PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2266.
Published online 2010 August 11. doi:  10.1107/S1600536810031119
PMCID: PMC3007883

5-(Hy­droxy­meth­yl)furan-2-carbaldehyde

Abstract

The title compound (HMF), C6H6O3, is one of the products of acid-catalyzed dehydration of high-fructose corn syrup, and has been shown to be toxic to honey bees. The compound was crystallized at 276 K, and it was found that the two independent mol­ecules in the asymmetric unit form an infinite O—H(...)O hydrogen-bonding chain that is linked into a three-dimensional network structure by weak inter­molecular C—H(...)O contacts.

Related literature

For the formation of HMF from high-fructose corn syrup, see: Le Blanc et al. (2009 [triangle]), and the story subsequently reported in Chemical & Engineering News by Kemsley (2009 [triangle]). The effect of HMF on honey bees was studied by Bailey (1966 [triangle]); for the mechanism of HMF formation from sugars, see: Antal et al. (1990 [triangle]); Haworth & Jones (1944 [triangle]); Ermolaeva & Sapronova (1982 [triangle]). For the effect of HMF on DNA, see: Durling et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2266-scheme1.jpg

Experimental

Crystal data

  • C6H6O3
  • M r = 126.11
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2266-efi1.jpg
  • a = 15.9126 (17) Å
  • b = 5.6166 (6) Å
  • c = 13.1722 (14) Å
  • β = 90.770 (2)°
  • V = 1177.2 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 125 K
  • 0.22 × 0.19 × 0.14 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.975, T max = 0.984
  • 15720 measured reflections
  • 2933 independent reflections
  • 2246 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.089
  • S = 1.04
  • 2933 reflections
  • 169 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810031119/si2283sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031119/si2283Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).

supplementary crystallographic information

Comment

5-(Hydroxymethyl)-2-furancarboxaldehyde (Scheme 1), or, as it is more commonly referred to as 5-hydroxymethylfurfural, HMF, is formed by acid-catalyzed dehydration of sugars, most notably of D-fructose (Antal et al., 1990; Bailey, 1966; Ermolaeva & Sapronova, 1982; Haworth & Jones, 1944). It is present in many foods such as dried fruit, coffee, and bread, and especially in food that has been heated (Durling et al., 2009). HMF is also formed by acid-catalyzed degradation of high-fructose corn syrup that has been subject to heat. It is toxic to honey bees, which are fed high-fructose corn syrup by beekeepers to promote colony growth and when nectar sources are scarce (Kemsley, 2009; Le Blanc et al., 2009). The toxicity presents itself to bees as intestinal ulcerations, which lead to dysentery and, soon after, death. One study by Durling et al., (2009) has shown that HMF may damage DNA.

The asymmetric unit contains two independent unique molecules of HMF (Figure 1) which are hydrogen bonded into an infinite one-dimensional screw-like chain along the crystallographic b axis (Figure 2, Table 1). The hydroxymethyl oxygen O23 is both a hydrogen bond donor and acceptor. The aldehyde oxygen of one of the independent molecules, O11, acts as a hydrogen bond acceptor from the proton on O23 of the second independent molecule, D···A 2.701 (1) Å. The proton on the hydroxylmethyl oxygen of the first independent molecule, O13, acts as a hydrogen bond donor to the hydroxymethyl oxygen O23, D···A 2.734 (1) Å. The aldehyde oxygen of the second molecule, O21, is not involved in classical hydrogen bonding, however it is involved in C—H···O interactions. Five weak intermolecular C—H···O contacts (Table 1) link the screw-like hydrogen bonded chains into a three-dimensional network structure.

Experimental

5-Hydroxymethylfurfural was purchased from Aldrich and used without further purification. The compound was placed in a 276 K cold room until crystallization occurred. A crystal suitable for diffraction was selected and mounted in a nylon loop with Paratone-N cryoprotectant oil with a microscope in the cold room before being placed immediately in a 125 K coldstream on the diffractometer.

Refinement

A suitable crystal was mounted in a nylon loop with Paratone-N cryoprotectant oil and data was collected on a Bruker APEXII CCD platform diffractometer. The structure was solved using direct methods and standard difference map techniques, and was refined by full-matrix least-squares procedures on F2 with SHELXTL Version 6.14 (Sheldrick, 2008). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on carbon were included in calculated positions with distances C—H = 0.95 - 0.99 Å and were refined using a riding model, with Uiso(H) = 1.2Ueq(C). Hydrogen atoms on oxygen were refined semifreely with the help of a distance restraint d(O–H) = 0.84 Å, and Uiso(H) = 1.2Ueq(O).The extinction parameter (EXTI) refined to zero and was removed from the refinement.

