Acta Cryst. (2009). E65, o2354 [ doi:10.1107/S1600536809034618 ]
In the title compound, C5H5NO3, the planar (maximum deviation = 0.075 Å for the ring O atom) molecules form N-H
O hydrogen bonds in a zigzag chain (C-ON bond angle ![[asymptotically equal to]](/logos/entities/sime_rmgif.gif)
140°) between glide-related molecules.
Citraconic anhydride (3-methylfuran-2,5-dione, 2.0 ml, 22 mmol) and trimethylsilyl azide (3.0 ml, 23 mmol) were added to 10 ml dichloromethane at 273 K and stirred under nitrogen for 4 h. Upon warming to room temperature over night, a white precipitate formed. Ethanol (2.5 ml) was added, the mixture stirred 2 additional hours, and then the solvent was removed under reduced pressure to obtain the title compound; yield: 1.7 g (13 mmol, 59%). Crystals of the title compound were grown from a solution of acetone at room temperature by slow evaporation.
Hydrogen positions were calculated and refined using a riding model using the following C—H distances: methyl 0.96 Å, methylene 0.93 Å, and N—H 0.88 Å with Uiso(H) = 1.2Ueq(C5/N3) and 1.5Ueq(C7).
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pv2197fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./pv2197fig2thm.gif)
| Fig. 2. The packing of the title compound viewed down the a axis; intermolecular hydrogen bonds have been represented by dashed lines. |
| C5H5NO3 | F(000) = 264 |
| Mr = 127.1 | Dx = 1.505 Mg m−3 Dm = 1.46 Mg m−3 Dm measured by floatation in bromoform/hexane solution |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 20 reflections |
| a = 7.254 (3) Å | θ = 10–12.5° |
| b = 6.683 (2) Å | µ = 0.13 mm−1 |
| c = 11.689 (5) Å | T = 293 K |
| β = 98.11 (4)° | Plates, colorless |
| V = 561.0 (4) Å3 | 0.46 × 0.30 × 0.10 mm |
| Z = 4 |
| Bruker R3/V diffractometer | Rint = 0.012 |
| Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 3.1° |
| graphite | h = 0→9 |
| θ – 2θ scans | k = 0→8 |
| 1410 measured reflections | l = −15→15 |
| 1294 independent reflections | 3 standard reflections every 97 reflections |
| 910 reflections with I > 2σ(I) | intensity decay: none |
| 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.191 | H-atom parameters constrained |
| S = 0.93 | w = 1/[σ2(Fo2) + (0.1301P)2 + 0.1905P] where P = (Fo2 + 2Fc2)/3 |
| 1294 reflections | (Δ/σ)max = 0.005 |
| 83 parameters | Δρmax = 0.23 e Å−3 |
| 0 restraints | Δρmin = −0.24 e Å−3 |
| C5H5NO3 | V = 561.0 (4) Å3 |
| Mr = 127.1 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.254 (3) Å | µ = 0.13 mm−1 |
| b = 6.683 (2) Å | T = 293 K |
| c = 11.689 (5) Å | 0.46 × 0.30 × 0.10 mm |
| β = 98.11 (4)° |
| Bruker R3/V diffractometer | Rint = 0.012 |
| 1410 measured reflections | θmax = 27.6° |
| 1294 independent reflections | 3 standard reflections every 97 reflections |
| 910 reflections with I > 2σ(I) | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.191 | Δρmax = 0.23 e Å−3 |
| S = 0.93 | Δρmin = −0.24 e Å−3 |
| 1294 reflections | Absolute structure: ? |
| 83 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.6042 (2) | 0.1383 (2) | 0.68042 (13) | 0.0466 (5) | |
| C2 | 0.4998 (3) | 0.2078 (3) | 0.58306 (19) | 0.0422 (5) | |
| O2 | 0.3337 (2) | 0.2161 (3) | 0.57888 (19) | 0.0694 (6) | |
| N3 | 0.5939 (2) | 0.2571 (3) | 0.49490 (14) | 0.0406 (5) | |
| H3 | 0.5305 | 0.2967 | 0.4312 | 0.049* | |
| C4 | 0.7833 (3) | 0.2477 (3) | 0.50089 (18) | 0.0392 (5) | |
