4-Ethoxy­carbonyl-3-furoic acid

Parkin, A.; Adam, M.; Harte, S.M.; Kennedy, J.L.; Wilson, C.C.

doi:10.1107/S1600536806004429

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 3| March 2006| Pages o987-o989

https://doi.org/10.1107/S1600536806004429

4-Ethoxycarbonyl-3-furoic acid

Andrew Parkin,^a ^* Martin Adam,^a Suzanne M. Harte,^a Jennifer L. Kennedy ^b ‡ and Chick C. Wilson ^a

^aWestCHEM Research School, Department of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, Scotland, and ^bBearsden Academy, Morven Road, Bearsden, Glasgow G61 3SU, Scotland
^*Correspondence e-mail: a.parkin@chem.gla.ac.uk

(Received 1 February 2006; accepted 6 February 2006; online 10 February 2006)

The structure of 4-ethoxycarbonyl-3-furoic acid, C₈H₈O₅, has been determined at 100 K.

Comment

The title compound, (I), represents the first example of a crystal structure of a mono-ester of furoic acid. Previous related crystal structures observed in the Cambridge Structural Database (CSD, Version 5.26; Allen, 2002 ) include the cyclohexane (CSD refcode CIHNIQ; Baldwin et al., 1997 ) and methyl (CSD refcode FURCAM; Okada et al., 1971 ) diesters, and the diacid (CSD refcode FURDCB and derivatives), although there has been some discussion as to the correct space group of this compound (Williams & Rundle, 1964 ; Semmingsen et al., 1986 ).

The molecular structure of the title compound is essentially flat, with all the non-H atoms coplanar. No intermolecular hydrogen bonding is observed, although there are a number of non-classical C—H⋯O interactions observed between molecules. The single hydrogen bond observed in the title structure is an intramolecular O11—H11⋯O71 hydrogen bond (Table 2 and Fig. 1), lying approximately perpendicular to the (021) plane. Much of our interest in such materials lies in the possibility of hydrogen-bond disorder. The difference Fourier map (Fig. 2) shows that no disorder is observed in this hydrogen bond at this temperature; there is also no disorder observed in the hydrogen bond at higher temperatures, as a difference Fourier map of the hydrogen bond from a data set collected at 293 K on the same crystal shows (Fig. 2). The data for the 293 K structure have been deposited with the Cambridge Crystallographic Data Centre.

The packing of the molecule in this structure is layered, with each layer having rows of the title molecule in alternating directions (Fig. 3a). The layers are then superimposed on each other, with alternating rows lying on top of one another (Fig. 3b). These layers are quite distinct throughout the structure (Fig. 3c).

Figure 1
The molecular structure of (I)

observed in the crystal structure, showing anisotropic displacement parameter ellipsoids and the numbering scheme used. The displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Difference Fourier map sections through the intramolecular hydrogen bond in the same crystal at (a) 100 K and (b) 293 K.

Figure 3
Packing diagrams showing (a) the layered structure of the molecule, (b) how the layers fit together and (c) a side view of the layers.

Experimental

The title material was prepared from diethyl-3,4-furandicarboxylate after exposure to moist air, the crystals being observed floating in the parent material a few days after exposure.

Crystal data

C₈H₈O₅
M_r = 184.15
Triclinic, $[P \overline 1]$
a = 7.0424 (11) Å
b = 7.4653 (12) Å
c = 9.0724 (14) Å
α = 111.236 (4)°
β = 93.207 (5)°
γ = 109.601 (4)°
V = 410.18 (11) Å³
Z = 2
D_x = 1.491 Mg m⁻³
Mo Kα radiation
Cell parameters from 2341 reflections
θ = 2–31°
μ = 0.13 mm⁻¹
T = 100 K
Block, colourless
0.50 × 0.40 × 0.20 mm

Data collection

Brüker APEX2 CCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Bruker, 1996 )T_min = 0.91, T_max = 0.98
5968 measured reflections
2461 independent reflections
1763 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 30.7°
h = −10 → 9
k = −10 → 10
l = −13 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.098
S = 0.93
2461 reflections
150 parameters
All H-atom parameters refined
w = 1/[σ²(F²) + 0.05]
(Δ/σ)_max < 0.001
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C6—C2	1.4527 (18)
C6—C5	1.3621 (19)
C6—C7	1.4669 (19)
C2—C1	1.4874 (18)
C2—C3	1.3557 (19)
C1—O12	1.2182 (17)
C1—O11	1.3327 (17)
C3—O4	1.3713 (16)
O4—C5	1.3634 (17)
C7—O8	1.3311 (16)
C7—O71	1.2289 (16)
O8—C9	1.4635 (17)
C9—C10	1.506 (2)

