7-Hydr­oxy-4-methyl-2H-chromen-2-one monohydrate

In the title compound, C₁₀H₈O₃·H₂O, the 2H-chromen-2-one ring system, also known as coumarin, is planar. Inter­molecular O—H...O hydrogen bonding between the solvent water mol­ecule, and the carbonyl and hydroxyl groups of the coumarin ring system links the mol­ecules into a two-dimensional network parallel to the (10) plane. In addition, the crystal packing is stabilized by π–π inter­action between the coumarin ring systems of the inversion-related mol­ecules stacked along the a axis, with a centroid–centroid separation of 3.536 (1) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.052
• wR factor = 0.135
• Data-to-parameter ratio = 20.1

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.794     1.000
            Tmin(prime) and Tmax expected:      0.946     0.979
            RR(prime) =      0.821
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.37
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Compounds incorporating benzopyrone structural units posses a wide range of biological activities. A coumarin nucleus is the basis of various compounds possessing anticoagulant and anti-inflammatory activities. 2H-2-Chromenone (coumarin) derivatives are widely used for production of highly effective fluorescent dyes for synthetic fibres and daylight fluorescent pigments. These derivatives also play a vital role in electrophotographic and electroluminiscent devices. Synthesis and investigation of new substituted 2H-2-chromenone derivatives make possible new ways for scientific and technical usage. The present day demand is for large and high quality ferroelectric, piezoelectric single crystals with minimum defects and inhomogenities. The important goal of crystal growth is the improvement of microscopic and macroscopic homogeneity, which is a necessity for any application. In addition, coumarin derivatives are known as bioactive compounds with weakly toxic, anticarcinogenic, anticoagulant and antibiotic activities. In continuation of our work on crystal structures of organic compounds and in view of the importance of the title compound, we report here its crystal structure.

The non-H atoms of the coumarin derivative are coplanar (Fig. 1), with a maximum deviation of 0.037 (1) Å for atom C4. The hydroxyl group is coplanar with the coumarin ring system. In the crystal structure, the molecules are linked into a two-dimensional network parallel to the (1 0 1) plane by O—H···O hydrogen bonds involving the water molecules (Fig. 2). In addition π-π stacking interaction is observed between the coumarin ring systems of the inversion related moleules stacked along the a axis, with a centroid-centroid separation of 3.536 (1) Å.

Related literature

For the synthesis of the title compound, see: Furniss et al. (1989). For related structures, see: Toffoli et al. (1985); Bruno et al. (2001); Baumer et al. (2003, 2004); Zhong et al. (2006). For background, see: Pawar & Mulwad (2004); Lin et al. (2006); Urano et al. (1995); Zhang et al. (2003); Aggarwal et al. (1996).

S2. Experimental

The title compound was synthesized according to the method reported in the literature (Furniss et al., 1989). The compound was recrystallized from acetone-toluene (2:1 v/v) (m.p. 457 K).

S3. Refinement

The water H atoms were located in a difference Fourier map and refined with O—H distance restraints of 0.85 (1) Å, and with U_iso(H) values of 1.5U_eq(O). The remaining H atoms were included in calculated positions (O—H = 0.84 Å and C—H = 0.95 or 0.98 Å) and refined in riding model approximation, with U_iso(H) = 1.17–1.48U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. Molecular structure of the title compound, showing atomic labeling and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound, viewed down the c axis. Dashed lines indicate C—H···O hydrogen bonds.

7-Hydroxy-4-methyl-2H-chromen-2-one monohydrate

Crystal data

C10H8O3·H2O	F(000) = 408
Mr = 194.18	Dx = 1.446 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7134 reflections
a = 6.9508 (5) Å	θ = 2.5–30.6°
b = 11.3074 (8) Å	µ = 0.11 mm^−1
c = 11.7833 (8) Å	T = 100 K
β = 105.643 (1)°	Chunk, pale yellow
V = 891.81 (11) Å^3	0.48 × 0.30 × 0.19 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2711 independent reflections
Radiation source: fine-focus sealed tube	2509 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 30.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.794, Tmax = 1.000	k = −16→16
10240 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.07P)^2 + 0.3396P] where P = (Fo^2 + 2Fc^2)/3
2711 reflections	(Δ/σ)max = 0.001
135 parameters	Δρmax = 0.55 e Å^−3
3 restraints	Δρmin = −0.23 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.02672 (15)	0.15966 (7)	0.42412 (8)	0.0226 (2)
O2	0.46265 (13)	0.69064 (7)	0.65463 (7)	0.0190 (2)
H2	0.4823	0.6504	0.7166	0.023*
O3	0.16176 (12)	0.33058 (7)	0.49034 (7)	0.01523 (18)
O1W	0.03518 (15)	−0.07764 (8)	0.35966 (8)	0.0228 (2)
H1W1	0.029 (3)	−0.0072 (13)	0.3744 (17)	0.034*
H1W2	0.006 (3)	−0.1104 (15)	0.4179 (15)	0.034*
C1	0.05814 (17)	0.26209 (10)	0.39892 (10)	0.0161 (2)
C2	−0.00631 (17)	0.31431 (10)	0.28374 (10)	0.0166 (2)
H2A	−0.0804	0.2677	0.2198	0.020*
C3	0.03567 (16)	0.42846 (10)	0.26368 (9)	0.0146 (2)
C4	−0.03490 (18)	0.48234 (11)	0.14348 (10)	0.0196 (2)
H4A	−0.1139	0.4242	0.0886	0.029*
H4B	0.0807	0.5063	0.1163	0.029*
H4C	−0.1176	0.5517	0.1469	0.029*
C5	0.14888 (16)	0.49870 (9)	0.36148 (9)	0.0132 (2)
C6	0.20288 (17)	0.61797 (10)	0.35288 (10)	0.0156 (2)
H6A	0.1667	0.6561	0.2783	0.019*
C7	0.30706 (17)	0.68003 (10)	0.45074 (10)	0.0161 (2)
H7A	0.3431	0.7601	0.4430	0.019*
C8	0.36036 (16)	0.62531 (10)	0.56205 (9)	0.0143 (2)
C9	0.30837 (16)	0.50774 (9)	0.57400 (9)	0.0139 (2)
H9A	0.3421	0.4702	0.6489	0.017*
C10	0.20606 (16)	0.44701 (9)	0.47347 (9)	0.0128 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0357 (5)	0.0129 (4)	0.0188 (4)	−0.0039 (3)	0.0067 (4)	−0.0007 (3)
O2	0.0258 (4)	0.0143 (4)	0.0146 (4)	−0.0039 (3)	0.0013 (3)	−0.0018 (3)
O3	0.0224 (4)	0.0105 (3)	0.0124 (4)	−0.0018 (3)	0.0039 (3)	0.0004 (3)
O1W	0.0376 (5)	0.0148 (4)	0.0164 (4)	0.0019 (3)	0.0079 (4)	0.0006 (3)
C1	0.0208 (5)	0.0136 (5)	0.0146 (5)	−0.0004 (4)	0.0059 (4)	−0.0017 (4)
C2	0.0208 (5)	0.0163 (5)	0.0124 (5)	−0.0011 (4)	0.0039 (4)	−0.0021 (4)
C3	0.0158 (5)	0.0169 (5)	0.0111 (4)	0.0011 (4)	0.0039 (3)	−0.0004 (4)
C4	0.0233 (5)	0.0217 (5)	0.0121 (5)	−0.0002 (4)	0.0020 (4)	0.0023 (4)
C5	0.0152 (5)	0.0127 (4)	0.0117 (4)	0.0015 (3)	0.0037 (3)	0.0008 (3)
C6	0.0179 (5)	0.0142 (5)	0.0144 (5)	0.0010 (4)	0.0039 (4)	0.0032 (4)
C7	0.0186 (5)	0.0123 (5)	0.0172 (5)	0.0000 (4)	0.0042 (4)	0.0021 (4)
C8	0.0152 (5)	0.0132 (5)	0.0145 (5)	0.0005 (4)	0.0039 (4)	−0.0009 (4)
C9	0.0173 (5)	0.0132 (4)	0.0115 (4)	0.0007 (4)	0.0041 (4)	0.0007 (3)
C10	0.0158 (5)	0.0100 (4)	0.0129 (4)	0.0009 (3)	0.0043 (4)	0.0010 (3)

