 (4)	0.91704 (11)	0.12989 (7)	0.0264 (3)
H13A	0.6985	0.9200	0.1658	0.040*
H13B	0.3471	0.9522	0.1373	0.040*
H13C	0.6735	0.9544	0.0976	0.040*
H1O2	0.886 (4)	0.4360 (15)	0.2387 (8)	0.029 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0297 (5)	0.0181 (4)	0.0201 (4)	−0.0013 (3)	−0.0067 (3)	0.0018 (3)
O2	0.0335 (5)	0.0222 (5)	0.0210 (5)	−0.0004 (4)	−0.0084 (4)	−0.0013 (4)
O3	0.0345 (5)	0.0247 (5)	0.0244 (5)	0.0003 (4)	−0.0086 (4)	0.0041 (4)
O4	0.0363 (5)	0.0201 (5)	0.0282 (5)	−0.0049 (4)	−0.0071 (4)	−0.0018 (4)
C1	0.0241 (5)	0.0180 (5)	0.0201 (6)	−0.0002 (4)	−0.0010 (4)	0.0013 (4)
C2	0.0222 (5)	0.0157 (5)	0.0203 (6)	0.0000 (4)	0.0006 (4)	0.0000 (4)
C3	0.0235 (5)	0.0182 (5)	0.0191 (6)	−0.0003 (4)	−0.0017 (4)	0.0001 (4)
C4	0.0213 (5)	0.0169 (5)	0.0198 (6)	0.0010 (4)	−0.0008 (4)	0.0015 (4)
C5	0.0222 (5)	0.0173 (5)	0.0197 (6)	0.0000 (4)	−0.0006 (4)	0.0000 (4)
C6	0.0225 (5)	0.0202 (5)	0.0182 (6)	−0.0002 (4)	−0.0020 (4)	0.0002 (4)
C7	0.0214 (5)	0.0182 (5)	0.0179 (6)	0.0014 (4)	0.0000 (4)	0.0019 (4)
C8	0.0214 (5)	0.0201 (5)	0.0163 (5)	−0.0002 (4)	−0.0016 (4)	−0.0002 (4)
C9	0.0211 (5)	0.0163 (5)	0.0177 (5)	0.0004 (4)	−0.0007 (4)	0.0013 (4)
C10	0.0229 (5)	0.0214 (6)	0.0212 (6)	0.0006 (4)	0.0000 (4)	0.0029 (4)
C11	0.0293 (6)	0.0178 (6)	0.0304 (7)	0.0002 (4)	−0.0035 (5)	0.0051 (5)
C12	0.0304 (6)	0.0196 (6)	0.0245 (6)	0.0015 (5)	−0.0060 (5)	0.0039 (5)
C13	0.0331 (6)	0.0182 (6)	0.0279 (7)	−0.0021 (5)	−0.0050 (5)	−0.0015 (5)

O1—C1	1.3797 (15)	C6—C7	1.4050 (17)
O1—C2	1.3819 (15)	C6—H6A	0.9300
O2—C8	1.3048 (15)	C7—C8	1.4366 (17)
O2—H1O2	1.277 (18)	C8—C9	1.4074 (17)
O3—C10	1.2590 (16)	C9—C10	1.4550 (17)
O3—H1O2	1.183 (18)	C10—C11	1.4840 (18)
O4—C1	1.2121 (15)	C11—H11B	0.9600
C1—C9	1.4415 (17)	C11—H11C	0.9600
C2—C3	1.3843 (17)	C11—H11D	0.9600
C2—C7	1.3884 (17)	C12—H12A	0.9600
C3—C4	1.3884 (17)	C12—H12B	0.9600
C3—H3A	0.9300	C12—H12C	0.9600
C4—C5	1.4133 (17)	C13—H13A	0.9600
C4—C12	1.5022 (17)	C13—H13B	0.9600
C5—C6	1.3831 (17)	C13—H13C	0.9600
C5—C13	1.5066 (17)
C1—O1—C2	121.83 (10)	C9—C8—C7	120.19 (11)
C8—O2—H1O2	97.4 (8)	C8—C9—C1	120.10 (11)
C10—O3—H1O2	101.7 (9)	C8—C9—C10	118.09 (11)
O4—C1—O1	115.58 (11)	C1—C9—C10	121.82 (11)
O4—C1—C9	126.59 (12)	O3—C10—C9	119.06 (12)
