5-(Hy-droxy-meth-yl)furan-2-carbaldehyde.

The title compound (HMF), C(6)H(6)O(3), 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 mol-ecules in the asymmetric unit form an infinite O-H⋯O hydrogen-bonding chain that is linked into a three-dimensional network structure by weak inter-molecular C-H⋯O contacts.

Related literature

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

Experimental

Crystal data

C6H6O3

M = 126.11

Monoclinic,

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

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

C6H6O3	F(000) = 528
Mr = 126.11	Dx = 1.423 Mg m−3
Monoclinic, P21/c	Melting point = 301–307 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.9126 (17) Å	Cell parameters from 5970 reflections
b = 5.6166 (6) Å	θ = 2.6–28.2°
c = 13.1722 (14) Å	µ = 0.12 mm−1
β = 90.770 (2)°	T = 125 K
V = 1177.2 (2) Å3	Block, colourless
Z = 8	0.22 × 0.19 × 0.14 mm

Bruker APEXII CCD diffractometer	2933 independent reflections
Radiation source: fine-focus sealed tube	2246 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −21→21
Tmin = 0.975, Tmax = 0.984	k = −7→7
15720 measured reflections	l = −17→17

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

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.

	x	y	z	Uiso*/Ueq
O11	1.11183 (6)	0.07149 (19)	0.62286 (8)	0.0320 (2)
O12	0.94229 (6)	0.19067 (16)	0.61025 (7)	0.0227 (2)
O13	0.77247 (6)	0.02624 (17)	0.68104 (8)	0.0268 (2)
H13O	0.7607 (10)	0.125 (3)	0.7278 (11)	0.032*
O21	0.44841 (6)	−0.14117 (17)	0.33477 (7)	0.0259 (2)
O22	0.38382 (5)	0.01084 (15)	0.52416 (6)	0.01771 (19)
O23	0.25895 (6)	−0.14054 (16)	0.67299 (7)	0.0229 (2)
H23O	0.2152 (9)	−0.064 (3)	0.6587 (12)	0.027*
C11	1.08966 (9)	0.2796 (3)	0.63013 (10)	0.0278 (3)
H11A	1.1321	0.3966	0.6401	0.033*
C12	1.00405 (9)	0.3586 (2)	0.62456 (10)	0.0246 (3)
C13	0.96973 (10)	0.5808 (3)	0.62951 (10)	0.0295 (3)
H13B	0.9989	0.7269	0.6386	0.035*
C14	0.88169 (10)	0.5496 (3)	0.61829 (10)	0.0290 (3)
H14A	0.8402	0.6713	0.6189	0.035*
C15	0.86787 (8)	0.3121 (2)	0.60650 (10)	0.0230 (3)
C16	0.79019 (9)	0.1669 (3)	0.59398 (10)	0.0271 (3)
H16A	0.7421	0.2743	0.5801	0.032*
H16B	0.7964	0.0608	0.5345	0.032*
C21	0.44388 (8)	0.0692 (2)	0.35668 (10)	0.0209 (3)
H21A	0.4642	0.1803	0.3085	0.025*
C22	0.41029 (7)	0.1641 (2)	0.44951 (9)	0.0187 (3)
C23	0.39749 (8)	0.3945 (2)	0.47805 (10)	0.0220 (3)
H23B	0.4111	0.5334	0.4405	0.026*
C24	0.35976 (8)	0.3853 (2)	0.57519 (10)	0.0235 (3)
H24A	0.3423	0.5172	0.6149	0.028*
C25	0.35344 (8)	0.1518 (2)	0.60018 (9)	0.0186 (3)
C26	0.32435 (8)	0.0284 (2)	0.69336 (10)	0.0215 (3)
H26A	0.3726	−0.0546	0.7257	0.026*
H26B	0.3037	0.1486	0.7420	0.026*

	U11	U22	U33	U12	U13	U23
O11	0.0247 (5)	0.0384 (6)	0.0327 (6)	0.0042 (4)	−0.0022 (4)	0.0009 (5)
O12	0.0223 (5)	0.0214 (5)	0.0244 (5)	0.0033 (4)	−0.0016 (4)	−0.0015 (4)
O13	0.0294 (5)	0.0216 (5)	0.0294 (5)	0.0024 (4)	0.0051 (4)	−0.0041 (4)
O21	0.0299 (5)	0.0234 (5)	0.0244 (5)	0.0013 (4)	0.0036 (4)	−0.0020 (4)
O22	0.0193 (4)	0.0157 (4)	0.0182 (4)	0.0001 (3)	0.0023 (3)	0.0005 (3)
O23	0.0216 (5)	0.0214 (5)	0.0258 (5)	0.0011 (4)	0.0041 (4)	0.0035 (4)
C11	0.0283 (7)	0.0353 (8)	0.0198 (7)	−0.0048 (6)	−0.0006 (5)	−0.0007 (6)
C12	0.0294 (7)	0.0252 (7)	0.0191 (6)	−0.0038 (5)	0.0012 (5)	−0.0004 (5)
C13	0.0409 (8)	0.0235 (7)	0.0244 (7)	−0.0023 (6)	0.0079 (6)	−0.0018 (6)
C14	0.0377 (8)	0.0245 (7)	0.0251 (7)	0.0083 (6)	0.0092 (6)	0.0022 (6)
C15	0.0264 (7)	0.0251 (7)	0.0176 (6)	0.0081 (5)	0.0022 (5)	0.0011 (5)
C16	0.0254 (7)	0.0320 (8)	0.0238 (7)	0.0056 (6)	−0.0001 (5)	−0.0014 (6)
C21	0.0186 (6)	0.0233 (7)	0.0210 (6)	0.0006 (5)	0.0012 (5)	0.0037 (5)
C22	0.0162 (6)	0.0192 (6)	0.0206 (6)	−0.0014 (5)	0.0007 (5)	0.0039 (5)
C23	0.0221 (6)	0.0175 (6)	0.0263 (7)	0.0003 (5)	0.0008 (5)	0.0029 (5)
C24	0.0241 (7)	0.0193 (6)	0.0273 (7)	0.0024 (5)	0.0024 (5)	−0.0026 (5)
C25	0.0164 (6)	0.0194 (6)	0.0200 (6)	0.0019 (5)	0.0003 (5)	−0.0020 (5)
C26	0.0215 (6)	0.0233 (6)	0.0197 (6)	0.0011 (5)	0.0013 (5)	−0.0014 (5)

O11—C11	1.2249 (18)	C14—C15	1.360 (2)
O12—C15	1.3670 (15)	C14—H14A	0.9500
O12—C12	1.3732 (16)	C15—C16	1.488 (2)
O13—C16	1.4239 (17)	C16—H16A	0.9900
O13—H13O	0.850 (13)	C16—H16B	0.9900
O21—C21	1.2188 (16)	C21—C22	1.4431 (17)
O22—C25	1.3698 (14)	C21—H21A	0.9500
O22—C22	1.3769 (14)	C22—C23	1.3639 (18)
O23—C26	1.4312 (16)	C23—C24	1.4217 (19)
O23—H23O	0.838 (13)	C23—H23B	0.9500
C11—C12	1.434 (2)	C24—C25	1.3561 (18)
C11—H11A	0.9500	C24—H24A	0.9500
C12—C13	1.364 (2)	C25—C26	1.4888 (18)
C13—C14	1.418 (2)	C26—H26A	0.9900
C13—H13B	0.9500	C26—H26B	0.9900
C15—O12—C12	106.27 (10)	C15—C16—H16B	109.0
C16—O13—H13O	105.8 (11)	H16A—C16—H16B	107.8
C25—O22—C22	105.96 (9)	O21—C21—C22	125.62 (12)
C26—O23—H23O	107.5 (11)	O21—C21—H21A	117.2
O11—C11—C12	124.46 (13)	C22—C21—H21A	117.2
O11—C11—H11A	117.8	C23—C22—O22	110.37 (11)
C12—C11—H11A	117.8	C23—C22—C21	129.96 (12)
C13—C12—O12	110.41 (12)	O22—C22—C21	119.65 (11)
C13—C12—C11	131.41 (14)	C22—C23—C24	106.27 (11)
O12—C12—C11	118.17 (12)	C22—C23—H23B	126.9
C12—C13—C14	106.13 (13)	C24—C23—H23B	126.9
C12—C13—H13B	126.9	C25—C24—C23	106.68 (11)
C14—C13—H13B	126.9	C25—C24—H24A	126.7
C15—C14—C13	106.91 (13)	C23—C24—H24A	126.7
C15—C14—H14A	126.5	C24—C25—O22	110.71 (11)
C13—C14—H14A	126.5	C24—C25—C26	132.47 (12)
C14—C15—O12	110.28 (12)	O22—C25—C26	116.75 (11)
C14—C15—C16	133.06 (13)	O23—C26—C25	112.81 (10)
O12—C15—C16	116.63 (11)	O23—C26—H26A	109.0
O13—C16—C15	112.84 (11)	C25—C26—H26A	109.0
O13—C16—H16A	109.0	O23—C26—H26B	109.0
C15—C16—H16A	109.0	C25—C26—H26B	109.0
O13—C16—H16B	109.0	H26A—C26—H26B	107.8

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13O···O23i	0.85 (1)	1.89 (1)	2.7341 (13)	175.(2)
O23—H23O···O11ii	0.84 (1)	1.87 (1)	2.7006 (14)	173.(2)
C14—H14A···O13iii	0.95	2.41	3.3029 (17)	156.
C21—H21A···O21iv	0.95	2.56	3.4726 (15)	160.
C23—H23B···O21iii	0.95	2.38	3.3258 (16)	175.
C24—H24A···O23iii	0.95	2.46	3.3734 (16)	160.
C26—H26A···O21v	0.99	2.53	3.4639 (16)	158.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13O⋯O23i	0.85 (1)	1.89 (1)	2.7341 (13)	175 (2)
O23—H23O⋯O11ii	0.84 (1)	1.87 (1)	2.7006 (14)	173 (2)
C14—H14A⋯O13iii	0.95	2.41	3.3029 (17)	156
C21—H21A⋯O21iv	0.95	2.56	3.4726 (15)	160
C23—H23B⋯O21iii	0.95	2.38	3.3258 (16)	175
C24—H24A⋯O23iii	0.95	2.46	3.3734 (16)	160
C26—H26A⋯O21v	0.99	2.53	3.4639 (16)	158

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .