Acta Cryst. (2007). E63, o4032 [ doi:10.1107/S1600536807043747 ]
The title compound, C5H8O3, was prepared as a potentially chelating molecule bearing the conformationally rigid cyclobutane group. The cyclobutane ring is arranged perpendicular to the carboxyl group. In the polar crystal structure, each molecule exhibits four hydrogen-bonded contacts to neighbouring molecules. Instead of the formation of typical carboxylic acid dimers, an infinite hydrogen-bonded chain with alternating O-H and O=C-O-H units is observed.
The title compound was prepared according to standard procedures (Becker et al., 2001) upon acidic hydrolysis of the cyanohydrin of cyclobutanone. Crystals suitable for X-ray analysis were directly obtained from the crystallized reaction product.
All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to Uiso(H) = 0.062 (3).
Due to the absence of significant anomalous scattering the absolute structure factor, which is −1.2 with an estimated standard deviation of 1.1 for the unmerged data set, is meaningless. Thus, Friedel opposites (327 pairs) have been merged.
Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
![[Figure 1]](./si2033fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms. |
| C5H8O3 | Z = 18 |
| Mr = 116.12 | F000 = 1116 |
| Trigonal, R3c | Dx = 1.351 Mg m−3 |
| Hall symbol: R 3 -2"c | Mo Kα radiation λ = 0.71073 Å |
| a = 10.158 (5) Å | Cell parameters from 8387 reflections |
| b = 10.158 (5) Å | θ = 3.1–27.5º |
| c = 28.747 (5) Å | µ = 0.11 mm−1 |
| α = 90º | T = 293 (2) K |
| β = 90º | Block, colourless |
| γ = 120º | 0.25 × 0.20 × 0.16 mm |
| V = 2568.9 (18) Å3 |
| Nonius KappaCCD diffractometer | 629 reflections with I > 2σ(I) |
| Radiation source: rotating anode | Rint = 0.013 |
| Monochromator: MONTEL, graded multilayered X-ray optics | θmax = 27.5º |
| T = 293(2) K | θmin = 3.7º |
| φ/ω–scan | h = −13→13 |
| Absorption correction: none | k = −10→10 |
| 2401 measured reflections | l = −37→37 |
| 657 independent reflections |
| Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.8981P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.029 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.079 | Δρmax = 0.15 e Å−3 |
| S = 1.07 | Δρmin = −0.11 e Å−3 |
| 657 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 82 parameters | Extinction coefficient: 0.0040 (11) |
| 1 restraint | |
| Primary atom site location: structure-invariant direct methods | |
| Secondary atom site location: difference Fourier map | |
| Hydrogen site location: difference Fourier map |
| C5H8O3 | γ = 120º |
| Mr = 116.12 | V = 2568.9 (18) Å3 |
| Trigonal, R3c | Z = 18 |
| a = 10.158 (5) Å | Mo Kα |
| b = 10.158 (5) Å | µ = 0.11 mm−1 |
| c = 28.747 (5) Å | T = 293 (2) K |
| α = 90º | 0.25 × 0.20 × 0.16 mm |
| β = 90º |
| Nonius KappaCCD diffractometer | 657 independent reflections |
| Absorption correction: none | 629 reflections with I > 2σ(I) |
| 2401 measured reflections | Rint = 0.013 |
| R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.079 | Δρmax = 0.15 e Å−3 |
| S = 1.07 | Δρmin = −0.11 e Å−3 |
| 657 reflections | Absolute structure: ? |
| 82 parameters | Flack parameter: |
| 1 restraint | Rogers parameter: ? |
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 > 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 | ||
| O2 | 0.18848 (17) | 0.15037 (16) | 0.00859 (5) | 0.0401 (4) | |
| H2 | 0.160 (4) | 0.079 (4) | 0.0286 (12) | 0.070 (9)* | |
| O11 | 0.2872 (2) | 0.4282 (2) | 0.09671 (6) | 0.0553 (5) | |
| H11 | 0.240 (4) | 0.439 (4) | 0.1225 (13) | 0.075 (10)* | |
| O12 | 0.06620 (18) | 0.22283 (19) | 0.07944 (6) | 0.0501 (4) | |
| C1 | 0.1989 (2) | 0.3086 (2) | 0.07142 (6) | 0.0351 (4) | |
| C2 | 0.2812 (2) | 0.2928 (2) | 0.02965 (6) | 0.0324 (4) | |
| C3 | 0.3344 (3) | 0.4280 (2) | −0.00422 (7) | 0.0412 (5) | |
| H31 | 0.3220 | 0.3988 | −0.0368 | 0.049* | |
| H32 | 0.2911 | 0.4922 | 0.0023 | 0.049* | |
| C4 | 0.4967 (3) | 0.4924 (3) | 0.01362 (11) | 0.0609 (6) | |
| H41 | 0.5287 | 0.5773 | 0.0348 | 0.073* | |
| H42 | 0.5711 | 0.5169 | −0.0109 | 0.073* | |
| C5 | 0.4496 (3) | 0.3412 (3) | 0.03797 (9) | 0.0459 (5) | |
| H51 | 0.4778 | 0.3519 | 0.0706 | 0.055* | |
| H52 | 0.4821 | 0.2784 | 0.0218 | 0.055* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O2 | 0.0480 (8) | 0.0331 (7) | 0.0344 (7) | 0.0166 (6) | 0.0051 (6) | −0.0051 (6) |
| O11 | 0.0485 (9) | 0.0572 (10) | 0.0458 (9) | 0.0155 (8) | 0.0085 (7) | −0.0200 (7) |
| O12 | 0.0431 (8) | 0.0510 (9) | 0.0465 (8) | 0.0163 (7) | 0.0117 (6) | −0.0083 (7) |
| C1 | 0.0388 (10) | 0.0363 (9) | 0.0316 (9) | 0.0199 (8) | 0.0040 (7) | 0.0000 (7) |
| C2 | 0.0372 (9) | 0.0332 (9) | 0.0291 (8) | 0.0193 (7) | 0.0024 (7) | −0.0013 (7) |
| C3 | 0.0492 (11) | 0.0400 (10) | 0.0381 (9) | 0.0250 (10) | 0.0093 (8) | 0.0063 (8) |
| C4 | 0.0431 (13) | 0.0529 (15) | 0.0701 (15) | 0.0115 (10) | 0.0060 (12) | 0.0073 (12) |
| C5 | 0.0402 (11) | 0.0539 (12) | 0.0503 (11) | 0.0284 (10) | −0.0026 (9) | −0.0069 (9) |
| O2—C2 | 1.409 (2) | C3—C4 | 1.527 (4) |
| O2—H2 | 0.85 (4) | C3—H31 | 0.9700 |
| O11—C1 | 1.311 (2) | C3—H32 | 0.9700 |
| O11—H11 | 0.92 (4) | C4—C5 | 1.531 (4) |
| O12—C1 | 1.207 (2) | C4—H41 | 0.9700 |
| C1—C2 | 1.517 (2) | C4—H42 | 0.9700 |
| C2—C3 | 1.544 (3) | C5—H51 | 0.9700 |
| C2—C5 | 1.544 (3) | C5—H52 | 0.9700 |
| C2—O2—H2 | 110 (2) | C2—C3—H32 | 113.7 |
| C1—O11—H11 | 114 (2) | H31—C3—H32 | 111.0 |
| O12—C1—O11 | 124.26 (18) | C3—C4—C5 | 89.70 (18) |
| O12—C1—C2 | 123.42 (17) | C3—C4—H41 | 113.7 |
| O11—C1—C2 | 112.28 (17) | C5—C4—H41 | 113.7 |
| O2—C2—C1 | 109.16 (15) | C3—C4—H42 | 113.7 |
| O2—C2—C3 | 113.53 (15) | C5—C4—H42 | 113.7 |
| C1—C2—C3 | 111.77 (15) | H41—C4—H42 | 110.9 |
| O2—C2—C5 | 117.34 (17) | C4—C5—C2 | 89.39 (17) |
| C1—C2—C5 | 115.15 (16) | C4—C5—H51 | 113.7 |
| C3—C2—C5 | 88.59 (15) | C2—C5—H51 | 113.7 |
| C4—C3—C2 | 89.54 (17) | C4—C5—H52 | 113.7 |
| C4—C3—H31 | 113.7 | C2—C5—H52 | 113.7 |
