In the title compound, C
12H
12O
3, the pyran ring adopts a half-chair conformation. In the crystal, the inversion-related molecules exist as O—H
O hydrogen-bonded dimers and these dimeric pairs are reinforced by C—H
O interactions.
Supporting information
CCDC reference: 214590
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.067
- wR factor = 0.198
- Data-to-parameter ratio = 14.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Acetylacetone (10 mmol) in ethanol was mixed with salicylaldehyde (10 mmol), to which was added 0.5 ml of piperidine. The solution mixture was stirred thoroughly for about 3 h with occasional cooling. This mixture was then kept in a refrigerator for 12 h. A yellow product was obtained and this was separated out, then filtered, washed with a small amount of ethanol and dried under vacuum. The title compound was recrystallized from a chloroform/petroleum ether (1:1 volume ratio) solution.
The H atoms were positioned geometrically and were treated as riding on their parent C and O atoms, with aromatic C—H distances of 0.93 Å, methyl C—H distances of 0.96 Å and O—H distance of 0.82 Å. Rotating-group refinement was used for the methyl and hydroxy groups.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
3-Acetyl-2-hydroxy-2-methylchromene
top
Crystal data top
C12H12O3 | Z = 2 |
Mr = 204.22 | F(000) = 216 |
Triclinic, P1 | Dx = 1.332 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.5418 Å |
a = 7.574 (2) Å | Cell parameters from 25 reflections |
b = 8.672 (2) Å | θ = 10–35° |
c = 8.789 (3) Å | µ = 0.79 mm−1 |
α = 106.32 (3)° | T = 293 K |
β = 110.99 (3)° | Prism, yellow |
γ = 93.28 (3)° | 0.25 × 0.25 × 0.25 mm |
V = 509.2 (2) Å3 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
Radiation source: Enraf-Nonius FR590 | θmax = 74.9°, θmin = 5.4° |
Graphite monochromator | h = −8→9 |
non–profiled ω/2θ scans | k = −10→10 |
2091 measured reflections | l = −10→0 |
2091 independent reflections | 2 standard reflections every 60 reflections |
1963 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.1509P)2 + 0.0906P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2091 reflections | Δρmax = 0.32 e Å−3 |
140 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.104 (12) |
Crystal data top
C12H12O3 | γ = 93.28 (3)° |
Mr = 204.22 | V = 509.2 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.574 (2) Å | Cu Kα radiation |
b = 8.672 (2) Å | µ = 0.79 mm−1 |
c = 8.789 (3) Å | T = 293 K |
α = 106.32 (3)° | 0.25 × 0.25 × 0.25 mm |
β = 110.99 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
2091 measured reflections | 2 standard reflections every 60 reflections |
2091 independent reflections | intensity decay: none |
1963 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
2091 reflections | Δρmin = −0.33 e Å−3 |
140 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 | Uiso*/Ueq | |
O1 | 0.77151 (15) | 0.09860 (13) | 0.39864 (16) | 0.0445 (4) | |
C2 | 0.8307 (2) | 0.26962 (17) | 0.5000 (2) | 0.0364 (4) | |
C3 | 0.6864 (2) | 0.32875 (17) | 0.57756 (19) | 0.0350 (4) | |
C4 | 0.5039 (2) | 0.24953 (18) | 0.5018 (2) | 0.0377 (4) | |
H4 | 0.4158 | 0.2868 | 0.5486 | 0.045* | |
C5 | 0.2484 (2) | 0.0368 (2) | 0.2492 (2) | 0.0491 (5) | |
H5 | 0.1527 | 0.0804 | 0.2811 | 0.059* | |
C6 | 0.1993 (3) | −0.0976 (2) | 0.1030 (2) | 0.0555 (5) | |
H6 | 0.0709 | −0.1440 | 0.0367 | 0.067* | |
C7 | 0.3413 (3) | −0.1628 (2) | 0.0560 (2) | 0.0547 (5) | |
H7 | 0.3076 | −0.2527 | −0.0427 | 0.066* | |
C8 | 0.5331 (3) | −0.0961 (2) | 0.1536 (2) | 0.0486 (5) | |
H8 | 0.6283 | −0.1413 | 0.1220 | 0.058* | |
C9 | 0.5814 (2) | 0.03956 (18) | 0.2996 (2) | 0.0378 (4) | |
C10 | 0.4410 (2) | 0.10749 (18) | 0.3491 (2) | 0.0379 (4) | |
O11 | 0.83018 (16) | 0.36112 (14) | 0.39158 (15) | 0.0451 (4) | |
H11 | 0.9329 | 0.3650 | 0.3800 | 0.068* | |
C12 | 1.0288 (2) | 0.2744 (2) | 0.6304 (2) | 0.0469 (5) | |
H12A | 1.1032 | 0.2176 | 0.5718 | 0.070* | |
H12B | 1.0169 | 0.2228 | 0.7104 | 0.070* | |
H12C | 1.0919 | 0.3858 | 0.6914 | 0.070* | |
C13 | 0.7453 (2) | 0.48739 (19) | 0.7176 (2) | 0.0414 (4) | |
O14 | 0.88717 (19) | 0.58295 (15) | 0.7476 (2) | 0.0619 (5) | |
C15 | 0.6240 (3) | 0.5332 (2) | 0.8216 (2) | 0.0532 (5) | |
H15A | 0.6928 | 0.6271 | 0.9208 | 0.080* | |
H15B | 0.5959 | 0.4436 | 0.8581 | 0.080* | |
H15C | 0.5062 | 0.5581 | 0.7521 | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0374 (6) | 0.0323 (6) | 0.0593 (8) | 0.0051 (4) | 0.0238 (5) | 0.0018 (5) |
C2 | 0.0319 (7) | 0.0306 (7) | 0.0465 (8) | 0.0013 (5) | 0.0202 (6) | 0.0064 (6) |
C3 | 0.0332 (7) | 0.0297 (7) | 0.0434 (8) | 0.0031 (5) | 0.0200 (6) | 0.0074 (6) |
C4 | 0.0335 (8) | 0.0345 (8) | 0.0477 (9) | 0.0033 (6) | 0.0227 (6) | 0.0088 (6) |
C5 | 0.0387 (9) | 0.0430 (9) | 0.0583 (10) | −0.0023 (7) | 0.0163 (7) | 0.0107 (7) |
C6 | 0.0506 (10) | 0.0451 (10) | 0.0528 (10) | −0.0102 (8) | 0.0061 (8) | 0.0111 (8) |
C7 | 0.0722 (12) | 0.0357 (9) | 0.0421 (9) | −0.0043 (8) | 0.0143 (8) | 0.0050 (7) |
C8 | 0.0609 (11) | 0.0349 (8) | 0.0484 (9) | 0.0051 (7) | 0.0255 (8) | 0.0064 (7) |
C9 | 0.0414 (8) | 0.0291 (7) | 0.0436 (8) | 0.0020 (6) | 0.0196 (6) | 0.0100 (6) |
C10 | 0.0368 (8) | 0.0317 (7) | 0.0445 (8) | −0.0007 (6) | 0.0177 (6) | 0.0104 (6) |
O11 | 0.0387 (6) | 0.0491 (7) | 0.0531 (7) | 0.0015 (5) | 0.0245 (5) | 0.0177 (5) |
C12 | 0.0330 (8) | 0.0486 (9) | 0.0592 (10) | 0.0076 (6) | 0.0200 (7) | 0.0151 (7) |
C13 | 0.0391 (8) | 0.0334 (8) | 0.0486 (9) | 0.0036 (6) | 0.0204 (6) | 0.0048 (6) |
O14 | 0.0518 (8) | 0.0439 (7) | 0.0755 (9) | −0.0107 (6) | 0.0323 (7) | −0.0081 (6) |
C15 | 0.0626 (11) | 0.0434 (9) | 0.0570 (10) | 0.0104 (8) | 0.0362 (9) | 0.0041 (7) |
Geometric parameters (Å, º) top
O1—C9 | 1.364 (2) | C7—C8 | 1.383 (3) |
O1—C2 | 1.4454 (18) | C7—H7 | 0.93 |
