The mol­ecule of the title compound, C5H8O2, a low-melting [alpha],[beta]-unsaturated carb­oxy­lic acid, is essentially planar [maximum displacement = 0.0239 (13) Å]. In the crystal, mol­ecules are linked into centrosymmetric dimers via pairs of O-H...O hydrogen bonds

Peppel, Tim

Sonneck, Marcel

Spannenberg, Anke

Wohlrab, Sebastian

Acta Crystallographica Section E Crystallographic Communications

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Repositorium für Naturwissenschaften und Technik

Crystal structure of (E)-pent-2-enoic acidTim Peppel,* Marcel Sonneck, Anke Spannenberg andSebastian WohlrabLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse29a, 18059 Rostock, Germany. *Correspondence e-mail: tim.peppel@catalysis.deReceived 9 April 2015; accepted 10 April 2015Edited by C. Rizzoli, Universita degli Studi di Parma, ItalyThe molecule of the title compound, C5H8O2, a low-melting,-unsaturated carboxylic acid, is essentially planar[maximum displacement = 0.0239 (13) Å]. In the crystal,molecules are linked into centrosymmetric dimers via pairs ofO—H  O hydrogen bonds.Keywords: crystal structure; hydrogen bond; dimer; unsaturated carboxylicacid.CCDC reference: 10588701. Related literatureFor the synthesis of unsaturated carboxylic acids including thetitle compound, see: Shabtai et al. (1981); Gastaminza et al.(1984); Outurquin & Paulmier (1989). For crystal structuredeterminations of acrylic acid, see: Higgs & Sass (1963);Chatani et al. (1963); Boese et al. (1999); Oswald & Urquhart(2011). For the structure of crotonic acid, see: Shimizu et al.(1974). For the structure of related hexenoic acid cocrystals,see: Aakeröy et al. (2003); Stanton & Bak (2008).2. Experimental2.1. Crystal dataC5H8O2Mr = 100.11Triclinic, P1a = 6.7336 (13) Åb = 6.7821 (13) Åc = 7.2349 (14) Å = 67.743 (2) = 75.518 (2) = 64.401 (2)V = 274.29 (9) Å3Z = 2Mo K radiation = 0.09 mm1T = 150 K0.51  0.35  0.27 mm2.2. Data collectionBruker APEXII CCDdiffractometerAbsorption correction: multi-scan(SADABS; Bruker, 2014)Tmin = 0.81, Tmax = 0.977544 measured reflections1323 independent reflections1122 reflections with I > 2(I)Rint = 0.0262.3. RefinementR[F 2 > 2(F 2)] = 0.037wR(F 2) = 0.113S = 1.101323 reflections69 parametersH atoms treated by a mixture ofindependent and constrainedrefinementmax = 0.36 e Å3min = 0.19 e Å3Table 1Hydrogen-bond geometry (Å, ).D—H  A D—H H  A D  A D—H  AO1—H1  O2i 0.95 (2) 1.69 (2) 2.6322 (13) 173.3 (19)Symmetry code: (i) x þ 1;yþ 2;zþ 1.Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT(Bruker, 2013); data reduction: SAINT; program(s) used to solvestructure: SHELXS97 (Sheldrick, 2008); program(s) used to refinestructure: SHELXL2014 (Sheldrick, 2015); molecular graphics:SHELXL2014; software used to prepare material for publication:SHELXL2014.AcknowledgementsThe authors thank P. Thiele (University of Rostock) for DSCmeasurements and Professor Dr J. G. de Vries (LIKAT) forhelpful support.Supporting information for this paper is available from the IUCrelectronic archives (Reference: RZ5155).ReferencesAakeröy, C. B., Beatty, A. M., Helfrich, B. A. & Nieuwenhuyzen, M. (2003).Cryst. Growth Des. 3, 159–165.Boese, R., Bläser, D., Steller, I., Latz, R. & Bäumen, A. (1999). Acta Cryst.C55, IUC9900006.Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.Bruker (2014). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin,USA.Chatani, Y., Sakata, Y. & Nitta, I. (1963). J. Polym. Sci. B Polym. Lett. 1, 419–421.Gastaminza, A. E., Ferracutti, N. N. & Rodriguez, N. M. (1984). J. Org. Chem.49, 3859–3860.Higgs, M. A. & Sass, R. L. (1963). Acta Cryst. 