Levulinic acid

Hachuła, B.; Polasz, A.; Dzida, M.; Nowak, M.; Kusz, J.

doi:10.1107/S1600536813021090

organic compounds

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Volume 69| Part 9| September 2013| Page o1406

doi:10.1107/S1600536813021090

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Levulinic acid

Barbara Hachuła,^a ^* Anna Polasz,^a Marzena Dzida,^a Maria Nowak ^b and Joachim Kusz ^b

^aInstitute of Chemistry, University of Silesia, 14 Bankowa Street, 40-006 Katowice, Poland, and ^bInstitute of Physics, University of Silesia, 4 Uniwersytecka Street, 40-007 Katowice, Poland
^*Correspondence e-mail: bhachula@o2.pl

(Received 19 July 2013; accepted 29 July 2013; online 10 August 2013)

The title compound (systematic name: 4-oxopentanoic acid), C₅H₈O₃, is close to planar (r.m.s. deviation = 0.0762 Å). In the crystal, the molecules interact via O—H⋯O hydrogen bonds in which the hydroxy O atoms act as donors and the ketone O atoms in adjacent molecules as acceptors, forming C(7) chains along [20-1].

Related literature

For uses of levulinic acid, see: Timokhin et al. (1999 ). For density functional and Møller–Plesset perturbation theory calculations for levulinic acid, see: Reichert et al. (2010 ); Kim et al. (2011 ). For typical bond lengths and angles, see: Allen et al. (1987 ); Borthwick (1980 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ); Etter et al. (1990 ). For background to the study, see: Flakus & Hachuła (2008 ); Flakus & Stachowska (2006 ).

Experimental

Crystal data

C₅H₈O₃
M_r = 116.11
Monoclinic, P 2₁ /c
a = 4.8761 (2) Å
b = 12.1025 (4) Å
c = 9.8220 (3) Å
β = 99.112 (3)°
V = 572.31 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.44 × 0.21 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ) T_min = 0.585, T_max = 1.000
7178 measured reflections
1013 independent reflections
902 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.06
1013 reflections
77 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.83 (2)	1.87 (2)	2.6977 (13)	176 (2)
Symmetry code: (i) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Wrocław, Poland.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813021090/ff2114sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021090/ff2114Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021090/ff2114Isup3.cml

checkCIF report

Comment top

Levulinic acid [systematic name: 4-oxopentanoic acid], (I), is a biogenic product of hexose acid hydrolysis at elevated temperatures that can be obtained from renewable resources. This functionalized carbon structure is widely used as chemical intermediate in the manufacture of fuel extenders, biodegradable polymers, herbicides, antibiotics, flavours and useful 5-carbon compounds (Timokhin et al., 1999; Reichert et al., 2010). Levulinic acid was investigated in a continuation of our studies of the IR spectra of hydrogen bonding in carboxylic acid derivatives (Flakus & Stachowska, 2006; Flakus & Hachuła, 2008). In order to study interactions occurring via hydrogen bonds and molecular packing in this compound, we have now determined the structure of (I) using diffraction data collected at 100 K.

The molecule of (I) is nearly planar (r.m.s. deviation of fitted all non-hydrogen atoms is equal to 0.0762 Å). The C—O (1.3373 (17) Å) and C=O (1.2044 (17) Å) bond distances differ slightly from the mean values given by Allen et al. (1987) for a variety of carboxylic acid groups (C—O 1.308 Å and C=O 1.214 Å). The bond-angle values at the central C atom in the carboxylic acid group of (I) (O2—C1—C2 124.51 (13) °; O1—C1—C2 112.48 (12)°) agree well with the mean values specified by Borthwick (1980) for a typical carboxylic acid group (O2—C1—C2 123 (2)°; O1—C1—C2 112 (2)°).

The monoclinic structure of (I) is composed of molecular sheets stacked along [101] direction. Atom O1 of the carboxylic group acts as a hydrogen-bond donor via H1 to carbonyl atom O3 belonging to the acetyl group of adjacent molecule. This interaction generates hydrogen-bonded chain with a graph-set motif of C(7) (Etter et al., 1990; Bernstein et al., 1995).

Related literature top

For uses of levulinic acid, see: Timokhin et al. (1999). For density functional and Møller–Plesset perturbation theory calculations for levulinic acid, see: Reichert et al. (2010); Kim et al. (2011). For typical bond lengths and angles, see: Allen et al. (1987); Borthwick (1980). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990). For background to the study, see: Flakus & Hachuła (2008); Flakus & Stachowska (2006).

Experimental top

Levulinic acid was purchased from Aldrich-Sigma. Crystals of title compound, suitable for X-ray diffraction, were selected directly from purchased sample.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme, showing 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure of (I), viewed along the a axis, showing the C(7) chains. The red lines indicate the hydrogen-bonding interactions. For the sake of clarity, all H atoms bonded to C atoms were omitted.

4-Oxopentanoic acid top

Crystal data top

C₅H₈O₃	F(000) = 248
M_r = 116.11	D_x = 1.348 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 303–306 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.8761 (2) Å	Cell parameters from 6623 reflections
b = 12.1025 (4) Å	θ = 3.4–34.5°
c = 9.8220 (3) Å	µ = 0.11 mm⁻¹
β = 99.112 (3)°	T = 100 K
V = 572.31 (3) Å³	Polyhedron, colourless
Z = 4	0.44 × 0.21 × 0.16 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 detector	1013 independent reflections
Radiation source: fine-focus sealed tube	902 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.0328 pixels mm^-1	θ_max = 25.1°, θ_min = 3.4°
ω scan	h = −5→4
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −14→14
T_min = 0.585, T_max = 1.000	l = −11→11
7178 measured reflections

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0797P)² + 0.128P] where P = (F_o² + 2F_c²)/3
1013 reflections	(Δ/σ)_max < 0.001
77 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₅H₈O₃	V = 572.31 (3) Å³
M_r = 116.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8761 (2) Å	µ = 0.11 mm⁻¹
b = 12.1025 (4) Å	T = 100 K
c = 9.8220 (3) Å	0.44 × 0.21 × 0.16 mm
β = 99.112 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 detector	1013 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	902 reflections with I > 2σ(I)
T_min = 0.585, T_max = 1.000	R_int = 0.034
7178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.23 e Å⁻³
1013 reflections	Δρ_min = −0.24 e Å⁻³
77 parameters

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2006). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O1	0.4194 (2)	0.16988 (8)	1.05179 (10)	0.0186 (3)
O2	0.3930 (2)	0.35384 (9)	1.06449 (12)	0.0286 (4)
O3	1.0589 (2)	0.31839 (8)	0.73324 (10)	0.0197 (3)
C1	0.4836 (3)	0.27238 (11)	1.01688 (14)	0.0159 (4)
C2	0.6782 (3)	0.27359 (12)	0.91177 (14)	0.0164 (4)
H2A	0.5932	0.2323	0.8288	0.020*
H2B	0.8537	0.2361	0.9505	0.020*
C3	0.7411 (3)	0.39098 (12)	0.87113 (14)	0.0170 (4)
H3A	0.5641	0.4276	0.8328	0.020*
H3B	0.8221	0.4319	0.9552	0.020*
C4	0.9364 (3)	0.39950 (11)	0.76733 (13)	0.0163 (4)
C5	0.9722 (3)	0.51213 (13)	0.70857 (16)	0.0242 (4)
H5A	1.1394	0.5130	0.6648	0.036*
H5B	0.9909	0.5671	0.7827	0.036*
H5C	0.8097	0.5299	0.6398	0.036*
H1	0.311 (4)	0.1766 (16)	1.108 (2)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0253 (6)	0.0186 (6)	0.0137 (5)	−0.0011 (4)	0.0093 (4)	0.0006 (4)
O2	0.0435 (7)	0.0204 (6)	0.0275 (7)	0.0010 (5)	0.0231 (5)	−0.0016 (5)
O3	0.0240 (6)	0.0218 (6)	0.0148 (5)	0.0025 (4)	0.0072 (4)	0.0001 (4)
C1	0.0200 (7)	0.0187 (7)	0.0088 (7)	−0.0002 (6)	0.0020 (5)	0.0003 (5)
C2	0.0202 (7)	0.0187 (8)	0.0112 (7)	0.0017 (5)	0.0050 (5)	−0.0009 (5)
C3	0.0218 (7)	0.0183 (8)	0.0118 (7)	−0.0002 (5)	0.0060 (6)	−0.0015 (5)
C4	0.0183 (7)	0.0207 (8)	0.0092 (7)	0.0000 (5)	0.0001 (5)	−0.0016 (6)
C5	0.0334 (8)	0.0224 (8)	0.0195 (8)	0.0008 (6)	0.0125 (6)	0.0036 (6)

Geometric parameters (Å, º) top

O1—C1	1.3373 (17)	C3—C4	1.5050 (19)
O1—H1	0.83 (2)	C3—H3A	0.9900
O2—C1	1.2044 (17)	C3—H3B	0.9900
O3—C4	1.2231 (17)	C4—C5	1.501 (2)
C1—C2	1.5092 (19)	C5—H5A	0.9800
C2—C3	1.520 (2)	C5—H5B	0.9800
C2—H2A	0.9900	C5—H5C	0.9800
C2—H2B	0.9900

C1—O1—H1	106.3 (14)	C4—C3—H3B	108.6
O2—C1—O1	123.01 (13)	C2—C3—H3B	108.6
O2—C1—C2	124.51 (13)	H3A—C3—H3B	107.6
O1—C1—C2	112.48 (12)	O3—C4—C5	122.14 (13)
C1—C2—C3	111.32 (12)	O3—C4—C3	121.30 (12)
C1—C2—H2A	109.4	C5—C4—C3	116.57 (12)
C3—C2—H2A	109.4	C4—C5—H5A	109.5
C1—C2—H2B	109.4	C4—C5—H5B	109.5
C3—C2—H2B	109.4	H5A—C5—H5B	109.5
H2A—C2—H2B	108.0	C4—C5—H5C	109.5
C4—C3—C2	114.68 (12)	H5A—C5—H5C	109.5
C4—C3—H3A	108.6	H5B—C5—H5C	109.5
C2—C3—H3A	108.6

O2—C1—C2—C3	−1.2 (2)	C2—C3—C4—O3	−8.66 (18)
O1—C1—C2—C3	178.42 (10)	C2—C3—C4—C5	171.36 (11)
C1—C2—C3—C4	179.46 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.83 (2)	1.87 (2)	2.6977 (13)	176 (2)

Symmetry code: (i) x−1, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.83 (2)	1.87 (2)	2.6977 (13)	176 (2)

Symmetry code: (i) x−1, −y+1/2, z+1/2.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1406

doi:10.1107/S1600536813021090

Open

access