C2—O11 | 1.3998 (19) | C8—C9 | 1.390 (2) |
C2—C12 | 1.517 (2) | C8—H8 | 0.93 |
C2—C3 | 1.5243 (19) | C9—C10 | 1.388 (2) |
C3—C4 | 1.343 (2) | O11—H11 | 0.82 |
C3—C13 | 1.480 (2) | C12—H12A | 0.96 |
C4—C10 | 1.446 (2) | C12—H12B | 0.96 |
C4—H4 | 0.93 | C12—H12C | 0.96 |
C5—C6 | 1.384 (3) | C13—O14 | 1.218 (2) |
C5—C10 | 1.397 (2) | C13—C15 | 1.509 (2) |
C5—H5 | 0.93 | C15—H15A | 0.96 |
C6—C7 | 1.380 (3) | C15—H15B | 0.96 |
C6—H6 | 0.93 | C15—H15C | 0.96 |
| | | |
C9—O1—C2 | 118.97 (11) | C9—C8—H8 | 120.5 |
O11—C2—O1 | 109.02 (13) | O1—C9—C10 | 120.74 (14) |
O11—C2—C12 | 114.01 (13) | O1—C9—C8 | 118.00 (15) |
O1—C2—C12 | 102.54 (13) | C10—C9—C8 | 121.15 (16) |
O11—C2—C3 | 105.64 (12) | C9—C10—C5 | 118.77 (16) |
O1—C2—C3 | 110.84 (11) | C9—C10—C4 | 117.51 (14) |
C12—C2—C3 | 114.79 (13) | C5—C10—C4 | 123.72 (15) |
C4—C3—C13 | 121.67 (13) | C2—O11—H11 | 109.5 |
C4—C3—C2 | 119.49 (13) | C2—C12—H12A | 109.5 |
C13—C3—C2 | 118.09 (13) | C2—C12—H12B | 109.5 |
C3—C4—C10 | 121.48 (14) | H12A—C12—H12B | 109.5 |
C3—C4—H4 | 119.3 | C2—C12—H12C | 109.5 |
C10—C4—H4 | 119.3 | H12A—C12—H12C | 109.5 |
C6—C5—C10 | 120.37 (17) | H12B—C12—H12C | 109.5 |
C6—C5—H5 | 119.8 | O14—C13—C3 | 121.16 (14) |
C10—C5—H5 | 119.8 | O14—C13—C15 | 119.52 (15) |
C7—C6—C5 | 119.85 (16) | C3—C13—C15 | 119.30 (14) |
C7—C6—H6 | 120.1 | C13—C15—H15A | 109.5 |
C5—C6—H6 | 120.1 | C13—C15—H15B | 109.5 |
C6—C7—C8 | 120.92 (16) | H15A—C15—H15B | 109.5 |
C6—C7—H7 | 119.5 | C13—C15—H15C | 109.5 |
C8—C7—H7 | 119.5 | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 118.94 (17) | H15B—C15—H15C | 109.5 |
C7—C8—H8 | 120.5 | | |
| | | |
C9—O1—C2—O11 | −76.84 (15) | C2—O1—C9—C8 | 152.92 (15) |
C9—O1—C2—C12 | 162.00 (13) | C7—C8—C9—O1 | 176.89 (14) |
C9—O1—C2—C3 | 39.03 (18) | C7—C8—C9—C10 | 0.5 (2) |
O11—C2—C3—C4 | 93.69 (17) | O1—C9—C10—C5 | −176.18 (14) |
O1—C2—C3—C4 | −24.25 (19) | C8—C9—C10—C5 | 0.1 (2) |
C12—C2—C3—C4 | −139.82 (16) | O1—C9—C10—C4 | 4.4 (2) |
O11—C2—C3—C13 | −76.60 (17) | C8—C9—C10—C4 | −179.37 (14) |
O1—C2—C3—C13 | 165.45 (13) | C6—C5—C10—C9 | −0.5 (3) |
C12—C2—C3—C13 | 49.88 (19) | C6—C5—C10—C4 | 178.93 (15) |
C13—C3—C4—C10 | 170.83 (14) | C3—C4—C10—C9 | 10.4 (2) |
C2—C3—C4—C10 | 0.9 (2) | C3—C4—C10—C5 | −169.04 (15) |
C10—C5—C6—C7 | 0.3 (3) | C4—C3—C13—O14 | −155.77 (17) |
C5—C6—C7—C8 | 0.4 (3) | C2—C3—C13—O14 | 14.3 (2) |
C6—C7—C8—C9 | −0.8 (3) | C4—C3—C13—C15 | 22.5 (2) |
C2—O1—C9—C10 | −30.7 (2) | C2—C3—C13—C15 | −167.43 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O14i | 0.82 | 2.15 | 2.899 (2) | 152 |
C12—H12C···O11i | 0.96 | 2.60 | 3.357 (2) | 136 |
C12—H12C···O14 | 0.96 | 2.44 | 2.990 (2) | 116 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C12H12O3 |
Mr | 204.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.574 (2), 8.672 (2), 8.789 (3) |
α, β, γ (°) | 106.32 (3), 110.99 (3), 93.28 (3) |