O1—C1—C9	117.83 (10)	O3—C10—C11	117.79 (11)
O1—C2—C3	116.52 (11)	C9—C10—C11	123.15 (11)
O1—C2—C7	122.39 (11)	C10—C11—H11B	109.5
C3—C2—C7	121.09 (11)	C10—C11—H11C	109.5
C2—C3—C4	119.64 (11)	H11B—C11—H11C	109.5
C2—C3—H3A	120.2	C10—C11—H11D	109.5
C4—C3—H3A	120.2	H11B—C11—H11D	109.5
C3—C4—C5	120.40 (11)	H11C—C11—H11D	109.5
C3—C4—C12	118.59 (11)	C4—C12—H12A	109.5
C5—C4—C12	121.00 (11)	C4—C12—H12B	109.5
C6—C5—C4	118.91 (11)	H12A—C12—H12B	109.5
C6—C5—C13	119.92 (11)	C4—C12—H12C	109.5
C4—C5—C13	121.17 (11)	H12A—C12—H12C	109.5
C5—C6—C7	120.90 (11)	H12B—C12—H12C	109.5
C5—C6—H6A	119.6	C5—C13—H13A	109.5
C7—C6—H6A	119.6	C5—C13—H13B	109.5
C2—C7—C6	118.99 (11)	H13A—C13—H13B	109.5
C2—C7—C8	117.43 (11)	C5—C13—H13C	109.5
C6—C7—C8	123.57 (11)	H13A—C13—H13C	109.5
O2—C8—C9	121.68 (11)	H13B—C13—H13C	109.5
O2—C8—C7	118.12 (11)
C2—O1—C1—O4	176.00 (11)	C5—C6—C7—C2	−0.86 (19)
C2—O1—C1—C9	−3.75 (17)	C5—C6—C7—C8	178.13 (11)
C1—O1—C2—C3	179.59 (11)	C2—C7—C8—O2	177.43 (11)
C1—O1—C2—C7	−0.62 (18)	C6—C7—C8—O2	−1.57 (19)
O1—C2—C3—C4	178.64 (11)	C2—C7—C8—C9	−1.77 (18)
C7—C2—C3—C4	−1.15 (19)	C6—C7—C8—C9	179.23 (11)
C2—C3—C4—C5	−1.35 (18)	O2—C8—C9—C1	178.30 (11)
C2—C3—C4—C12	177.66 (11)	C7—C8—C9—C1	−2.53 (18)
C3—C4—C5—C6	2.68 (18)	O2—C8—C9—C10	−1.45 (18)
C12—C4—C5—C6	−176.30 (11)	C7—C8—C9—C10	177.72 (11)
C3—C4—C5—C13	−176.65 (12)	O4—C1—C9—C8	−174.46 (13)
C12—C4—C5—C13	4.36 (19)	O1—C1—C9—C8	5.26 (17)
C4—C5—C6—C7	−1.57 (19)	O4—C1—C9—C10	5.3 (2)
C13—C5—C6—C7	177.78 (11)	O1—C1—C9—C10	−175.00 (11)
O1—C2—C7—C6	−177.53 (11)	C8—C9—C10—O3	−0.23 (18)
C3—C2—C7—C6	2.25 (19)	C1—C9—C10—O3	−179.98 (12)
O1—C2—C7—C8	3.42 (18)	C8—C9—C10—C11	−179.43 (12)
C3—C2—C7—C8	−176.80 (11)	C1—C9—C10—C11	0.82 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O3	1.277 (18)	1.183 (18)	2.4299 (14)	162.0 (16)
C6—H6A···O3i	0.93	2.58	3.4603 (17)	159
C11—H11B···O2ii	0.96	2.59	3.5458 (18)	172
C12—H12A···O4iii	0.96	2.53	3.4751 (17)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O3	1.277 (18)	1.183 (18)	2.4299 (14)	162.0 (16)
C6—H6A⋯O3i	0.93	2.58	3.4603 (17)	159
C11—H11B⋯O2ii	0.96	2.59	3.5458 (18)	172
C12—H12A⋯O4iii	0.96	2.53	3.4751 (17)	168

Symmetry codes: (i) ; (ii) ; (iii) .