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

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ISSN: 2056-9890

Oxonium 2-carb­­oxy-3-(2-fur­yl)acrylate

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: quzr@seu.edu.cn

(Received 27 April 2009; accepted 12 May 2009; online 20 May 2009)

In the title compound, H3O+·C8H5O5, neighbouring cations and anions are linked by O—H⋯O hydrogen bonds, forming a one-dimensional chain framework along [001]. The crystal structure is further stabilized by ππ inter­actions, with centroid–centroid distances of 3.734 (3) Å.

Related literature

For the synthesis of β-amino­acids as precursors of novel biologically active compounds, see: O'Callaghan, et al. (1998[O'Callaghan, C. N., McMurry, T. B. H., O'Brien, J. E. & Draper, S. M. (1998). J. Chem. Res. (S), pp. 732-733.]); Cohen et al. (2002[Cohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett. 43, 1977-1981.]); Zeller et al. (1965[Zeller, E. A., Ramachander, G., Fleisher, G. A., Ishimaru, T. & Zeller, V. (1965). Biochem. J. 95, 262-269.]).

[Scheme 1]

Experimental

Crystal data
  • H3O+·C8H5O5

  • Mr = 200.14

  • Monoclinic, P 21 /c

  • a = 13.664 (3) Å

  • b = 8.7518 (18) Å

  • c = 7.4664 (15) Å

  • β = 99.13 (3)°

  • V = 881.5 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 293 K

  • 0.50 × 0.45 × 0.15 mm

Data collection
  • Rigaku SCXmini diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.935, Tmax = 0.980

  • 7954 measured reflections

  • 1727 independent reflections

  • 1406 reflections with I > 2σ(I)

  • Rint = 0.030

Refinement
  • R[F2 > 2σ(F2)] = 0.071

  • wR(F2) = 0.218

  • S = 1.06

  • 1727 reflections

  • 128 parameters

  • H-atom parameters constrained

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.75 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1WB⋯O4i 0.85 2.58 3.044 (4) 115
O1W—H1WA⋯O3i 0.85 2.42 3.188 (4) 150
O1W—H1WC⋯O4ii 0.85 2.48 3.201 (4) 143
O2—H2A⋯O4iii 0.82 1.74 2.552 (3) 169
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x, y, z+1; (iii) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

2-[(Furan-2-yl)methylene]malonic acid is a important bicarboxylic acid widely used in coordination chemistry and as an intermediate product in the synthesis of β-aminoacids. Recently, there has been an increased interest in the enantiomeric preparation of β-aminoacids as precursors for the synthesis of novel biologically active compounds (O'Callaghan et al., 1998; Cohen et al., 2002; Zeller et al., 1965). We report here the crystal structure of the title compound, which was prepared by the reaction of furan-2-carbaldehyde and malonic acid.

The asymmetric unit of the title compound (Fig.1) consists of a 2-[(furan-2-yl)methylene]malonate anion and a oxonium cation. The values of the C–O bond lengths in the carboxylic groups are consistent with a single bond character of the C8–O2 bond (1.308 (4)Å) and with a delocalized double bond character for the C7–O4 and C7–O5 bonds (1.262 (4) and 1.240 (4) Å, respectively). In the crystal packing (Fig. 2), classical intermolecular O—H···O hydrogen bonds connect neighbouring cations and anions, resulting in a one-dimensional chain framework along the c axis (Table 1). The crystal structure is further stabilized by ππ stacking interactions (Table 2) involving adjacent furane rings.

Related literature top

For the synthesis of β-aminoacids as precursors of novel biologically active compounds, see: O'Callaghan, et al. (1998); Cohen et al. (2002); Zeller et al. (1965).

Experimental top

A mixture of furan-2-carbaldehyde (0.5 mol, 0.48 g) and malonic acid (0.5 mol, 0.52 g) in ethanol (20 ml) was added in a flask and refluxed for 24 h. The resulting precipitate was separated and dissolved in an ethanol/water (5:1 v/v). Colourless single crystals of the title compound suitable for X-ray analysis were obtained on slow evaporation of the solvents over a period of 48 h.

Refinement top

The H atoms bound to O atoms were located in a difference Fourier map and refined with O—H = 0.82-0.85 Å and Uiso(H) = 1.5Uiso(O). All other H atoms were placed geometrically and allowed, with C—H = 0.93 Å and Uiso(H) = 1.2Uiso(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines.
Oxonium 2-carboxy-3-(2-furyl)acrylate top
Crystal data top
H3O+·C8H5O5F(000) = 416
Mr = 200.14Dx = 1.508 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1406 reflections
a = 13.664 (3) Åθ = 3.1–27.4°
b = 8.7518 (18) ŵ = 0.13 mm1
c = 7.4664 (15) ÅT = 293 K
β = 99.13 (3)°Prism, colourless
V = 881.5 (3) Å30.50 × 0.45 × 0.15 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
1727 independent reflections
Radiation source: fine-focus sealed tube1406 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 3.0°
CCD profile fitting scansh = 1616
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1010
Tmin = 0.935, Tmax = 0.980l = 99
7954 measured reflections
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)] = 0.071H-atom parameters constrained
wR(F2) = 0.218 w = 1/[σ2(Fo2) + (0.1228P)2 + 1.0867P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1727 reflectionsΔρmax = 0.46 e Å3
128 parametersΔρmin = 0.75 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0014 (2)
Crystal data top
H3O+·C8H5O5V = 881.5 (3) Å3
Mr = 200.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.664 (3) ŵ = 0.13 mm1
b = 8.7518 (18) ÅT = 293 K
c = 7.4664 (15) Å0.50 × 0.45 × 0.15 mm
β = 99.13 (3)°
Data collection top
Rigaku SCXmini
diffractometer
1727 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1406 reflections with I > 2σ(I)
Tmin = 0.935, Tmax = 0.980Rint = 0.030
7954 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0710 restraints
wR(F2) = 0.218H-atom parameters constrained
S = 1.06Δρmax = 0.46 e Å3
1727 reflectionsΔρmin = 0.75 e Å3
128 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6364 (2)0.3648 (4)0.3879 (4)0.0326 (7)
C20.6705 (3)0.2258 (4)0.3518 (5)0.0471 (9)
H20.73340.20210.32750.057*
C30.5905 (3)0.1220 (4)0.3582 (6)0.0552 (10)
H30.59180.01680.34080.066*
C40.5149 (3)0.2026 (5)0.3932 (6)0.0548 (10)
H40.45300.16260.40320.066*
C50.6780 (2)0.5157 (3)0.4112 (4)0.0316 (7)
H50.63930.58940.45620.038*
C60.7666 (2)0.5621 (3)0.3751 (4)0.0294 (7)
C70.8392 (2)0.4604 (3)0.3007 (4)0.0281 (7)
C80.8008 (2)0.7221 (3)0.4080 (4)0.0299 (7)
O10.53944 (18)0.3521 (3)0.4129 (4)0.0502 (7)
O20.73994 (16)0.8126 (3)0.4760 (3)0.0389 (6)
H2A0.76940.89020.51530.058*
O30.88184 (17)0.7637 (3)0.3750 (3)0.0436 (7)
O40.84296 (16)0.4683 (2)0.1332 (3)0.0354 (6)
O50.89313 (18)0.3763 (3)0.4078 (3)0.0431 (6)
O1W0.9457 (2)0.4115 (3)0.7823 (4)0.0579 (8)
H1WC0.94630.41300.89630.087*
H1WA0.97970.33620.75490.087*
H1WB0.97030.49410.74950.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0310 (16)0.0324 (16)0.0356 (16)0.0014 (12)0.0094 (12)0.0014 (12)
C20.0446 (19)0.0367 (19)0.059 (2)0.0089 (15)0.0065 (16)0.0065 (16)
C30.068 (3)0.0307 (18)0.064 (2)0.0096 (18)0.001 (2)0.0026 (17)
C40.050 (2)0.048 (2)0.067 (3)0.0196 (18)0.0112 (18)0.0031 (19)
C50.0362 (17)0.0269 (15)0.0333 (15)0.0027 (12)0.0106 (12)0.0005 (12)
C60.0336 (16)0.0230 (14)0.0319 (15)0.0023 (12)0.0062 (12)0.0003 (11)
C70.0301 (15)0.0205 (13)0.0344 (16)0.0016 (11)0.0074 (12)0.0002 (11)
C80.0331 (16)0.0250 (14)0.0318 (15)0.0008 (12)0.0061 (12)0.0013 (12)
O10.0416 (14)0.0451 (15)0.0675 (17)0.0090 (11)0.0199 (12)0.0047 (12)
O20.0382 (12)0.0280 (11)0.0521 (14)0.0001 (9)0.0120 (10)0.0121 (10)
O30.0409 (13)0.0333 (12)0.0602 (16)0.0059 (10)0.0195 (11)0.0077 (11)
O40.0447 (13)0.0290 (12)0.0352 (12)0.0061 (9)0.0149 (9)0.0025 (9)
O50.0481 (14)0.0401 (13)0.0397 (12)0.0148 (11)0.0030 (10)0.0027 (10)
O1W0.0586 (17)0.0583 (17)0.0589 (17)0.0026 (14)0.0162 (13)0.0010 (13)
Geometric parameters (Å, º) top
C1—C21.345 (5)C6—C81.485 (4)
C1—O11.372 (4)C6—C71.503 (4)
C1—C51.437 (4)C7—O51.240 (4)
C2—C31.428 (6)C7—O41.262 (4)
C2—H20.9300C8—O31.226 (4)
C3—C41.311 (6)C8—O21.308 (4)
C3—H30.9300O2—H2A0.8200
C4—O11.352 (5)O1W—H1WC0.8500
C4—H40.9300O1W—H1WA0.8500
C5—C61.344 (4)O1W—H1WB0.8500
C5—H50.9300
C2—C1—O1109.0 (3)C5—C6—C8121.5 (3)
C2—C1—C5135.4 (3)C5—C6—C7124.3 (3)
O1—C1—C5115.5 (3)C8—C6—C7114.3 (2)
C1—C2—C3106.1 (3)O5—C7—O4123.9 (3)
C1—C2—H2126.9O5—C7—C6118.2 (3)
C3—C2—H2126.9O4—C7—C6117.8 (3)
C4—C3—C2107.2 (3)O3—C8—O2123.2 (3)
C4—C3—H3126.4O3—C8—C6121.1 (3)
C2—C3—H3126.4O2—C8—C6115.6 (3)
C3—C4—O1110.7 (3)C4—O1—C1107.0 (3)
C3—C4—H4124.7C8—O2—H2A109.5
O1—C4—H4124.7H1WC—O1W—H1WA109.5
C6—C5—C1127.2 (3)H1WC—O1W—H1WB109.5
C6—C5—H5116.4H1WA—O1W—H1WB109.5
C1—C5—H5116.4
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O4i0.852.583.044 (4)115
O1W—H1WA···O3i0.852.423.188 (4)150
O1W—H1WC···O4ii0.852.483.201 (4)143
O2—H2A···O4iii0.821.742.552 (3)169
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y, z+1; (iii) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaH3O+·C8H5O5
Mr200.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.664 (3), 8.7518 (18), 7.4664 (15)
β (°) 99.13 (3)
V3)881.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.50 × 0.45 × 0.15
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.935, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
7954, 1727, 1406
Rint0.030
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.071, 0.218, 1.06
No. of reflections1727
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.75

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O4i0.852.583.044 (4)115.2
O1W—H1WA···O3i0.852.423.188 (4)150.2
O1W—H1WC···O4ii0.852.483.201 (4)143.2
O2—H2A···O4iii0.821.742.552 (3)168.7
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y, z+1; (iii) x, y+3/2, z+1/2.
π-π stacking interactions ( α is the dihedral angle between the planes, DCC is the length of the CC vector (centroid-to-centroid), τ is the angle subtended by the plane normal to CC. Cg1 is the centroid of the O1–C1/C4 ring) top
Group 1Group 2αDCC /Åτ
Cg1Cg1i16.423.734 (3)19.96
Symmetry code: (i) x, 1/2-y, -1/2+z
 

Acknowledgements

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

References

First citationCohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett. 43, 1977–1981.  Web of Science CrossRef CAS Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationO'Callaghan, C. N., McMurry, T. B. H., O'Brien, J. E. & Draper, S. M. (1998). J. Chem. Res. (S), pp. 732–733.  Web of Science CrossRef Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZeller, E. A., Ramachander, G., Fleisher, G. A., Ishimaru, T. & Zeller, V. (1965). Biochem. J. 95, 262–269.  PubMed CAS Web of Science Google Scholar

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ISSN: 2056-9890
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