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

Liang, W.-X.; Wang, G.; Qu, Z.-R.

doi:10.1107/S1600536809017760

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1310

doi:10.1107/S1600536809017760

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

Wen-Xian Liang,^a Gang Wang ^a and Zhi-Rong Qu ^a ^*

^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 π–π 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 ); Cohen et al. (2002 ); Zeller et al. (1965 ).

Experimental

Crystal data

H₃O⁺·C₈H₅O₅⁻
M_r = 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 ) T_min = 0.935, T_max = 0.980
7954 measured reflections
1727 independent reflections
1406 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.218
S = 1.06
1727 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017760/rz2321sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017760/rz2321Isup2.hkl

checkCIF report

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 π–π 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.

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

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	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⁺·C₈H₅O₅⁻	F(000) = 416
M_r = 200.14	D_x = 1.508 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1406 reflections
a = 13.664 (3) Å	θ = 3.1–27.4°
b = 8.7518 (18) Å	µ = 0.13 mm⁻¹
c = 7.4664 (15) Å	T = 293 K
β = 99.13 (3)°	Prism, colourless
V = 881.5 (3) Å³	0.50 × 0.45 × 0.15 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1727 independent reflections
Radiation source: fine-focus sealed tube	1406 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
CCD profile fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.935, T_max = 0.980	l = −9→9
7954 measured reflections

Refinement top

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)] = 0.071	H-atom parameters constrained
wR(F²) = 0.218	w = 1/[σ²(F_o²) + (0.1228P)² + 1.0867P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1727 reflections	Δρ_max = 0.46 e Å⁻³
128 parameters	Δρ_min = −0.75 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (2)

Crystal data top

H₃O⁺·C₈H₅O₅⁻	V = 881.5 (3) Å³
M_r = 200.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.664 (3) Å	µ = 0.13 mm⁻¹
b = 8.7518 (18) Å	T = 293 K
c = 7.4664 (15) Å	0.50 × 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)
T_min = 0.935, T_max = 0.980	R_int = 0.030
7954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.06	Δρ_max = 0.46 e Å⁻³
1727 reflections	Δρ_min = −0.75 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.6364 (2)	0.3648 (4)	0.3879 (4)	0.0326 (7)
C2	0.6705 (3)	0.2258 (4)	0.3518 (5)	0.0471 (9)
H2	0.7334	0.2021	0.3275	0.057*
C3	0.5905 (3)	0.1220 (4)	0.3582 (6)	0.0552 (10)
H3	0.5918	0.0168	0.3408	0.066*
C4	0.5149 (3)	0.2026 (5)	0.3932 (6)	0.0548 (10)
H4	0.4530	0.1626	0.4032	0.066*
C5	0.6780 (2)	0.5157 (3)	0.4112 (4)	0.0316 (7)
H5	0.6393	0.5894	0.4562	0.038*
C6	0.7666 (2)	0.5621 (3)	0.3751 (4)	0.0294 (7)
C7	0.8392 (2)	0.4604 (3)	0.3007 (4)	0.0281 (7)
C8	0.8008 (2)	0.7221 (3)	0.4080 (4)	0.0299 (7)
O1	0.53944 (18)	0.3521 (3)	0.4129 (4)	0.0502 (7)
O2	0.73994 (16)	0.8126 (3)	0.4760 (3)	0.0389 (6)
H2A	0.7694	0.8902	0.5153	0.058*
O3	0.88184 (17)	0.7637 (3)	0.3750 (3)	0.0436 (7)
O4	0.84296 (16)	0.4683 (2)	0.1332 (3)	0.0354 (6)
O5	0.89313 (18)	0.3763 (3)	0.4078 (3)	0.0431 (6)
O1W	0.9457 (2)	0.4115 (3)	0.7823 (4)	0.0579 (8)
H1WC	0.9463	0.4130	0.8963	0.087*
H1WA	0.9797	0.3362	0.7549	0.087*
H1WB	0.9703	0.4941	0.7495	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0310 (16)	0.0324 (16)	0.0356 (16)	−0.0014 (12)	0.0094 (12)	0.0014 (12)
C2	0.0446 (19)	0.0367 (19)	0.059 (2)	0.0089 (15)	0.0065 (16)	−0.0065 (16)
C3	0.068 (3)	0.0307 (18)	0.064 (2)	−0.0096 (18)	0.001 (2)	−0.0026 (17)
C4	0.050 (2)	0.048 (2)	0.067 (3)	−0.0196 (18)	0.0112 (18)	−0.0031 (19)
C5	0.0362 (17)	0.0269 (15)	0.0333 (15)	0.0027 (12)	0.0106 (12)	−0.0005 (12)
C6	0.0336 (16)	0.0230 (14)	0.0319 (15)	0.0023 (12)	0.0062 (12)	−0.0003 (11)
C7	0.0301 (15)	0.0205 (13)	0.0344 (16)	−0.0016 (11)	0.0074 (12)	0.0002 (11)
C8	0.0331 (16)	0.0250 (14)	0.0318 (15)	0.0008 (12)	0.0061 (12)	−0.0013 (12)
O1	0.0416 (14)	0.0451 (15)	0.0675 (17)	−0.0090 (11)	0.0199 (12)	−0.0047 (12)
O2	0.0382 (12)	0.0280 (11)	0.0521 (14)	0.0001 (9)	0.0120 (10)	−0.0121 (10)
O3	0.0409 (13)	0.0333 (12)	0.0602 (16)	−0.0059 (10)	0.0195 (11)	−0.0077 (11)
O4	0.0447 (13)	0.0290 (12)	0.0352 (12)	0.0061 (9)	0.0149 (9)	0.0025 (9)
O5	0.0481 (14)	0.0401 (13)	0.0397 (12)	0.0148 (11)	0.0030 (10)	0.0027 (10)
O1W	0.0586 (17)	0.0583 (17)	0.0589 (17)	−0.0026 (14)	0.0162 (13)	0.0010 (13)

Geometric parameters (Å, º) top

C1—C2	1.345 (5)	C6—C8	1.485 (4)
C1—O1	1.372 (4)	C6—C7	1.503 (4)
C1—C5	1.437 (4)	C7—O5	1.240 (4)
C2—C3	1.428 (6)	C7—O4	1.262 (4)
C2—H2	0.9300	C8—O3	1.226 (4)
C3—C4	1.311 (6)	C8—O2	1.308 (4)
C3—H3	0.9300	O2—H2A	0.8200
C4—O1	1.352 (5)	O1W—H1WC	0.8500
C4—H4	0.9300	O1W—H1WA	0.8500
C5—C6	1.344 (4)	O1W—H1WB	0.8500
C5—H5	0.9300

C2—C1—O1	109.0 (3)	C5—C6—C8	121.5 (3)
C2—C1—C5	135.4 (3)	C5—C6—C7	124.3 (3)
O1—C1—C5	115.5 (3)	C8—C6—C7	114.3 (2)
C1—C2—C3	106.1 (3)	O5—C7—O4	123.9 (3)
C1—C2—H2	126.9	O5—C7—C6	118.2 (3)
C3—C2—H2	126.9	O4—C7—C6	117.8 (3)
C4—C3—C2	107.2 (3)	O3—C8—O2	123.2 (3)
C4—C3—H3	126.4	O3—C8—C6	121.1 (3)
C2—C3—H3	126.4	O2—C8—C6	115.6 (3)
C3—C4—O1	110.7 (3)	C4—O1—C1	107.0 (3)
C3—C4—H4	124.7	C8—O2—H2A	109.5
O1—C4—H4	124.7	H1WC—O1W—H1WA	109.5
C6—C5—C1	127.2 (3)	H1WC—O1W—H1WB	109.5
C6—C5—H5	116.4	H1WA—O1W—H1WB	109.5
C1—C5—H5	116.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	H₃O⁺·C₈H₅O₅⁻
M_r	200.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.664 (3), 8.7518 (18), 7.4664 (15)
β (°)	99.13 (3)
V (Å³)	881.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.50 × 0.45 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.935, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	7954, 1727, 1406
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.218, 1.06
No. of reflections	1727
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O4ⁱ	0.85	2.58	3.044 (4)	115.2
O1W—H1WA···O3ⁱ	0.85	2.42	3.188 (4)	150.2
O1W—H1WC···O4ⁱⁱ	0.85	2.48	3.201 (4)	143.2
O2—H2A···O4ⁱⁱⁱ	0.82	1.74	2.552 (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 1	Group 2	α /°	DCC /Å	τ /°
Cg1	Cg1ⁱ	16.42	3.734 (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

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