organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

1-[2-Hy­dr­oxy-4-(prop-2-yn-1-yl­­oxy)phen­yl]ethanone

aChemistry Research Centre, National Engineering College, K.R. Nagar, Kovilpatti 628 503, India, and bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: drmaneelakantan@gmail.com

(Received 18 November 2013; accepted 30 November 2013; online 7 December 2013)

In the title compound, C11H10O3, there is an intra­molecular O—H⋯O hydrogen bond generating an S(6) ring motif. The O atom of the hy­droxy group deviates by 0.0200 (1) Å from the benzene ring to which it is attached. The propyne group is almost linear, the C—C≡C angle being 177.83 (15)°, and is almost coplanar with the benzene ring; the C—C—O—C torsion angle being only −1.1 (2)°. In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, forming infinite C(11) chains running parallel to [103]. These chains are linked by a pair of C—H⋯O hydrogen bonds, enclosing R22(8) inversion dimers, forming a corrugated two-dimensional network lying parallel to (103).

Related literature

For the biological activity of benzaldehyde derivatives, see: Zhao et al. (2007[Zhao, X., Song, D. K., Radbil, A. B. & Radbil, B. A. (2007). Russ. J. Appl. Chem. 80, 1373-1375.]); Ley & Bertram (2001[Ley, J. P. & Bertram, H. J. (2001). Bioorg. Med. Chem. Lett. 9, 1879-1885.]); Delogu et al. (2010[Delogu, G., Podda, G., Corda, M., Fadda, M. B., Fais, A. & Era, B. (2010). Bioorg. Med. Chem. Lett. 20, 6138-6140.]). For a related structure, see: Esakkiammal et al. (2012[Esakkiammal, M., Selvarani, V., Neelakantan, M. A., Silambarasan, V. & Velmurugan, D. (2012). Acta Cryst. E68, o2465.]). For graph-set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C11H10O3

  • Mr = 190.19

  • Monoclinic, P 21 /n

  • a = 4.9975 (2) Å

  • b = 10.4305 (4) Å

  • c = 18.8467 (7) Å

  • β = 97.257 (2)°

  • V = 974.54 (7) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 K

  • 0.35 × 0.30 × 0.20 mm

Data collection
  • Bruker SMART APEXII area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.968, Tmax = 0.981

  • 9316 measured reflections

  • 2451 independent reflections

  • 1898 reflections with I > 2σ(I)

  • Rint = 0.021

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.130

  • S = 1.05

  • 2451 reflections

  • 138 parameters

  • 3 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O2 0.82 1.83 2.5551 (14) 146
C4—H4⋯O3i 0.93 2.54 3.4609 (16) 172
C11—H11⋯O2ii 0.93 2.32 3.2337 (18) 168
Symmetry codes: (i) -x+3, -y+2, -z; (ii) [x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Schiff bases derived from amines and substituted benzaldehydes exhibit antibacterial, anticancer and antitumour activities (Zhao et al., 2007). Several benzaldoximes, benzaldehyde-O-ethyloximes and acetophenone oximes were synthesized and evaluated as tyrosinase inhibitors (Ley & Bertram, 2001). Bis-salicylaldehydes has been shown to exhibited greater inhibitory activity than salicylaldehyde (Delogu et al., 2010). In view of these potential applications and in continuation of our work on the crystal structures of benzaldehyde derivatives, we synthesized the title compound and report herein on its crystal structure.

The molecular structure of the title compound is stabilized by an O—H···O intramolecular hydrogen bond (Fig. 1 and Table 1), which forms an S(6) graph-set motif (Bernstein et al., 1995). The hydroxyl O atom, O1, deviates by 0.0200 (1) Å from the benzene ring (C1-C6) to which it is attached. The oxygen atom substituted propyne group is slightly twisted from the benzene ring (C1–C6) to which it is attached as evidenced by the torsion angle C6–C5–O3–C9 = -1.1 (2) °. The propyne group is almost linear, the C9–C10C11 angle being 177.83 (15)°, and it is also in the flagpole position on atom O3. The mean plane of the acetaldehyde group makes a dihedral angle of 0.39 (9)° with the benzene ring (C1–C6), indicating that they are almost coplanar.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming infinite C(11) chains running parallel to direction [103]. These chains are linked via a pair of C—H···O hydrogen bonds, enclosing R22(8) inversion dimers, forming wave-like two-dimensional networks lying parallel to (103); see Table 1 and Fig. 2.

