Acta Cryst. (2009). E65, o1201 [ doi:10.1107/S1600536809015372 ]
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.
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).
The hydrogen atoms were located in difference maps but positioned with idealized geometry and refined using the riding model, with C—H = 0.98–1.00 Å or N—H = 0.90 Å and Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(Cmethyl).
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).
![[Figure 1]](./bt2937fig1thm.gif)
| Fig. 1. ORTEP representation of the title compound with atomic labeling of, shown with 50% probability displacement ellipsoids. |
![[Figure 2]](./bt2937fig2thm.gif)
| Fig. 2. View of the unit cell of the title compound along [100], showing the hydrogen-bonded chains running along the twofold screw axis. |
| C8H13NO2 | F000 = 168 |
| Mr = 155.19 | Dx = 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 = 67–69º |
| b = 7.7961 (4) Å | µ = 0.71 mm−1 |
| c = 10.9919 (10) Å | T = 193 K |
| β = 95.778 (4)º | Block, yellow |
| V = 427.26 (6) Å3 | 0.44 × 0.16 × 0.16 mm |
| Z = 2 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.040 |
| Monochromator: graphite | θmax = 69.9º |
| T = 193 K | θmin = 4.0º |
| ω/2θ scans | h = −6→5 |
| Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971) | k = −8→9 |
| Tmin = 0.744, Tmax = 0.993 | l = −13→13 |
| 1866 measured reflections | 3 standard reflections |
| 1571 independent reflections | every 60 min |
| 1558 reflections with I > 2σ(I) | intensity decay: 2% |
| 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(Fo2) + (0.0616P)2 + 0.0771P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
| S = 1.06 | Δρmax = 0.22 e Å−3 |
| 1571 reflections | Δρmin = −0.16 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 | Flack parameter: 0.1 (2) |
| C8H13NO2 | V = 427.26 (6) Å3 |
| Mr = 155.19 | Z = 2 |
| Monoclinic, P21 | Cu Kα |
| 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)º |
| Enraf–Nonius CAD-4 diffractometer | 1558 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971) | Rint = 0.040 |
| Tmin = 0.744, Tmax = 0.993 | 3 standard reflections |
| 1866 measured reflections | every 60 min |
| 1571 independent reflections | intensity decay: 2% |
| R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
| wR(F2) = 0.098 | Δρmax = 0.22 e Å−3 |
| S = 1.06 | Δρmin = −0.16 e Å−3 |
| 1571 reflections | Absolute structure: Flack (1983), 697 Friedel pairs |
| 103 parameters | Flack parameter: 0.1 (2) |
| 1 restraint |
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 | ||
| 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* |
| 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) |
| 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) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.90 | 2.02 | 2.8963 (18) | 164 |
| Symmetry codes: (i) −x, y−1/2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.90 | 2.02 | 2.8963 (18) | 164 |
| Symmetry codes: (i) −x, y−1/2, −z+1. |
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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).