3-Acetyl-4-hy­droxy-6,7-dimethyl-2H-chromen-2-one

Mohammad Asad; Chuan-Wei Oo; Hasnah Osman; Jia Hao Goh; Hoong-Kun Fun

doi:10.1107/S1600536810045010

. 2010 Nov 13;66(Pt 12):o3129–o3130. doi: 10.1107/S1600536810045010

3-Acetyl-4-hydroxy-6,7-dimethyl-2H-chromen-2-one

Mohammad Asad ^a, Chuan-Wei Oo ^a,^‡, Hasnah Osman ^a, Jia Hao Goh ^b,^§, Hoong-Kun Fun ^b,^*,^¶

PMCID: PMC3011552 PMID: 21589432

Abstract

In the title coumarin derivative, C₁₃H₁₂O₄, the 2H-chromene ring system is essentially planar [maximum deviation = 0.047 (1) Å]. An intramolecular hydrogen bond is observed between the hydroxy and the ketonic O atoms. In the crystal, pairs of intermolecular C—H⋯O hydrogen bonds link inversion-related molecules into dimers. Additional intermolecular C—H⋯O hydrogen bonds further interconnect 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 _r = 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
Δρ_max = 0.64 e Å⁻³
Δρ_min = −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 ▶).

Supplementary Material

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

e-66-o3129-sup1.cif^{(17.6KB, cif)}

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

e-66-o3129-Isup2.hkl^{(154KB, hkl)}

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

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

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

Acknowledgments

The authors are thankful to Universiti Sains Malaysia (USM) for providing the necessary research facilities and RU research funding under grant No. 1001/PKIMIA/811134. JHG and HKF also thank USM for the Research University Grant (No. 1001/PFIZIK/811160) and MA also thanks USM for the award of a post doctoral fellowship.

supplementary crystallographic information

Comment

We report here a new 4-hydroxycoumarin derivative, which has been synthesized by acetylation process (Eisenhauer & Link, 1953). Recently, coumarin and its derivatives have been extensively used in industrial products as dyes/laser materials (Wang et al., 2007), photosensitizers (Frontiera et al., 2009), pesticides (Franz et al., 1981), in pharmacology (Maurer & Arlt, 1998) and in enzymology as biological probes (Tamura et al., 1982).

In the title coumarin compound, (Fig. 1), the 2H-chromene ring system (C1-C9/O1) is essentially planar, as indicated by the maximum deviation of -0.047 (1) Å at atom C1. Bond length of C10═O3 [1.2590 (16) Å] is longer than normal value due to the delocalization of atom H1O2 between the hydroxyl oxygen atom (O2) and the ketonic oxygen atom (O3), as observed in a related structure (Mechi et al., 2009). However, the bond lengths of O2—H1O2 = 1.277 (18) and O3—H1O2 = 1.183 (18) Å are inconsistent with the respective values observed in Mechi et al., 2009. All other bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure, (Fig. 2), pairs of intermolecular C12—H12A···O4 hydrogen bonds (Table 1) link inversion-related molecules into dimers, producing R₂²(16) ring motifs (Bernstein et al., 1995). Intermolecular C6—H16A···O3 and C11—H11B···O2 hydrogen bonds (Table 1) further interconnect these dimers into two-dimensional arrays incorporating R₂²(9) hydrogen bond ring motifs (Bernstein et al., 1995).

Experimental

Acetyl chloride (1 ml) was added to a solution of 4-hydroxy-6,7-dimethylcoumarin (5.2 mmol, 1.0 g) in pyridine (10 ml) which contains piperidine (one drop) on ice bath. The reaction mixture was kept at room temperature for 7 days. The solution was then poured into ice-cold water and hydrochloric acid was added to afford the precipitate, which was washed with water, dried and recrystallized from ethanol to get the pure title compound in 70% yield.