Related literature top

For the biological activity of benzaldehyde derivatives, see: Zhao et al. (2007); Ley & Bertram (2001); Delogu et al. (2010). For a related structure, see: Esakkiammal et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Equimolar amounts of 3-bromopropyne (10 mmol), 2,4-dihydroxyacetophenone (10 mmol) and potassium carbonate (15 mmol) were suspended in dried acetone (30 ml) and refluxed for 5 h. The reaction mixture was filtered while hot to remove insoluble impurities, neutralized with water and then extracted with ethyl acetate and dried with Na2SO4. The extracts were concentrated to obtain a brown solid which was then purified by column chromatography over SiO2 by eluting with a mixture of 5% ethyl acetate in n-hexane. Evaporation of the purified extract yielded the title compound in the form of a pure white solid [Yield: 83%]. Colourless block-like crystals, suitable for X-ray diffraction analysis, were obtained by the slow evaporation of a solution in ethyl acetate.

Refinement top

All H atoms could be located in difference Fourier maps. The methyl H atoms were refined with Uiso(H) = 1.5Ueq(C). The OH and other C-bound H atoms were included in calculated positions are refined as riding atoms: O-H = 0.82 Å, C-H = 0.93 and 0.97 Å for CH and CH2 H atoms, respectively, with Uiso(H) = 1.5Ueq(O) and = 1.2Ueq(C) for other H atoms.

Structure description top

Schiff bases derived from amines and substituted benzaldehydes exhibit antibacterial, anticancer and antitumour activities (Zhao et al., 2007). Several benzaldoximes, benzaldehyde-O-ethyloximes and acetophenone oximes were synthesized and evaluated as tyrosinase inhibitors (Ley & Bertram, 2001). Bis-salicylaldehydes has been shown to exhibited greater inhibitory activity than salicylaldehyde (Delogu et al., 2010). In view of these potential applications and in continuation of our work on the crystal structures of benzaldehyde derivatives, we synthesized the title compound and report herein on its crystal structure.

The molecular structure of the title compound is stabilized by an O—H···O intramolecular hydrogen bond (Fig. 1 and Table 1), which forms an S(6) graph-set motif (Bernstein et al., 1995). The hydroxyl O atom, O1, deviates by 0.0200 (1) Å from the benzene ring (C1-C6) to which it is attached. The oxygen atom substituted propyne group is slightly twisted from the benzene ring (C1–C6) to which it is attached as evidenced by the torsion angle C6–C5–O3–C9 = -1.1 (2) °. The propyne group is almost linear, the C9–C10C11 angle being 177.83 (15)°, and it is also in the flagpole position on atom O3. The mean plane of the acetaldehyde group makes a dihedral angle of 0.39 (9)° with the benzene ring (C1–C6), indicating that they are almost coplanar.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming infinite C(11) chains running parallel to direction [103]. These chains are linked via a pair of C—H···O hydrogen bonds, enclosing R22(8) inversion dimers, forming wave-like two-dimensional networks lying parallel to (103); see Table 1 and Fig. 2.