V (Å3) | 509.2 (2) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.25 × 0.25 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2091, 2091, 1963 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.198, 1.05 |
No. of reflections | 2091 |
No. of parameters | 140 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.33 |
Selected geometric parameters (Å, º) topO1—C9 | 1.364 (2) | C3—C4 | 1.343 (2) |
O1—C2 | 1.4454 (18) | C13—O14 | 1.218 (2) |
C2—O11 | 1.3998 (19) | | |
| | | |
O11—C2—O1 | 109.02 (13) | O11—C2—C3 | 105.64 (12) |
O11—C2—C12 | 114.01 (13) | O1—C2—C3 | 110.84 (11) |
O1—C2—C12 | 102.54 (13) | C12—C2—C3 | 114.79 (13) |
| | | |
C9—O1—C2—C3 | 39.03 (18) | C3—C4—C10—C9 | 10.4 (2) |
O1—C2—C3—C4 | −24.25 (19) | C4—C3—C13—O14 | −155.77 (17) |
C2—C3—C4—C10 | 0.9 (2) | C2—C3—C13—O14 | 14.3 (2) |
C2—O1—C9—C10 | −30.7 (2) | C4—C3—C13—C15 | 22.5 (2) |
O1—C9—C10—C4 | 4.4 (2) | C2—C3—C13—C15 | −167.43 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O14i | 0.82 | 2.15 | 2.899 (2) | 152 |
C12—H12C···O11i | 0.96 | 2.60 | 3.357 (2) | 136 |
C12—H12C···O14 | 0.96 | 2.44 | 2.990 (2) | 116 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Chromene derivatives exhibit antifeedant activity against larvae of Spilarctia obliqua (Agarwal et al., 2000) and some 2H-chromene derivatives are found to possess antimicrobial activities (El-Gaby et al., 2000). Endothelin-A (ETA) selective receptor antagonists contain the 2H-chromene moiety (Ishizuka et al., 2002). Apart from the above activities, the chromene derivatives possess photochromic properties. The structure determination of the title compound, (I), was undertaken as part of our studies on chromene derivatives.
In (I) (Fig. 1), the pyran ring adopts a half-chair conformation, with asymmetry parameter Δ2(C2—O1)= 0.009 (1) (Nardelli, 1983). Atoms O1 and C2 deviate from the weighted least-squares plane through the remaining four atoms of the pyran ring by −0.253 (1) and 0.214 (2) Å, respectively. The hydroxy and methyl groups at C2 adopt pseudo-axial and pseudo-equatorial orientations, respectively. The acetyl group is planar and makes a dihedral angle of 28.6 (1)° with the mean plane passing through atoms C3–C10. The bond angles at sp3-hybridized atom C2 show substantial distortion from the ideal tetrahedral value of 109.5°. Similar observations have been noted in the crystal structures of related chromene derivatives (Aldosin et al., 1995, 1996; Yogavel et al., 2003). The C3—C4 [1.343 (2) Å] bond length is comparable with the previously reported value of 1.350 (4) Å for 3-benzoyl-2-hydroxy-2-methylchromene (Yogavel et al., 2003).
The distinctive feature of the crystal structure of (I) is that the inversion-related intermolecular O—H···O hydrogen bonds (Table 2) lead to the formation of dimeric pairs with graph-set R22(12) (Etter et al., 1990) and these dimeric pairs are further reinforced by weak C—H···O interactions.