organic compounds
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
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).
CCDC reference: 966316
Related literature
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
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; 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 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 966316
https://doi.org/10.1107/S1600536813032613/su2668sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032613/su2668Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032613/su2668Isup3.cml
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
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 were obtained by the slow evaporation of a solution in ethyl acetate.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.
Schiff bases derived from
and substituted benzaldehydes exhibit antibacterial, anticancer and antitumour activities (Zhao et al., 2007). Several benzaldoximes, benzaldehyde-O-ethyloximes and acetophenone 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–C10≡C11 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).
Data collection: APEX2 (Bruker, 2008); cell
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).C11H10O3 | F(000) = 400 |
Mr = 190.19 | Dx = 1.296 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2451 reflections |
a = 4.9975 (2) Å | θ = 2.2–28.4° |
b = 10.4305 (4) Å | µ = 0.10 mm−1 |
c = 18.8467 (7) Å | T = 293 K |
β = 97.257 (2)° | Block, colourless |
V = 974.54 (7) Å3 | 0.35 × 0.30 × 0.20 mm |
Z = 4 |
Bruker SMART APEXII area-detector diffractometer | 2451 independent reflections |
Radiation source: fine-focus sealed tube | 1898 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω and φ scans | θmax = 28.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −6→6 |
Tmin = 0.968, Tmax = 0.981 | k = −13→13 |
9316 measured reflections | l = −25→25 |
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)] = 0.043 | H 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 reflections | Δρmax = 0.17 e Å−3 |
138 parameters | Δρmin = −0.21 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.020 (4) |
C11H10O3 | V = 974.54 (7) Å3 |
Mr = 190.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.9975 (2) Å | µ = 0.10 mm−1 |
b = 10.4305 (4) Å | T = 293 K |
c = 18.8467 (7) Å | 0.35 × 0.30 × 0.20 mm |
β = 97.257 (2)° |
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 = 0.981 | Rint = 0.021 |
9316 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 3 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.17 e Å−3 |
2451 reflections | Δρmin = −0.21 e Å−3 |
138 parameters |
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 | ||
C1 | 0.9425 (3) | 0.69719 (11) | 0.08613 (7) | 0.0455 (3) | |
C2 | 0.9120 (2) | 0.81055 (10) | 0.12463 (6) | 0.0421 (3) | |
C3 | 1.0579 (3) | 0.91806 (11) | 0.10720 (6) | 0.0475 (3) | |
H3 | 1.0417 | 0.9941 | 0.1320 | 0.057* | |
C4 | 1.2229 (3) | 0.91474 (11) | 0.05494 (7) | 0.0506 (3) | |
H4 | 1.3186 | 0.9874 | 0.0446 | 0.061* | |
C5 | 1.2467 (3) | 0.80135 (11) | 0.01728 (6) | 0.0446 (3) | |
C6 | 1.1094 (3) | 0.69245 (11) | 0.03266 (6) | 0.0468 (3) | |
H6 | 1.1283 | 0.6169 | 0.0076 | 0.056* | |
C7 | 0.7340 (3) | 0.81464 (12) | 0.18017 (6) | 0.0485 (3) | |
C8 | 0.7041 (4) | 0.93600 (15) | 0.22030 (9) | 0.0632 (4) | |
H8A | 0.595 (4) | 0.9292 (18) | 0.2554 (11) | 0.095* | |
H8B | 0.648 (4) | 1.005 (2) | 0.1896 (10) | 0.095* | |
H8C | 0.872 (4) | 0.9636 (19) | 0.2446 (10) | 0.095* | |
C9 | 1.4462 (3) | 0.69606 (12) | −0.07557 (7) | 0.0527 (3) | |
H9A | 1.2727 | 0.6639 | −0.0972 | 0.063* | |
H9B | 1.5342 | 0.6298 | −0.0449 | 0.063* | |
C10 | 1.6120 (3) | 0.73056 (13) | −0.13064 (7) | 0.0546 (3) | |
C11 | 1.7405 (3) | 0.75594 (16) | −0.17657 (8) | 0.0680 (4) | |
H11 | 1.8424 | 0.7761 | −0.2130 | 0.082* | |
