organic compounds
3-Chloro-4-hydroxyfuran-2(5H)-one
aDepartment of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China, and bState Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, People's Republic of China
*Correspondence e-mail: zywu@xmu.edu.cn
In the title compound, C4H3ClO3, molecules are linked via O—H⋯O hydrogen bonds into an infinite chain with graph-set motif C(6) along the c axis.
Related literature
4-Hydroxy-5H-furan-2-one (tetronic acid) forms a subclass of β-hydroxybutenolides with a generic structure, see: Haynes & Plimmer (1960). A great number of these compounds and their metabolites are found in many natural products and exhibit a wide array of biological properties, see: Sodeoka et al. (2001). For related structures, see: Ma et al. (2004). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2009).
Supporting information
10.1107/S1600536809028724/bx2226sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809028724/bx2226Isup2.hkl
All reagents and solvents were used as obtained commercially without further purification. To a stirred solution of monochloroacetic acid(2 mmol, 137µL) in 5 mL dry THF is added sodium(1 mmol, 23 mg) under N2. After the solution has been stirred at room temperature for 24 h, the resulting pale yellow solution was kept in darkness for four days, yellow well formed block-shaped crystals were obtained.
The aromatic H atoms were generated geometrically (C—H 0.93 Å) and were allowed to ride on their parent atoms in the riding model approximations, with their temperature factors set to 1.2 times those of the parent atoms. The position and Ueq of the hydroxyl H atom were refined with O—H distance restrained to 0.85 Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).C4H3ClO3 | F(000) = 272 |
Mr = 134.51 | Dx = 1.774 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 1627 reflections |
a = 12.0437 (6) Å | θ = 3.1–28.9° |
b = 6.5453 (4) Å | µ = 0.65 mm−1 |
c = 6.3886 (4) Å | T = 298 K |
V = 503.61 (5) Å3 | Block, yellow |
Z = 4 | 0.50 × 0.50 × 0.30 mm |
Oxford Gemini S Ultra diffractometer | 531 independent reflections |
Radiation source: fine-focus sealed tube | 500 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
Detector resolution: 16.1903 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −7→8 |
Tmin = 0.736, Tmax = 0.828 | l = −7→7 |
1932 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0374P)2 + 0.1215P] where P = (Fo2 + 2Fc2)/3 |
531 reflections | (Δ/σ)max < 0.001 |
52 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C4H3ClO3 | V = 503.61 (5) Å3 |
Mr = 134.51 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.0437 (6) Å | µ = 0.65 mm−1 |
b = 6.5453 (4) Å | T = 298 K |
c = 6.3886 (4) Å | 0.50 × 0.50 × 0.30 mm |
Oxford Gemini S Ultra diffractometer | 531 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 500 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 0.828 | Rint = 0.012 |
1932 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.25 e Å−3 |
531 reflections | Δρmin = −0.20 e Å−3 |
52 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.34253 (4) | 0.7500 | 0.60829 (9) | 0.0400 (2) | |
O1 | 0.10530 (15) | 0.7500 | 0.8246 (3) | 0.0531 (5) | |
O2 | 0.24683 (15) | 0.7500 | 0.1417 (2) | 0.0409 (4) | |
O3 | 0.02339 (12) | 0.7500 | 0.5138 (2) | 0.0410 (4) | |
C1 | 0.05689 (17) | 0.7500 | 0.2974 (3) | 0.0348 (5) | |
H1A | 0.0295 | 0.8706 | 0.2259 | 0.042* | 0.50 |
H1B | 0.0295 | 0.6294 | 0.2259 | 0.042* | 0.50 |
C2 | 0.18096 (17) | 0.7500 | 0.3064 (3) | 0.0288 (4) | |
C3 | 0.21185 (17) | 0.7500 | 0.5069 (3) | 0.0289 (4) | |
C4 | 0.11471 (18) | 0.7500 | 0.6361 (3) | 0.0335 (5) | |
H2 | 0.210 (3) | 0.7500 | 0.037 (5) | 0.059 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0274 (3) | 0.0523 (4) | 0.0403 (3) | 0.000 | −0.0084 (2) | 0.000 |
O1 | 0.0421 (9) | 0.0940 (14) | 0.0231 (8) | 0.000 | 0.0033 (6) | 0.000 |
O2 | 0.0376 (8) | 0.0614 (11) | 0.0238 (8) | 0.000 | 0.0062 (7) | 0.000 |
O3 | 0.0260 (8) | 0.0679 (10) | 0.0292 (9) | 0.000 | 0.0011 (6) | 0.000 |
C1 | 0.0308 (10) | 0.0487 (12) | 0.0249 (11) | 0.000 | −0.0042 (8) | 0.000 |
C2 | 0.0284 (10) | 0.0337 (10) | 0.0241 (10) | 0.000 | 0.0019 (8) | 0.000 |
C3 | 0.0251 (10) | 0.0355 (10) | 0.0261 (11) | 0.000 | −0.0006 (7) | 0.000 |
C4 | 0.0299 (10) | 0.0460 (12) | 0.0247 (11) | 0.000 | 0.0006 (8) | 0.000 |
Cl1—C3 | 1.702 (2) | C1—C2 | 1.495 (3) |
O1—C4 | 1.210 (3) | C1—H1A | 0.9700 |
O2—C2 | 1.318 (2) | C1—H1B | 0.9700 |
O2—H2 | 0.80 (3) | C2—C3 | 1.334 (3) |
O3—C4 | 1.349 (3) | C3—C4 | 1.431 (3) |
O3—C1 | 1.440 (3) | ||
C2—O2—H2 | 109 (2) | O2—C2—C1 | 124.82 (18) |
C4—O3—C1 | 109.11 (16) | C3—C2—C1 | 108.38 (17) |
O3—C1—C2 | 104.08 (16) | C2—C3—C4 | 109.00 (19) |
O3—C1—H1A | 110.9 | C2—C3—Cl1 | 128.55 (17) |
C2—C1—H1A | 110.9 | C4—C3—Cl1 | 122.45 (15) |
O3—C1—H1B | 110.9 | O1—C4—O3 | 120.0 (2) |
C2—C1—H1B | 110.9 | O1—C4—C3 | 130.6 (2) |
H1A—C1—H1B | 109.0 | O3—C4—C3 | 109.43 (17) |
O2—C2—C3 | 126.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.80 (3) | 1.85 (3) | 2.647 (2) | 171 (3) |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C4H3ClO3 |
Mr | 134.51 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 298 |
a, b, c (Å) | 12.0437 (6), 6.5453 (4), 6.3886 (4) |
V (Å3) | 503.61 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.50 × 0.50 × 0.30 |
Data collection | |
Diffractometer | Oxford Gemini S Ultra diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.736, 0.828 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1932, 531, 500 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.067, 1.17 |
No. of reflections | 531 |
No. of parameters | 52 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.20 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.80 (3) | 1.85 (3) | 2.647 (2) | 171 (3) |
Symmetry code: (i) x, y, z−1. |
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Haynes, L. J. & Plimmer, J. R. (1960). Q. Rev. Chem. Soc. 14, 292–315. CrossRef CAS Web of Science Google Scholar
Ma, S. M., Wu, B. & Shi, Z. J. (2004). J. Org. Chem. 69, 1429–1431. Web of Science CSD CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sodeoka, M., Sampe, R., Kojima, S., Baba, Y., Usui, T., Ueda, K. & Osada, H. (2001). J. Med. Chem. 44, 3216–3222. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. (2009). publCIF. In preparation. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
4-hydroxy-5H-furan-2-one (Tetronic acid) form a subclass of β-hydroxybutenolides with the generic structure (Haynes & Plimmer, 1960). The best known members of this family are vitamin C (ascorbic acid) and pennicillic acid. A great number of these compounds and their metabolites are found in many natural products, which exhibit a wide array of biological properties (Sodeoka et al., 2001). In the present study, the title comound (I) has been determined as product of double-molecular ring closure of monochloroacetic acid which is halo-substituted tetronic acid.
The molecular structure is depicted in Fig. 1. Bond lengths and angles are in good agreement with previous reported for similar compounds (Ma et al., 2004). The crystal structure is stabilized by O—H···O hydrogen bonding and the molecules are linked in an infinite chain along the c axis, with graph-set motifs C(6) through O— H··· O hydrogen bonds (Bernstein et al., 1995) (Fig. 2, Table 1).