16, 657–661.Oswald, I. D. H. & Urquhart, A. J. (2011). CrystEngComm, 13, 4503–4507.Outurquin, F. & Paulmier, C. (1989). Synthesis, pp. 690–691.Shabtai, J., Ney-Igner, E. & Pines, H. (1981). J. Org. Chem. 46, 3795–3802.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.Shimizu, S., Kekka, S., Kashino, S. & Haisa, M. (1974). Bull. Chem. Soc. Jpn,47, 1627–1631.Stanton, M. K. & Bak, A. (2008). Cryst. Growth Des. 8, 3856–3862.data reportso316 Peppel et al. doi:10.1107/S2056989015007203 Acta Cryst. (2015). E71, o316ISSN 2056-9890supporting informationsup-1Acta Cryst. (2015). E71, o316    supporting informationActa Cryst. (2015). E71, o316    [https://doi.org/10.1107/S2056989015007203]Crystal structure of (E)-pent-2-enoic acidTim Peppel, Marcel Sonneck, Anke Spannenberg and Sebastian WohlrabS1. Synthesis and crystallization Malonic acid (24.8 g, 237.8 mmol, 1eq) was dissolved in dry pyridine (37.6 g, 475.7 mmol, 2 eq) at room temperature in a three-necked flask equipped with a magnetic stir bar and a reflux condenser under a mild flow of argon. Propanal (13.8 g, 240.2 mmol, 1 eq) was then added in one portion and the resulting clear solution further stirred for 72 h at room temperature under argon. Afterwards, the resulting light yellow to orange solution was brought to an acidic pH value by adding phosphoric acid at 0°C (42.5 wt.-%, 582.7 mmol, 2.45 eq). The resulting two layers were extracted three times with 150 mL portions of ethyl acetate and reduced to a volume of ca. 150 mL. To remove impurities from aldol condensation the raw acid was converted into the corresponding sodium salt by addition of an aqueous solution of sodium carbonate (18.9 g, 178.4 mmol, 0.75 eq in 200 mL). After stirring for 30 minutes the water phase was separated und extracted three times with 150 mL portions of ethyl acetate. The water phase was then acidified with concentrated hydrochloric acid (35.2 g, 356.7 mmol, 1.5 eq), the organic phase was separated and the water phase was again extracted three times with 150 mL portions of ethyl acetate. The combined organic phases were dried over Na2SO4 and evaporated to dryness under diminished pressure. The resulting raw product was further purified by distillation in vacuo yielding the product in purity >99% (GC). M. p. 10°C. 1H NMR (400 MHz, CDCl3): δ = 12.35 (br s, 1H, OH); 7.14 (dt, 3J = 15.6 Hz, 3J = 6.3 Hz, 1H, -CH-); 5.82 (dt, 3J = 15.6 Hz, 4J = 1.7 Hz, 1H, -CH-); 2.30-2.21 (m, 2H, -CH2-); 1.08 (t, 3J = 7.4 Hz, 3H, -CH3-). 13C NMR (100 MHz, CDCl3): δ = 172.69 (CO); 153.77 (CH); 119.76 (CH); 25.54 (CH2); 21.10 (CH3). MS (EI, 70 eV): m/z = 100 (M+, 50), 83 (13), 82 (23), 81 (10), 58 (11), 57 (17), 56 (23), 55 (100), 54 (43), 53 (35), 52 (12), 51 (25), 50 (28), 45 (77), 41 (36), 40 (13), 39 (99), 38 (25), 37 (11), 29 (61). HRMS (ESI-TOF/MS): calculated for C5H8O2 (M+) 99.04515, found 99.04529. Elemental analysis for C5H8O2 % (calc.): C 59.99 (59.98); H 8.05 (8.05). Suitable single crystals were grown by slow evaporation of an ethanolic solution at -30 °C over one week. S2. Refinement The carboxylic H atom could be found in a difference Fourier map and was refined freely. All other H atoms were placed in idealized positions with d(C—H) = 0.95 Å (CH), 0.99 Å (CH2), 0.98 Å (CH3) and refined using a riding model with Uiso(H) fixed at 1.2 Ueq(C) for CH and CH2 and 1.5 Ueq(C) for CH3. A rotating model was used for the methyl group. supporting informationsup-2Acta Cryst. (2015). E71, o316    Figure 1The molecular structure of the title compound with displacement ellipsoids drawn at 50% probability level. Figure 2ORTEP representation of a dimer formed by intermolecular O—H···O hydrogen bonds. (E)-Pent-2-enoic acid Crystal data C5H8O2Mr = 100.11Triclinic, P1a = 6.7336 (13) Åb = 6.7821 (13) Åc = 7.2349 (14) Åα = 