O1 | 0.8072 (2) | 0.58946 (8) | 0.09853 (6) | 0.0691 (4) | |
H1 | 0.7187 | 0.6017 | 0.1317 | 0.104* | |
O2 | 0.6074 (2) | 0.71799 (10) | 0.19459 (5) | 0.0624 (3) | |
O3 | 1.4107 (2) | 0.80891 (8) | −0.03494 (5) | 0.0574 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0506 (7) | 0.0372 (5) | 0.0508 (6) | −0.0075 (5) | 0.0149 (5) | 0.0001 (4) |
C2 | 0.0460 (6) | 0.0395 (5) | 0.0418 (5) | −0.0015 (5) | 0.0098 (5) | 0.0009 (4) |
C3 | 0.0570 (7) | 0.0372 (5) | 0.0501 (6) | −0.0056 (5) | 0.0140 (5) | −0.0060 (4) |
C4 | 0.0595 (8) | 0.0385 (6) | 0.0569 (7) | −0.0126 (5) | 0.0196 (6) | −0.0035 (5) |
C5 | 0.0457 (7) | 0.0431 (6) | 0.0472 (6) | −0.0071 (5) | 0.0149 (5) | −0.0022 (4) |
C6 | 0.0531 (7) | 0.0370 (5) | 0.0531 (6) | −0.0072 (5) | 0.0177 (6) | −0.0073 (4) |
C7 | 0.0549 (8) | 0.0484 (6) | 0.0438 (6) | 0.0027 (5) | 0.0127 (5) | 0.0033 (5) |
C8 | 0.0781 (11) | 0.0589 (8) | 0.0572 (8) | 0.0039 (8) | 0.0270 (8) | −0.0065 (6) |
C9 | 0.0567 (8) | 0.0491 (7) | 0.0558 (7) | −0.0084 (6) | 0.0200 (6) | −0.0096 (5) |
C10 | 0.0569 (8) | 0.0544 (7) | 0.0553 (7) | −0.0037 (6) | 0.0179 (6) | −0.0085 (6) |
C11 | 0.0790 (11) | 0.0666 (9) | 0.0649 (8) | −0.0040 (8) | 0.0339 (8) | −0.0095 (7) |
O1 | 0.0912 (8) | 0.0423 (5) | 0.0835 (7) | −0.0214 (5) | 0.0488 (6) | −0.0082 (4) |
O2 | 0.0751 (7) | 0.0571 (6) | 0.0612 (6) | −0.0077 (5) | 0.0334 (5) | 0.0043 (4) |
O3 | 0.0673 (6) | 0.0475 (5) | 0.0644 (6) | −0.0165 (4) | 0.0354 (5) | −0.0110 (4) |
C1—O1 | 1.3469 (14) | C7—O2 | 1.2384 (15) |
C1—C6 | 1.3879 (16) | C7—C8 | 1.4918 (18) |
C1—C2 | 1.4056 (16) | C8—H8A | 0.91 (2) |
C2—C3 | 1.3991 (16) | C8—H8B | 0.94 (2) |
C2—C7 | 1.4573 (16) | C8—H8C | 0.95 (2) |
C3—C4 | 1.3627 (17) | C9—O3 | 1.4275 (14) |
C3—H3 | 0.9300 | C9—C10 | 1.4529 (18) |
C4—C5 | 1.3920 (16) | C9—H9A | 0.9700 |
C4—H4 | 0.9300 | C9—H9B | 0.9700 |
C5—O3 | 1.3602 (14) | C10—C11 | 1.1712 (19) |
C5—C6 | 1.3765 (16) | C11—H11 | 0.9300 |
C6—H6 | 0.9300 | O1—H1 | 0.8200 |
O1—C1—C6 | 117.20 (10) | O2—C7—C8 | 119.53 (12) |
O1—C1—C2 | 121.51 (11) | C2—C7—C8 | 119.89 (11) |
C6—C1—C2 | 121.27 (10) | C7—C8—H8A | 114.1 (12) |
C3—C2—C1 | 117.34 (11) | C7—C8—H8B | 112.2 (12) |
C3—C2—C7 | 121.92 (10) | H8A—C8—H8B | 110.2 (17) |
C1—C2—C7 | 120.75 (10) | C7—C8—H8C | 111.3 (12) |
C4—C3—C2 | 122.03 (10) | H8A—C8—H8C | 104.4 (16) |
C4—C3—H3 | 119.0 | H8B—C8—H8C | 103.9 (17) |
C2—C3—H3 | 119.0 | O3—C9—C10 | 107.45 (10) |
C3—C4—C5 | 119.24 (10) | O3—C9—H9A | 110.2 |
C3—C4—H4 | 120.4 | C10—C9—H9A | 110.2 |
C5—C4—H4 | 120.4 | O3—C9—H9B | 110.2 |
O3—C5—C6 | 124.19 (10) | C10—C9—H9B | 110.2 |
O3—C5—C4 | 114.68 (10) | H9A—C9—H9B | 108.5 |
C6—C5—C4 | 121.13 (10) | C11—C10—C9 | 177.83 (15) |
C5—C6—C1 | 118.99 (10) | C10—C11—H11 | 180.0 |
C5—C6—H6 | 120.5 | C1—O1—H1 | 109.5 |
C1—C6—H6 | 120.5 | C5—O3—C9 | 117.87 (9) |
O2—C7—C2 | 120.59 (11) | ||
O1—C1—C2—C3 | −179.06 (12) | C4—C5—C6—C1 | 0.8 (2) |
C6—C1—C2—C3 | −0.40 (19) | O1—C1—C6—C5 | 178.60 (12) |
O1—C1—C2—C7 | 0.7 (2) | C2—C1—C6—C5 | −0.1 (2) |
C6—C1—C2—C7 | 179.39 (12) | C3—C2—C7—O2 | −179.90 (12) |
C1—C2—C3—C4 | 0.3 (2) | C1—C2—C7—O2 | 0.3 (2) |
C7—C2—C3—C4 | −179.52 (12) | C3—C2—C7—C8 | −0.1 (2) |
C2—C3—C4—C5 | 0.4 (2) | C1—C2—C7—C8 | −179.89 (13) |
C3—C4—C5—O3 | 178.37 (12) | C6—C5—O3—C9 | −1.1 (2) |
C3—C4—C5—C6 | −0.9 (2) | C4—C5—O3—C9 | 179.62 (12) |
O3—C5—C6—C1 | −178.44 (12) | C10—C9—O3—C5 | 175.97 (12) |
D—H···A | D—H | H···A | D···A | 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+3/2, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | 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+3/2, −y+3/2, z−1/2. |
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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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–C10≡C11 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.