| C2—C3—H31 | 113.7 | H51—C5—H52 | 111.0 |
| C4—C3—H32 | 113.7 | ||
| O12—C1—C2—O2 | −11.5 (3) | C1—C2—C3—C4 | 104.08 (19) |
| O11—C1—C2—O2 | 170.40 (18) | C5—C2—C3—C4 | −12.53 (19) |
| O12—C1—C2—C3 | 114.9 (2) | C2—C3—C4—C5 | 12.64 (18) |
| O11—C1—C2—C3 | −63.2 (2) | C3—C4—C5—C2 | −12.64 (18) |
| O12—C1—C2—C5 | −146.0 (2) | O2—C2—C5—C4 | 128.41 (19) |
| O11—C1—C2—C5 | 35.9 (2) | C1—C2—C5—C4 | −101.0 (2) |
| O2—C2—C3—C4 | −131.90 (19) | C3—C2—C5—C4 | 12.50 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O12i | 0.85 (4) | 2.07 (4) | 2.895 (2) | 163 (3) |
| O2—H2···O2i | 0.85 (4) | 2.51 (3) | 3.037 (3) | 121 (3) |
| O11—H11···O2ii | 0.92 (4) | 1.74 (4) | 2.6488 (19) | 170 (4) |
| Symmetry codes: (i) −x+y, −x, z; (ii) −y+1/3, −x+2/3, z+1/6. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O12i | 0.85 (4) | 2.07 (4) | 2.895 (2) | 163 (3) |
| O2—H2···O2i | 0.85 (4) | 2.51 (3) | 3.037 (3) | 121 (3) |
| O11—H11···O2ii | 0.92 (4) | 1.74 (4) | 2.6488 (19) | 170 (4) |
| Symmetry codes: (i) −x+y, −x, z; (ii) −y+1/3, −x+2/3, z+1/6. |
The authors thank Dr Peter Mayer for professional support. The coeditor (H. Schmalle) is acknowledged for his support regarding graph theory.
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.
Becker, H. G. O., Beckert, R., Domschke, G., Fanghänel, E., Habicher, W. D., Metz, P., Pavel, D. & Schwetlick, K. (2001). Organikum – Organisch-chemisches Grundpraktikum. Weinheim, Germany: Wiley-VCH.
Bernstein, J., Davies, R. E. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
Betz, R. & Klüfers, P. (2007a). Acta Cryst. E63, o3891–?.
Betz, R. & Klüfers, P. (2007b). Acta Cryst. E63, o3932–?.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Muranishi, Y. & Okabe, N. (2004). Acta Cryst. C60, m47–m50.
Nonius (2004). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
The title compound, C5H8O3, was prepared as a potential chelating molecule bearing the conformational rigid cyclobutane group.
The cyclobutane ring adopts a perpendicular orientation to the carboxyl group (Fig. 1). One carbon atom of the cyclobutane ring shows a comparatively high anisotropic displacement parameter – a finding, which is in agreement with the results obtained for a palladium complex including cyclobutane moieties (Muranishi & Okabe, 2004). The observed bond lengths are in agreement with valence considerations. Intermolecular hydrogen bonds determine the crystal structure. Due to the trigonal 3-axes symmetry, trimer ring systems with graph set notation R33(5) and infinite chains C(5) (Bernstein et al., 1995) form the three-dimensional network. The formation of dimeric units upon hydrogen-bond formation – as is apparent in the structures of 1-hydroxycyclopropane-1-carboxylic acid (Betz & Klüfers, 2007a) and the cyclopentane analogue (Betz & Klüfers, 2007b) – is not observed. Instead, infinite bonding sequences of the type (···O=C—O–H···O–H···)n with alternating carboxy and hydroxy functions are formed.