67.743 (2)°β = 75.518 (2)°γ = 64.401 (2)°V = 274.29 (9) Å3Z = 2F(000) = 108Dx = 1.212 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 4399 reflectionsθ = 3.1–28.7°µ = 0.09 mm−1T = 150 KPrism, colourless0.51 × 0.35 × 0.27 mmData collection Bruker APEXII CCD diffractometerRadiation source: fine-focus sealed tubeDetector resolution: 8.3333 pixels mm-1φ and ω scansAbsorption correction: multi-scan (SADABS; Bruker, 2014)Tmin = 0.81, Tmax = 0.977544 measured reflections1323 independent reflections1122 reflections with I > 2σ(I)Rint = 0.026θmax = 28.0°, θmin = 3.1°h = −8→8k = −8→8l = −9→9supporting informationsup-3Acta Cryst. (2015). E71, o316    Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.037wR(F2) = 0.113S = 1.101323 reflections69 parameters0 restraintsHydrogen site location: mixedH atoms treated by a mixture of independent and constrained refinementw = 1/[σ2(Fo2) + (0.0562P)2 + 0.0602P] where P = (Fo2 + 2Fc2)/3(Δ/σ)max < 0.001Δρmax = 0.36 e Å−3Δρmin = −0.19 e Å−3Special 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.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/UeqC1 0.36613 (18) 0.77456 (19) 0.59878 (16) 0.0284 (3)C2 0.25933 (18) 0.6065 (2) 0.66526 (16) 0.0295 (3)H2 0.1507 0.6289 0.5893 0.035*C3 0.31028 (18) 0.4243 (2) 0.82842 (16) 0.0290 (3)H3 0.4190 0.4066 0.9018 0.035*C4 0.2111 (2) 0.2446 (2) 0.90640 (17) 0.0323 (3)H4A 0.1414 0.2401 1.0450 0.039*H4B 0.3320 0.0930 0.9135 0.039*C5 0.0389 (2) 0.2791 (2) 0.78294 (19) 0.0372 (3)H5A −0.0864 0.4244 0.7812 0.056*H5B −0.0133 0.1517 0.8430 0.056*H5C 0.1055 0.2834 0.6452 0.056*O1 0.30172 (15) 0.93766 (15) 0.42861 (12) 0.0357 (3)O2 0.50223 (14) 0.76619 (15) 0.69113 (12) 0.0361 (3)H1 0.376 (3) 1.039 (4) 0.395 (3) 0.071 (6)*Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23C1 0.0277 (5) 0.0275 (6) 0.0251 (5) −0.0060 (4) −0.0070 (4) −0.0056 (4)C2 0.0270 (5) 0.0326 (6) 0.0272 (5) −0.0093 (5) −0.0077 (4) −0.0066 (4)C3 0.0265 (5) 0.0325 (6) 0.0257 (5) −0.0086 (4) −0.0067 (4) −0.0071 (4)C4 0.0321 (6) 0.0332 (6) 0.0267 (5) −0.0121 (5) −0.0087 (4) −0.0010 (4)C5 0.0378 (6) 0.0382 (7) 0.0355 (6) −0.0177 (5) −0.0135 (5) −0.0013 (5)O1 0.0406 (5) 0.0339 (5) 0.0295 (4) −0.0147 (4) −0.0153 (3) 0.0015 (3)O2 0.0402 (5) 0.0345 (5) 0.0332 (5) −0.0155 (4) −0.0166 (4) −0.0005 (3)Geometric parameters (Å, º) C1—O2 1.2337 (14) C4—C5 1.5239 (16)C1—O1 1.3223 (13) C4—H4A 0.9900supporting informationsup-4Acta Cryst. (2015). E71, o316    C1—C2 1.4723 (16) C4—H4B 0.9900C2—C3 1.3301 (16) C5—H5A 0.9800C2—H2 0.9500 C5—H5B 0.9800C3—C4 1.4981 (16) C5—H5C 0.9800C3—H3 0.9500 O1—H1 0.95 (2)O2—C1—O1 122.75 (11) C5—C4—H4A 108.4O2—C1—C2 123.99 (10) C3—C4—H4B 108.4O1—C1—C2 113.26 (10) C5—C4—H4B 108.4C3—C2—C1 122.03 (10) H4A—C4—H4B 107.5C3—C2—H2 119.0 C4—C5—H5A 109.5C1—C2—H2 119.0 C4—C5—H5B 109.5C2—C3—C4 125.63 (10) H5A—C5—H5B 109.5C2—C3—H3 117.2 C4—C5—H5C 109.5C4—C3—H3 117.2 H5A—C5—H5C 109.5C3—C4—C5 115.33 (10) H5B—C5—H5C 109.5C3—C4—H4A 108.4 C1—O1—H1 108.7 (12)O2—C1—C2—C3 −3.05 (19) C1—C2—C3—C4 −179.72 (10)O1—C1—C2—C3 176.98 (11) C2—C3—C4—C5 0.45 (18)Hydrogen-bond geometry (Å, º) D—H···A D—H H···A D···A D—H···AO1—H1···O2i 0.95 (2) 1.69 (2) 2.6322 (13) 173.3 (19)Symmetry code: (i) −x+1, −y+2, −z+1.

Crystal structure of (E)-pent-2-enoic acid

The molecule of the title compound, C5H8O2, a low-melting α,β-unsaturated carboxylic acid, is essentially planar [maximum displacement = 0.0239 (13) Å]. In the crystal, molecules are linked into centrosymmetric dimers via pairs of O—H...O hydrogen bonds

Tim Peppel

Marcel Sonneck

Anke Spannenberg

Sebastian Wohlrab

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Crystal structure of (E)-pent-2-enoic acid

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