For the biological activity of benzaldehyde derivatives, see: Zhao et al. (2007); Ley & Bertram (2001); Delogu et al. (2010). For a related structure, see: Esakkiammal et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular O-H···O hydrogen bond is shown as a dashed line (see Table 1 for details)
[Figure 2] Fig. 2. A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been excluded for clarity).
1-[2-Hydroxy-4-(prop-2-yn-1-yloxy)phenyl]ethan-one top
Crystal data top
C11H10O3F(000) = 400
Mr = 190.19Dx = 1.296 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2451 reflections
a = 4.9975 (2) Åθ = 2.2–28.4°
b = 10.4305 (4) ŵ = 0.10 mm1
c = 18.8467 (7) ÅT = 293 K
β = 97.257 (2)°Block, colourless
V = 974.54 (7) Å30.35 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker SMART APEXII area-detector
diffractometer
2451 independent reflections
Radiation source: fine-focus sealed tube1898 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω and φ scansθmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 66
Tmin = 0.968, Tmax = 0.981k = 1313
9316 measured reflectionsl = 2525
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130 w = 1/[σ2(Fo2) + (0.0637P)2 + 0.1394P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2451 reflectionsΔρmax = 0.17 e Å3
138 parametersΔρmin = 0.21 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.020 (4)
Crystal data top
C11H10O3V = 974.54 (7) Å3
Mr = 190.19Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.9975 (2) ŵ = 0.10 mm1
b = 10.4305 (4) ÅT = 293 K
c = 18.8467 (7) Å0.35 × 0.30 × 0.20 mm
β = 97.257 (2)°
Data collection top
Bruker SMART APEXII area-detector
diffractometer
2451 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1898 reflections with I > 2σ(I)
Tmin = 0.968, Tmax = 0.981Rint = 0.021
9316 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0433 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.17 e Å3
2451 reflectionsΔρmin = 0.21 e Å3
138 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.9425 (3)0.69719 (11)0.08613 (7)0.0455 (3)
C20.9120 (2)0.81055 (10)0.12463 (6)0.0421 (3)
C31.0579 (3)0.91806 (11)0.10720 (6)0.0475 (3)
H31.04170.99410.13200.057*
C41.2229 (3)0.91474 (11)0.05494 (7)0.0506 (3)
H41.31860.98740.04460.061*
C51.2467 (3)0.80135 (11)0.01728 (6)0.0446 (3)
C61.1094 (3)0.69245 (11)0.03266 (6)0.0468 (3)
H61.12830.61690.00760.056*
C70.7340 (3)0.81464 (12)0.18017 (6)0.0485 (3)
C80.7041 (4)0.93600 (15)0.22030 (9)0.0632 (4)
H8A0.595 (4)0.9292 (18)0.2554 (11)0.095*
H8B0.648 (4)1.005 (2)0.1896 (10)0.095*
H8C0.872 (4)0.9636 (19)0.2446 (10)0.095*
C91.4462 (3)0.69606 (12)0.07557 (7)0.0527 (3)
H9A1.27270.66390.09720.063*
H9B1.53420.62980.04490.063*
C101.6120 (3)0.73056 (13)0.13064 (7)0.0546 (3)
C111.7405 (3)0.75594 (16)0.17657 (8)0.0680 (4)
H111.84240.77610.21300.082*
O10.8072 (2)0.58946 (8)0.09853 (6)0.0691 (4)
H10.71870.60170.13170.104*
O20.6074 (2)0.71799 (10)0.19459 (5)0.0624 (3)
O31.4107 (2)0.80891 (8)0.03494 (5)0.0574 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0506 (7)0.0372 (5)0.0508 (6)0.0075 (5)0.0149 (5)0.0001 (4)