Figures

Fig. 1.
A view of the two independent moleucles of HMF, with displacement ellipsoids shown at the 50% probability level. H atoms on carbon, except for the H atoms on the aldehydes, have been omitted for clarity.
Fig. 2.
A view of the one-dimensional hydrogen bonding chain formed by the two independent moleucles of HMF. H atoms on carbon have been omitted for clarity.

Crystal data

C6H6O3F(000) = 528
Mr = 126.11Dx = 1.423 Mg m3
Monoclinic, P21/cMelting point = 301–307 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 15.9126 (17) ÅCell parameters from 5970 reflections
b = 5.6166 (6) Åθ = 2.6–28.2°
c = 13.1722 (14) ŵ = 0.12 mm1
β = 90.770 (2)°T = 125 K
V = 1177.2 (2) Å3Block, colourless
Z = 80.22 × 0.19 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer2933 independent reflections
Radiation source: fine-focus sealed tube2246 reflections with I > 2σ(I)
graphiteRint = 0.042
[var phi] and ω scansθmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −21→21
Tmin = 0.975, Tmax = 0.984k = −7→7
15720 measured reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3118P] where P = (Fo2 + 2Fc2)/3
2933 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.25 e Å3
2 restraintsΔρmin = −0.21 e Å3

Special details

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)

xyzUiso*/Ueq
O111.11183 (6)0.07149 (19)0.62286 (8)0.0320 (2)
O120.94229 (6)0.19067 (16)0.61025 (7)0.0227 (2)
O130.77247 (6)0.02624 (17)0.68104 (8)0.0268 (2)
H13O0.7607 (10)0.125 (3)0.7278 (11)0.032*
O210.44841 (6)−0.14117 (17)0.33477 (7)0.0259 (2)
O220.38382 (5)0.01084 (15)0.52416 (6)0.01771 (19)
O230.25895 (6)−0.14054 (16)0.67299 (7)0.0229 (2)
H23O0.2152 (9)−0.064 (3)0.6587 (12)0.027*
C111.08966 (9)0.2796 (3)0.63013 (10)0.0278 (3)
H11A1.13210.39660.64010.033*
C121.00405 (9)0.3586 (2)0.62456 (10)0.0246 (3)
C130.96973 (10)0.5808 (3)0.62951 (10)0.0295 (3)
H13B0.99890.72690.63860.035*
C140.88169 (10)0.5496 (3)0.61829 (10)0.0290 (3)
H14A0.84020.67130.61890.035*
C150.86787 (8)0.3121 (2)0.60650 (10)0.0230 (3)
C160.79019 (9)0.1669 (3)0.59398 (10)0.0271 (3)
H16A0.74210.27430.58010.032*
H16B0.79640.06080.53450.032*
C210.44388 (8)0.0692 (2)0.35668 (10)0.0209 (3)
H21A0.46420.18030.30850.025*
C220.41029 (7)0.1641 (2)0.44951 (9)0.0187 (3)
C230.39749 (8)0.3945 (2)0.47805 (10)0.0220 (3)
H23B0.41110.53340.44050.026*
C240.35976 (8)0.3853 (2)0.57519 (10)0.0235 (3)
H24A0.34230.51720.61490.028*
C250.35344 (8)0.1518 (2)0.60018 (9)0.0186 (3)
C260.32435 (8)0.0284 (2)0.69336 (10)0.0215 (3)
H26A0.3726−0.05460.72570.026*
H26B0.30370.14860.74200.026*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O110.0247 (5)0.0384 (6)0.0327 (6)0.0042 (4)−0.0022 (4)0.0009 (5)
O120.0223 (5)0.0214 (5)0.0244 (5)0.0033 (4)−0.0016 (4)−0.0015 (4)
O130.0294 (5)0.0216 (5)0.0294 (5)0.0024 (4)0.0051 (4)−0.0041 (4)
O210.0299 (5)0.0234 (5)0.0244 (5)0.0013 (4)0.0036 (4)−0.0020 (4)
O220.0193 (4)0.0157 (4)0.0182 (4)0.0001 (3)0.0023 (3)0.0005 (3)
O230.0216 (5)0.0214 (5)0.0258 (5)0.0011 (4)0.0041 (4)0.0035 (4)
C110.0283 (7)0.0353 (8)0.0198 (7)−0.0048 (6)−0.0006 (5)−0.0007 (6)
C120.0294 (7)0.0252 (7)0.0191 (6)−0.0038 (5)0.0012 (5)−0.0004 (5)
C130.0409 (8)0.0235 (7)0.0244 (7)−0.0023 (6)0.0079 (6)−0.0018 (6)
C140.0377 (8)0.0245 (7)0.0251 (7)0.0083 (6)0.0092 (6)0.0022 (6)
C150.0264 (7)0.0251 (7)0.0176 (6)0.0081 (5)0.0022 (5)0.0011 (5)
C160.0254 (7)0.0320 (8)0.0238 (7)0.0056 (6)−0.0001 (5)−0.0014 (6)
C210.0186 (6)0.0233 (7)0.0210 (6)0.0006 (5)0.0012 (5)0.0037 (5)
C220.0162 (6)0.0192 (6)0.0206 (6)−0.0014 (5)0.0007 (5)0.0039 (5)
C230.0221 (6)0.0175 (6)0.0263 (7)0.0003 (5)0.0008 (5)0.0029 (5)
C240.0241 (7)0.0193 (6)0.0273 (7)0.0024 (5)0.0024 (5)−0.0026 (5)
C250.0164 (6)0.0194 (6)0.0200 (6)0.0019 (5)0.0003 (5)−0.0020 (5)
C260.0215 (6)0.0233 (6)0.0197 (6)0.0011 (5)0.0013 (5)−0.0014 (5)

Geometric parameters (Å, °)

O11—C111.2249 (18)C14—C151.360 (2)
O12—C151.3670 (15)C14—H14A0.9500
O12—C121.3732 (16)C15—C161.488 (2)
O13—C161.4239 (17)C16—H16A0.9900
O13—H13O0.850 (13)C16—H16B0.9900
O21—C211.2188 (16)C21—C221.4431 (17)
O22—C251.3698 (14)C21—H21A0.9500
O22—C221.3769 (14)C22—C231.3639 (18)
O23—C261.4312 (16)C23—C241.4217 (19)
O23—H23O0.838 (13)C23—H23B0.9500
C11—C121.434 (2)C24—C251.3561 (18)
C11—H11A0.9500C24—H24A0.9500
C12—C131.364 (2)C25—C261.4888 (18)
C13—C141.418 (2)C26—H26A0.9900
C13—H13B0.9500C26—H26B0.9900
C15—O12—C12106.27 (10)C15—C16—H16B109.0
C16—O13—H13O105.8 (11)H16A—C16—H16B107.8
C25—O22—C22105.96 (9)O21—C21—C22125.62 (12)
C26—O23—H23O107.5 (11)O21—C21—H21A117.2
O11—C11—C12124.46 (13)C22—C21—H21A117.2
O11—C11—H11A117.8C23—C22—O22110.37 (11)
C12—C11—H11A117.8C23—C22—C21129.96 (12)
C13—C12—O12110.41 (12)O22—C22—C21119.65 (11)
C13—C12—C11131.41 (14)C22—C23—C24106.27 (11)
O12—C12—C11118.17 (12)C22—C23—H23B126.9
C12—C13—C14106.13 (13)C24—C23—H23B126.9
C12—C13—H13B126.9C25—C24—C23106.68 (11)
C14—C13—H13B126.9C25—C24—H24A126.7
C15—C14—C13106.91 (13)C23—C24—H24A126.7
C15—C14—H14A126.5C24—C25—O22110.71 (11)
C13—C14—H14A126.5C24—C25—C26132.47 (12)
C14—C15—O12110.28 (12)O22—C25—C26116.75 (11)
C14—C15—C16133.06 (13)O23—C26—C25112.81 (10)
O12—C15—C16116.63 (11)O23—C26—H26A109.0
O13—C16—C15112.84 (11)C25—C26—H26A109.0
O13—C16—H16A109.0O23—C26—H26B109.0
C15—C16—H16A109.0C25—C26—H26B109.0
O13—C16—H16B109.0H26A—C26—H26B107.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O13—H13O···O23i0.85 (1)1.89 (1)2.7341 (13)175.(2)
O23—H23O···O11ii0.84 (1)1.87 (1)2.7006 (14)173.(2)
C14—H14A···O13iii0.952.413.3029 (17)156.
C21—H21A···O21iv0.952.563.4726 (15)160.
C23—H23B···O21iii0.952.383.3258 (16)175.
C24—H24A···O23iii0.952.463.3734 (16)160.
C26—H26A···O21v0.992.533.4639 (16)158.

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y−1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2283).

References

  • Antal, M. J. Jr, Mok, W. S. & Richards, G. N. (1990). Carbohydr. Res.199, 91–109. [PubMed]
  • Bailey, L. (1966). J. Apic. Res.5, 127–136.
  • Bruker (2007). APEX2, SADABS and SAINT BrukerAXS Inc., Madison, Wisconsin, USA.
  • Durling, L. J. K., Busk, L. & Hellman, B. E. (2009). Food Chem. Toxicol.47, 880–884. [PubMed]
  • Ermolaeva, G. A. & Sapronova, L. A. (1982). Sakh. Prom-st pp. 31–32.
  • Haworth, W. N. & Jones, W. G. M. (1944). J. Chem. Soc. pp. 667–670.
  • Kemsley, J. N. (2009). Chem. Eng. News, 87, 37.
  • Le Blanc, B. W., Eggleston, G., Sammataro, D., Cornett, C., Dufault, R., Deeby, T. & St Cyr, E. (2009). J. Agric. Food Chem.57, 7369–7376. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography