Deacetyl­ tenuazonic acid

Siegel, D.; Koch, M.; Emmerling, F.; Nehls, I.

doi:10.1107/S1600536809015372

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1201

doi:10.1107/S1600536809015372

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Deacetyl tenuazonic acid

David Siegel,^a ^* Matthias Koch,^a Franziska Emmerling ^a and Irene Nehls ^a

^aBundesanstalt für Materialforschung und -prüfung, Abteilung Analytische Chemie; Referenzmaterialien, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
^*Correspondence e-mail: david.siegel@bam.de

(Received 23 April 2009; accepted 24 April 2009; online 7 May 2009)

The heterocycle in the title compound {systematic name: (5S)-5-[(1S)-1-methylpropyl]pyrrolidine-2,4-dione}, C₈H₁₃NO₂, is planar (r.m.s. deviation for all non-H atoms = 0.008 Å). The crystal structure is stabilized by N—H⋯O hydrogen bonding.

Related literature

Tenuazonic acid (TA) is an Alternaria mycotoxin commonly encountered in food (Siegel, Rasenko et al., 2009 ; Weidenbörner, 2001 ). The title compound is known to be formed upon boiling TA in 0.1 M HCl (Stickings, 1959 ). For the synthesis of the title compound, see: Lebrun et al. (1988 ). For the crystal structure of the tenuazonic acid copper (II) salt, see: Dippenaar et al. (1977 ) and for the 2,4-dinitrophenylhydrazone, see: Siegel, Merkel et al. (2009 ). For the structures of other pyrrolidine-2,4-diones, see, for example: Yu et al. (2007 ); Zhu et al. (2004 ); Ellis & Spek (2001 ).

Experimental

Crystal data

C₈H₁₃NO₂
M_r = 155.19
Monoclinic, P 2₁
a = 5.0114 (4) Å
b = 7.7961 (4) Å
c = 10.9919 (10) Å
β = 95.778 (4)°
V = 427.26 (6) Å³
Z = 2
Cu Kα radiation
μ = 0.71 mm⁻¹
T = 193 K
0.44 × 0.16 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ) T_min = 0.744, T_max = 0.993 (expected range = 0.669–0.893)
1866 measured reflections
1571 independent reflections
1558 reflections with I > 2σ(I)
R_int = 0.040
3 standard reflections frequency: 60 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.06
1571 reflections
103 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 697 Friedel pairs
Flack parameter: 0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.90	2.02	2.8963 (18)	164
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015372/bt2937sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015372/bt2937Isup2.hkl

checkCIF report

Comment top

Tenuazonic acid (TA) is an Alternaria mycotoxin commonly encountered in food (Siegel, Rasenko et al., 2009; Weidenbörner, 2001). The title compound is known to be formed upon boiling of TA in 0.1 M HCl (Stickings, 1959). It is therefore a possible degradation product which might also be encountered in food matrices.

Whereas TA itself could so far only be crystallized as its copper (II) salt (Dippenaar et al., 1977) or 2,4-dinitrophenylhydrazone (Siegel, Merkel et al., 2009), the title compound is conveniently crystallized from hexane/ethyl acetate.

Each molecule (Fig. 1) is connected to two adjacent molecules via N—H···O hydrogen bonds. Along the b axis chains of symmetry equivalent molecules are formed (Fig. 2).

Related literature top

Tenuazonic acid (TA) is an Alternaria mycotoxin commonly encountered in food (Siegel, Rasenko et al., 2009; Weidenbörner, 2001). The title compound is known to be formed upon boiling of the Alternaria mycotoxin tenuazonic acid in 0.1 M HCl (Stickings, 1959). For the synthesis of the title compound, see: Lebrun et al. (1988). For the crystal structure of the tenuazonic acid copper (II) salt, see: Dippenaar et al. (1977) and for the 2,4-dinitrophenylhydrazone, see: Siegel, Merkel et al. (2009). For the structures of other pyrrolidine-2,4-diones, see, for example: Yu et al. (2007); Zhu et al. (2004); Ellis & Spek (2001).

Experimental top

The title compound was supplied by the workgroup of Professor R. Faust (University of Kassel, Germany) by synthesis according to a literature procedure (Lebrun et al., 1988). For x-ray analysis, it was recrystallized several times from hexane:ethyl acetate 50:50 (v:v).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP representation of the title compound with atomic labeling of, shown with 50% probability displacement ellipsoids.
	Fig. 2. View of the unit cell of the title compound along [100], showing the hydrogen-bonded chains running along the twofold screw axis.

(5S)-5-[(1S)-1-methylpropyl]pyrrolidine-2,4-dione top

Crystal data top

C₈H₁₃NO₂	F(000) = 168
M_r = 155.19	D_x = 1.206 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 5.0114 (4) Å	θ = 67–69°
b = 7.7961 (4) Å	µ = 0.71 mm⁻¹
c = 10.9919 (10) Å	T = 193 K
β = 95.778 (4)°	Block, yellow
V = 427.26 (6) Å³	0.44 × 0.16 × 0.16 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1558 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.040
Graphite monochromator	θ_max = 69.9°, θ_min = 4.0°
ω/2θ scans	h = −6→5
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	k = −8→9
T_min = 0.744, T_max = 0.993	l = −13→13
1866 measured reflections	3 standard reflections every 60 min
1571 independent reflections	intensity decay: 2%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0616P)² + 0.0771P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.22 e Å⁻³
1571 reflections	Δρ_min = −0.17 e Å⁻³
103 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.017 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 697 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (2)

Crystal data top

C₈H₁₃NO₂	V = 427.26 (6) Å³
M_r = 155.19	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 5.0114 (4) Å	µ = 0.71 mm⁻¹
b = 7.7961 (4) Å	T = 193 K
c = 10.9919 (10) Å	0.44 × 0.16 × 0.16 mm
β = 95.778 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1558 reflections with I > 2σ(I)
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	R_int = 0.040
T_min = 0.744, T_max = 0.993	3 standard reflections every 60 min
1866 measured reflections	intensity decay: 2%
1571 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.098	Δρ_max = 0.22 e Å⁻³
S = 1.06	Δρ_min = −0.17 e Å⁻³
1571 reflections	Absolute structure: Flack (1983), 697 Friedel pairs
103 parameters	Absolute structure parameter: 0.1 (2)
1 restraint

Special details top

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	−0.0559 (2)	0.66044 (16)	0.50335 (11)	0.0386 (3)
O2	0.5911 (3)	0.74694 (19)	0.22570 (14)	0.0494 (4)
N1	0.2318 (3)	0.48864 (18)	0.41048 (11)	0.0303 (3)
H1	0.1866	0.3946	0.4519	0.036*
C1	0.1196 (3)	0.6392 (2)	0.43372 (14)	0.0305 (3)
C2	0.2400 (3)	0.7779 (2)	0.36022 (15)	0.0360 (4)
H2A	0.1012	0.8320	0.3021	0.043*
H2B	0.3265	0.8675	0.4145	0.043*
C3	0.4437 (3)	0.6853 (2)	0.29328 (15)	0.0335 (4)
C4	0.4354 (3)	0.4941 (2)	0.32393 (13)	0.0296 (3)
H4	0.6122	0.4594	0.3672	0.036*
C5	0.3757 (3)	0.3822 (2)	0.20975 (14)	0.0317 (4)
H5	0.5040	0.4161	0.1500	0.038*
C6	0.0924 (4)	0.4130 (3)	0.14885 (16)	0.0425 (4)
H6A	−0.0373	0.3594	0.1995	0.051*
H6B	0.0571	0.5380	0.1467	0.051*
C7	0.0441 (6)	0.3429 (4)	0.0202 (2)	0.0761 (8)
H7A	0.1721	0.3946	−0.0307	0.114*
H7B	−0.1391	0.3706	−0.0138	0.114*
H7C	0.0679	0.2181	0.0219	0.114*
C8	0.4266 (4)	0.1937 (2)	0.2416 (2)	0.0474 (5)
H8A	0.6088	0.1804	0.2821	0.071*
H8B	0.4071	0.1250	0.1666	0.071*
H8C	0.2967	0.1549	0.2966	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0498 (7)	0.0316 (6)	0.0377 (6)	−0.0010 (5)	0.0201 (5)	−0.0054 (5)
O2	0.0530 (8)	0.0418 (8)	0.0576 (8)	−0.0067 (6)	0.0262 (6)	0.0115 (6)
N1	0.0349 (7)	0.0268 (7)	0.0303 (6)	−0.0028 (5)	0.0094 (5)	0.0017 (5)
C1	0.0374 (8)	0.0264 (8)	0.0279 (7)	−0.0056 (6)	0.0046 (6)	−0.0030 (6)
C2	0.0462 (9)	0.0253 (8)	0.0378 (8)	−0.0062 (7)	0.0104 (7)	−0.0022 (7)
C3	0.0348 (8)	0.0312 (8)	0.0347 (8)	−0.0065 (6)	0.0043 (6)	0.0024 (7)
C4	0.0268 (7)	0.0308 (8)	0.0321 (7)	−0.0025 (6)	0.0063 (5)	0.0042 (7)
C5	0.0310 (8)	0.0312 (8)	0.0346 (8)	0.0006 (6)	0.0120 (6)	−0.0011 (6)
C6	0.0373 (9)	0.0512 (11)	0.0391 (9)	0.0028 (7)	0.0037 (7)	−0.0102 (8)
C7	0.0824 (18)	0.087 (2)	0.0547 (14)	0.0218 (14)	−0.0144 (12)	−0.0302 (13)
C8	0.0558 (11)	0.0317 (9)	0.0573 (12)	0.0060 (8)	0.0182 (8)	−0.0003 (8)

Geometric parameters (Å, º) top

O1—C1	1.2338 (19)	C5—C8	1.526 (2)
O2—C3	1.199 (2)	C5—C6	1.526 (2)
N1—C1	1.337 (2)	C5—H5	1.0000
N1—C4	1.4640 (18)	C6—C7	1.512 (3)
N1—H1	0.9038	C6—H6A	0.9900
C1—C2	1.511 (2)	C6—H6B	0.9900
C2—C3	1.501 (2)	C7—H7A	0.9800
C2—H2A	0.9900	C7—H7B	0.9800
C2—H2B	0.9900	C7—H7C	0.9800
C3—C4	1.530 (2)	C8—H8A	0.9800
C4—C5	1.533 (2)	C8—H8B	0.9800
C4—H4	1.0000	C8—H8C	0.9800

C1—N1—C4	115.63 (14)	C6—C5—C4	111.45 (13)
C1—N1—H1	119.0	C8—C5—H5	107.6
C4—N1—H1	125.2	C6—C5—H5	107.6
O1—C1—N1	125.18 (14)	C4—C5—H5	107.6
O1—C1—C2	125.70 (14)	C7—C6—C5	114.04 (16)
N1—C1—C2	109.12 (14)	C7—C6—H6A	108.7
C3—C2—C1	104.25 (14)	C5—C6—H6A	108.7
C3—C2—H2A	110.9	C7—C6—H6B	108.7
C1—C2—H2A	110.9	C5—C6—H6B	108.7
C3—C2—H2B	110.9	H6A—C6—H6B	107.6
C1—C2—H2B	110.9	C6—C7—H7A	109.5
H2A—C2—H2B	108.9	C6—C7—H7B	109.5
O2—C3—C2	127.06 (17)	H7A—C7—H7B	109.5
O2—C3—C4	123.96 (16)	C6—C7—H7C	109.5
C2—C3—C4	108.98 (13)	H7A—C7—H7C	109.5
N1—C4—C3	101.98 (13)	H7B—C7—H7C	109.5
N1—C4—C5	115.10 (13)	C5—C8—H8A	109.5
C3—C4—C5	112.44 (13)	C5—C8—H8B	109.5
N1—C4—H4	109.0	H8A—C8—H8B	109.5
C3—C4—H4	109.0	C5—C8—H8C	109.5
C5—C4—H4	109.0	H8A—C8—H8C	109.5
C8—C5—C6	112.26 (15)	H8B—C8—H8C	109.5
C8—C5—C4	110.21 (14)

C4—N1—C1—O1	179.64 (15)	C2—C3—C4—N1	−1.75 (16)
C4—N1—C1—C2	0.22 (18)	O2—C3—C4—C5	−57.6 (2)
O1—C1—C2—C3	179.26 (14)	C2—C3—C4—C5	122.08 (14)
N1—C1—C2—C3	−1.33 (18)	N1—C4—C5—C8	−75.53 (17)
C1—C2—C3—O2	−178.44 (17)	C3—C4—C5—C8	168.27 (14)
C1—C2—C3—C4	1.90 (17)	N1—C4—C5—C6	49.81 (19)
C1—N1—C4—C3	0.95 (16)	C3—C4—C5—C6	−66.39 (17)
C1—N1—C4—C5	−121.07 (15)	C8—C5—C6—C7	−70.6 (3)
O2—C3—C4—N1	178.57 (16)	C4—C5—C6—C7	165.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.90	2.02	2.8963 (18)	164

Symmetry code: (i) −x, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₁₃NO₂
M_r	155.19
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	5.0114 (4), 7.7961 (4), 10.9919 (10)
β (°)	95.778 (4)
V (Å³)	427.26 (6)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.44 × 0.16 × 0.16

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (CORINC; Dräger & Gattow, 1971)
T_min, T_max	0.744, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	1866, 1571, 1558
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.06
No. of reflections	1571
No. of parameters	103
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17
Absolute structure	Flack (1983), 697 Friedel pairs
Absolute structure parameter	0.1 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Dräger & Gattow, 1971), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.90	2.02	2.8963 (18)	164

Symmetry code: (i) −x, y−1/2, −z+1.

References

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1201

doi:10.1107/S1600536809015372

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