C2—C6—C5	106.07 (12)
C2—C6—C7	129.92 (12)
C5—C6—C7	124.01 (12)
C6—C2—C1	132.51 (12)
C6—C2—C3	105.77 (11)
C1—C2—C3	121.70 (12)
C2—C1—O12	121.56 (12)
C2—C1—O11	118.18 (12)
O12—C1—O11	120.26 (12)
C2—C3—O4	110.72 (12)
C3—O4—C5	106.99 (10)
O4—C5—C6	110.44 (12)
C6—C7—O8	111.88 (11)
C6—C7—O71	124.32 (12)
O8—C7—O71	123.79 (12)
C7—O8—C9	116.73 (11)
O8—C9—C10	107.16 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O71	0.94 (2)	1.70 (2)	2.6267 (16)	172 (2)

All H atoms were found in difference density syntheses and were refined isotropically without restraints.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: MERCURY (Bruno et al., 2002 ), ORTEP-3 for Windows (Farrugia, 1997 ) and WinGX (Farrugia, 1999 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806004429/hg6304sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806004429/hg6304Isup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: Mercury (Bruno et al., 2002), ORTEP-3 for Windows (Farrugia, 1997) and WinGX (Farrugia, 1999); software used to prepare material for publication: CRYSTALS.

4-ethoxycarbonyl-3-furoic acid top

Crystal data top

C₈H₈O₅	Z = 2
M_r = 184.15	F(000) = 192
Triclinic, P1	D_x = 1.491 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0424 (11) Å	Cell parameters from 2341 reflections
b = 7.4653 (12) Å	θ = 2–31°
c = 9.0724 (14) Å	µ = 0.13 mm⁻¹
α = 111.236 (4)°	T = 100 K
β = 93.207 (5)°	Block, colourless
γ = 109.601 (4)°	0.50 × 0.40 × 0.20 mm
V = 410.18 (11) Å³

Data collection top

Brüker APEX2 CCD diffractometer	1763 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 30.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1996)	h = −10→9
T_min = 0.91, T_max = 0.98	k = −10→10
5968 measured reflections	l = −13→12
2461 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	All H-atom parameters refined
wR(F²) = 0.098	w = 1/[σ²(F²) + 0.05]
S = 0.93	(Δ/σ)_max = 0.000192
2461 reflections	Δρ_max = 0.54 e Å⁻³
150 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C6	0.70076 (19)	0.1024 (2)	0.41479 (16)	0.0154
C2	0.65366 (19)	−0.1080 (2)	0.29745 (16)	0.0153
C1	0.6760 (2)	−0.2927 (2)	0.31147 (17)	0.0178
O12	0.62826 (16)	−0.45688 (15)	0.19436 (13)	0.0236
O11	0.74836 (16)	−0.27534 (16)	0.45702 (13)	0.0216
C3	0.5715 (2)	−0.1164 (2)	0.15520 (17)	0.0178
O4	0.56311 (16)	0.07133 (15)	0.17399 (12)	0.0209
C5	0.6426 (2)	0.2022 (2)	0.33238 (16)	0.0191
C7	0.7916 (2)	0.1998 (2)	0.58785 (16)	0.0164
O8	0.81253 (15)	0.39804 (15)	0.65420 (12)	0.0205
C9	0.9021 (2)	0.5115 (2)	0.82699 (18)	0.0227
C10	0.9139 (3)	0.7307 (2)	0.8735 (2)	0.0276
O71	0.84080 (15)	0.10958 (15)	0.66351 (12)	0.0199
H31	0.517 (2)	−0.230 (3)	0.049 (2)	0.022 (4)*
H51	0.654 (2)	0.346 (3)	0.3662 (19)	0.019 (4)*
H91	1.036 (3)	0.504 (3)	0.844 (2)	0.024 (4)*
H92	0.811 (2)	0.442 (3)	0.881 (2)	0.022 (4)*
H101	0.976 (3)	0.819 (3)	0.990 (3)	0.044 (6)*
H102	1.010 (3)	0.804 (3)	0.817 (2)	0.039 (5)*
H103	0.780 (3)	0.733 (3)	0.857 (2)	0.035 (5)*
H11	0.781 (3)	−0.143 (3)	0.538 (3)	0.052 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C6	0.0192 (6)	0.0132 (6)	0.0130 (6)	0.0059 (5)	0.0026 (5)	0.0048 (5)
C2	0.0190 (6)	0.0122 (6)	0.0153 (6)	0.0069 (5)	0.0036 (5)	0.0052 (5)
C1	0.0187 (6)	0.0151 (6)	0.0208 (7)	0.0075 (5)	0.0033 (5)	0.0080 (5)
O12	0.0316 (5)	0.0137 (5)	0.0225 (6)	0.0105 (4)	0.0007 (4)	0.0032 (4)
O11	0.0318 (5)	0.0168 (5)	0.0190 (5)	0.0121 (4)	0.0009 (4)	0.0082 (4)
C3	0.0238 (7)	0.0137 (6)	0.0160 (7)	0.0087 (5)	0.0040 (5)	0.0048 (5)
O4	0.0333 (5)	0.0165 (5)	0.0142 (5)	0.0118 (4)	0.0014 (4)	0.0062 (4)
C5	0.0288 (7)	0.0140 (6)	0.0137 (7)	0.0089 (5)	0.0021 (5)	0.0042 (5)
C7	0.0182 (6)	0.0132 (6)	0.0164 (7)	0.0055 (5)	0.0037 (5)	0.0047 (5)
O8	0.0296 (5)	0.0137 (5)	0.0147 (5)	0.0089 (4)	−0.0007 (4)	0.0022 (4)
C9	0.0266 (7)	0.0195 (7)	0.0145 (7)	0.0070 (6)	−0.0002 (6)	0.0012 (6)
C10	0.0299 (8)	0.0187 (7)	0.0251 (8)	0.0073 (6)	0.0049 (6)	0.0009 (6)
O71	0.0252 (5)	0.0178 (5)	0.0165 (5)	0.0091 (4)	−0.0006 (4)	0.0067 (4)

Geometric parameters (Å, º) top

C6—C2	1.4527 (18)	C5—H51	0.978 (16)
C6—C5	1.3621 (19)	C7—O8	1.3311 (16)
C6—C7	1.4669 (19)	C7—O71	1.2289 (16)
C2—C1	1.4874 (18)	O8—C9	1.4635 (17)
C2—C3	1.3557 (19)	C9—C10	1.506 (2)
C1—O12	1.2182 (17)	C9—H91	0.971 (17)
C1—O11	1.3327 (17)	C9—H92	0.957 (16)
O11—H11	0.94 (2)	C10—H101	1.00 (2)
C3—O4	1.3713 (16)	C10—H102	1.004 (19)
C3—H31	0.971 (17)	C10—H103	0.955 (19)
O4—C5	1.3634 (17)

C2—C6—C5	106.07 (12)	C6—C7—O8	111.88 (11)
C2—C6—C7	129.92 (12)	C6—C7—O71	124.32 (12)
C5—C6—C7	124.01 (12)	O8—C7—O71	123.79 (12)
C6—C2—C1	132.51 (12)	C7—O8—C9	116.73 (11)
C6—C2—C3	105.77 (11)	O8—C9—C10	107.16 (12)
C1—C2—C3	121.70 (12)	O8—C9—H91	107.5 (10)
C2—C1—O12	121.56 (12)	C10—C9—H91	112.9 (10)
C2—C1—O11	118.18 (12)	O8—C9—H92	106.8 (10)
O12—C1—O11	120.26 (12)	C10—C9—H92	111.5 (10)
C1—O11—H11	113.3 (13)	H91—C9—H92	110.7 (14)
C2—C3—O4	110.72 (12)	C9—C10—H101	112.0 (12)
C2—C3—H31	131.4 (10)	C9—C10—H102	111.4 (11)
O4—C3—H31	117.8 (10)	H101—C10—H102	103.1 (15)
C3—O4—C5	106.99 (10)	C9—C10—H103	111.0 (11)
O4—C5—C6	110.44 (12)	H101—C10—H103	106.1 (15)
O4—C5—H51	117.8 (10)	H102—C10—H103	112.9 (16)
C6—C5—H51	131.7 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O71	0.94 (2)	1.70 (2)	2.6267 (16)	172 (2)

Footnotes

‡Also affiliated to WestCHEM Research School, Department of Chemistry, University of Glasgow, University Avenue Glasgow, G12 8QQ, Scotland

Acknowledgements

The authors thank the Nuffield Foundation for funding for JLK.

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