Geometric parameters (Å, º)

O1—C1	1.2298 (14)	C4—H4A	0.98
O2—C8	1.3501 (13)	C4—H4B	0.98
O2—H2	0.84	C4—H4C	0.98
O3—C1	1.3641 (13)	C5—C10	1.3993 (14)
O3—C10	1.3786 (12)	C5—C6	1.4108 (15)
O1W—H1W1	0.819 (14)	C6—C7	1.3770 (15)
O1W—H1W2	0.851 (14)	C6—H6A	0.95
C1—C2	1.4365 (15)	C7—C8	1.4065 (15)
C2—C3	1.3579 (15)	C7—H7A	0.95
C2—H2A	0.95	C8—C9	1.3947 (15)
C3—C5	1.4454 (15)	C9—C10	1.3879 (14)
C3—C4	1.4978 (15)	C9—H9A	0.95
C8—O2—H2	109.5	C10—C5—C6	116.98 (10)
C1—O3—C10	121.28 (8)	C10—C5—C3	118.52 (9)
H1W1—O1W—H1W2	102.4 (16)	C6—C5—C3	124.49 (10)
O1—C1—O3	115.74 (10)	C7—C6—C5	121.13 (10)
O1—C1—C2	125.80 (10)	C7—C6—H6A	119.4
O3—C1—C2	118.46 (10)	C5—C6—H6A	119.4
C3—C2—C1	121.89 (10)	C6—C7—C8	120.24 (10)
C3—C2—H2A	119.1	C6—C7—H7A	119.9
C1—C2—H2A	119.1	C8—C7—H7A	119.9
C2—C3—C5	118.68 (10)	O2—C8—C9	122.30 (10)
C2—C3—C4	121.35 (10)	O2—C8—C7	117.49 (10)
C5—C3—C4	119.97 (10)	C9—C8—C7	120.21 (10)
C3—C4—H4A	109.5	C10—C9—C8	118.20 (10)
C3—C4—H4B	109.5	C10—C9—H9A	120.9
H4A—C4—H4B	109.5	C8—C9—H9A	120.9
C3—C4—H4C	109.5	O3—C10—C9	115.62 (9)
H4A—C4—H4C	109.5	O3—C10—C5	121.15 (9)
H4B—C4—H4C	109.5	C9—C10—C5	123.23 (10)
C10—O3—C1—O1	−179.87 (10)	C6—C7—C8—O2	179.91 (10)
C10—O3—C1—C2	−0.59 (15)	C6—C7—C8—C9	0.13 (17)
O1—C1—C2—C3	−179.79 (12)	O2—C8—C9—C10	−178.93 (10)
O3—C1—C2—C3	1.00 (17)	C7—C8—C9—C10	0.84 (16)
C1—C2—C3—C5	0.13 (17)	C1—O3—C10—C9	178.66 (10)
C1—C2—C3—C4	−179.12 (11)	C1—O3—C10—C5	−0.98 (15)
C2—C3—C5—C10	−1.65 (16)	C8—C9—C10—O3	178.91 (9)
C4—C3—C5—C10	177.62 (10)	C8—C9—C10—C5	−1.46 (17)
C2—C3—C5—C6	179.90 (10)	C6—C5—C10—O3	−179.33 (9)
C4—C3—C5—C6	−0.84 (17)	C3—C5—C10—O3	2.09 (15)
C10—C5—C6—C7	−0.03 (16)	C6—C5—C10—C9	1.06 (16)
C3—C5—C6—C7	178.45 (10)	C3—C5—C10—C9	−177.51 (10)
C5—C6—C7—C8	−0.54 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W2···O1^i	0.85 (1)	2.01 (2)	2.8509 (13)	168 (2)
O1W—H1W1···O1	0.82 (1)	1.98 (2)	2.7936 (13)	175 (2)
O2—H2···O1W^ii	0.84	1.82	2.6583 (12)	174

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