organic compounds
4-Ethoxycarbonyl-3-furoic acid
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
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 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 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).
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
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Refinement
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All H atoms were found in difference density syntheses and were refined isotropically without restraints.
Data collection: APEX2 (Bruker, 2005); cell 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
https://doi.org/10.1107/S1600536806004429/hg6304sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806004429/hg6304Isup2.hkl
Data collection: APEX2 (Bruker, 2005); cell
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.C8H8O5 | Z = 2 |
Mr = 184.15 | F(000) = 192 |
Triclinic, P1 | Dx = 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 |
Brüker APEX2 CCD diffractometer | 1763 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
φ and ω scans | θmax = 30.7°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1996) | h = −10→9 |
Tmin = 0.91, Tmax = 0.98 | k = −10→10 |
5968 measured reflections | l = −13→12 |
2461 independent reflections |
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 | Δρmax = 0.54 e Å−3 |
150 parameters | Δρmin = −0.48 e Å−3 |
0 restraints |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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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