C20.0460 (6)0.0395 (5)0.0418 (5)0.0015 (5)0.0098 (5)0.0009 (4)
C30.0570 (7)0.0372 (5)0.0501 (6)0.0056 (5)0.0140 (5)0.0060 (4)
C40.0595 (8)0.0385 (6)0.0569 (7)0.0126 (5)0.0196 (6)0.0035 (5)
C50.0457 (7)0.0431 (6)0.0472 (6)0.0071 (5)0.0149 (5)0.0022 (4)
C60.0531 (7)0.0370 (5)0.0531 (6)0.0072 (5)0.0177 (6)0.0073 (4)
C70.0549 (8)0.0484 (6)0.0438 (6)0.0027 (5)0.0127 (5)0.0033 (5)
C80.0781 (11)0.0589 (8)0.0572 (8)0.0039 (8)0.0270 (8)0.0065 (6)
C90.0567 (8)0.0491 (7)0.0558 (7)0.0084 (6)0.0200 (6)0.0096 (5)
C100.0569 (8)0.0544 (7)0.0553 (7)0.0037 (6)0.0179 (6)0.0085 (6)
C110.0790 (11)0.0666 (9)0.0649 (8)0.0040 (8)0.0339 (8)0.0095 (7)
O10.0912 (8)0.0423 (5)0.0835 (7)0.0214 (5)0.0488 (6)0.0082 (4)
O20.0751 (7)0.0571 (6)0.0612 (6)0.0077 (5)0.0334 (5)0.0043 (4)
O30.0673 (6)0.0475 (5)0.0644 (6)0.0165 (4)0.0354 (5)0.0110 (4)
Geometric parameters (Å, º) top
C1—O11.3469 (14)C7—O21.2384 (15)
C1—C61.3879 (16)C7—C81.4918 (18)
C1—C21.4056 (16)C8—H8A0.91 (2)
C2—C31.3991 (16)C8—H8B0.94 (2)
C2—C71.4573 (16)C8—H8C0.95 (2)
C3—C41.3627 (17)C9—O31.4275 (14)
C3—H30.9300C9—C101.4529 (18)
C4—C51.3920 (16)C9—H9A0.9700
C4—H40.9300C9—H9B0.9700
C5—O31.3602 (14)C10—C111.1712 (19)
C5—C61.3765 (16)C11—H110.9300
C6—H60.9300O1—H10.8200
O1—C1—C6117.20 (10)O2—C7—C8119.53 (12)
O1—C1—C2121.51 (11)C2—C7—C8119.89 (11)
C6—C1—C2121.27 (10)C7—C8—H8A114.1 (12)
C3—C2—C1117.34 (11)C7—C8—H8B112.2 (12)
C3—C2—C7121.92 (10)H8A—C8—H8B110.2 (17)
C1—C2—C7120.75 (10)C7—C8—H8C111.3 (12)
C4—C3—C2122.03 (10)H8A—C8—H8C104.4 (16)
C4—C3—H3119.0H8B—C8—H8C103.9 (17)
C2—C3—H3119.0O3—C9—C10107.45 (10)
C3—C4—C5119.24 (10)O3—C9—H9A110.2
C3—C4—H4120.4C10—C9—H9A110.2
C5—C4—H4120.4O3—C9—H9B110.2
O3—C5—C6124.19 (10)C10—C9—H9B110.2
O3—C5—C4114.68 (10)H9A—C9—H9B108.5
C6—C5—C4121.13 (10)C11—C10—C9177.83 (15)
C5—C6—C1118.99 (10)C10—C11—H11180.0
C5—C6—H6120.5C1—O1—H1109.5
C1—C6—H6120.5C5—O3—C9117.87 (9)
O2—C7—C2120.59 (11)
O1—C1—C2—C3179.06 (12)C4—C5—C6—C10.8 (2)
C6—C1—C2—C30.40 (19)O1—C1—C6—C5178.60 (12)
O1—C1—C2—C70.7 (2)C2—C1—C6—C50.1 (2)
C6—C1—C2—C7179.39 (12)C3—C2—C7—O2179.90 (12)
C1—C2—C3—C40.3 (2)C1—C2—C7—O20.3 (2)
C7—C2—C3—C4179.52 (12)C3—C2—C7—C80.1 (2)
C2—C3—C4—C50.4 (2)C1—C2—C7—C8179.89 (13)
C3—C4—C5—O3178.37 (12)C6—C5—O3—C91.1 (2)
C3—C4—C5—C60.9 (2)C4—C5—O3—C9179.62 (12)
O3—C5—C6—C1178.44 (12)C10—C9—O3—C5175.97 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.832.5551 (14)146
C4—H4···O3i0.932.543.4609 (16)172
C11—H11···O2ii0.932.323.2337 (18)168
Symmetry codes: (i) x+3, y+2, z; (ii) x+3/2, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.832.5551 (14)146
C4—H4···O3i0.932.543.4609 (16)172
C11—H11···O2ii0.932.323.2337 (18)168
Symmetry codes: (i) x+3, y+2, z; (ii) x+3/2, y+3/2, z1/2.
 

Acknowledgements

The authors thank the TBI X-ray facility and the UGC (SAP) CAS in Crystallography and Biophysics, University of Madras, India, for the data collection and other facilities. TS thanks the DST for an Inspire Fellowship.

References

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