| C5 | 0.8847 (3) | 0.1896 (3) | 0.59971 (19) | 0.0430 (5) | |
| H5 | 1.0137 | 0.1846 | 0.6048 | 0.052* | |
| C6 | 0.7988 (3) | 0.1357 (3) | 0.69668 (18) | 0.0435 (5) | |
| O6 | 0.8682 (3) | 0.0868 (3) | 0.79242 (15) | 0.0695 (7) | |
| C7 | 0.8619 (4) | 0.3002 (5) | 0.3938 (2) | 0.0630 (8) | |
| H7A | 0.9955 | 0.2979 | 0.4093 | 0.095* | |
| H7B | 0.8210 | 0.4317 | 0.3687 | 0.095* | |
| H7C | 0.8201 | 0.2050 | 0.3343 | 0.095* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0448 (9) | 0.0555 (10) | 0.0417 (8) | −0.0028 (7) | 0.0137 (6) | 0.0020 (7) |
| C2 | 0.0329 (10) | 0.0455 (12) | 0.0490 (11) | 0.0003 (8) | 0.0086 (8) | −0.0068 (9) |
| O2 | 0.0324 (9) | 0.0847 (14) | 0.0936 (15) | −0.0020 (9) | 0.0174 (9) | −0.0026 (11) |
| N3 | 0.0342 (9) | 0.0511 (10) | 0.0350 (9) | 0.0041 (7) | 0.0003 (7) | 0.0010 (7) |
| C4 | 0.0374 (10) | 0.0384 (10) | 0.0445 (11) | 0.0029 (8) | 0.0152 (8) | −0.0025 (9) |
| C5 | 0.0294 (9) | 0.0458 (12) | 0.0534 (12) | 0.0012 (9) | 0.0049 (8) | −0.0021 (10) |
| C6 | 0.0447 (11) | 0.0395 (11) | 0.0435 (11) | −0.0024 (9) | −0.0038 (9) | −0.0025 (9) |
| O6 | 0.0831 (14) | 0.0687 (13) | 0.0494 (10) | −0.0096 (10) | −0.0167 (9) | 0.0110 (9) |
| C7 | 0.0651 (16) | 0.0733 (18) | 0.0573 (14) | 0.0053 (13) | 0.0313 (12) | 0.0133 (13) |
| O1—C2 | 1.357 (3) | C4—C7 | 1.489 (3) |
| O1—C6 | 1.398 (3) | C5—C6 | 1.415 (3) |
| C2—O2 | 1.200 (3) | C5—H5 | 0.9300 |
| C2—N3 | 1.354 (3) | C6—O6 | 1.206 (3) |
| N3—C4 | 1.368 (3) | C7—H7A | 0.9600 |
| N3—H3 | 0.8600 | C7—H7B | 0.9600 |
| C4—C5 | 1.337 (3) | C7—H7C | 0.9600 |
| C2—O1—C6 | 123.50 (17) | C4—C5—H5 | 119.5 |
| O2—C2—N3 | 124.6 (2) | C6—C5—H5 | 119.5 |
| O2—C2—O1 | 119.2 (2) | O6—C6—O1 | 114.3 (2) |
| N3—C2—O1 | 116.10 (18) | O6—C6—C5 | 129.7 (2) |
| C2—N3—C4 | 124.08 (18) | O1—C6—C5 | 115.99 (18) |
| C2—N3—H3 | 118.0 | C4—C7—H7A | 109.5 |
| C4—N3—H3 | 118.0 | C4—C7—H7B | 109.5 |
| C5—C4—N3 | 118.95 (18) | H7A—C7—H7B | 109.5 |
| C5—C4—C7 | 124.5 (2) | C4—C7—H7C | 109.5 |
| N3—C4—C7 | 116.6 (2) | H7A—C7—H7C | 109.5 |
| C4—C5—C6 | 121.03 (19) | H7B—C7—H7C | 109.5 |
| C6—O1—C2—O2 | −175.5 (2) | N3—C4—C5—C6 | 0.9 (3) |
| C6—O1—C2—N3 | 6.7 (3) | C7—C4—C5—C6 | −177.8 (2) |
| O2—C2—N3—C4 | 179.7 (2) | C2—O1—C6—O6 | 173.2 (2) |
| O1—C2—N3—C4 | −2.6 (3) | C2—O1—C6—C5 | −6.9 (3) |
| C2—N3—C4—C5 | −1.1 (3) | C4—C5—C6—O6 | −177.3 (2) |
| C2—N3—C4—C7 | 177.7 (2) | C4—C5—C6—O1 | 2.8 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3···O6i | 0.86 | 2.02 | 2.877 (3) | 173 |
| Symmetry codes: (i) x−1/2, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3···O6i | 0.86 | 2.02 | 2.877 (3) | 173 |
| Symmetry codes: (i) x−1/2, −y+1/2, z−1/2. |
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Parrish, D., Leuschner, F., Rehberg, G. M. & Kastner, M. E. (2009). Acta Cryst. E65, o2356.
Parrish, D., Tivitmahaisoon, P., Rehberg, G. M. & Kastner, M. E. (2009). Acta Cryst. E65, o2355.
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The synthesis of derivatives of 3-oxauracil has previously been reported (Warren et al., 1975) and an improved synthesis of the unsubstituted 3-oxauracil was reported by Rehberg & Glass (1995). The structure of the unsubstituted 3-oxauracil and its monohydrate have been reported (Copley et al., 2005). Three derivatives of 3-oxauracil (4-methyl, 4-bromo, and 4,5-dichloro) have been prepared in our laboratory in route to the synthesis of 1-aza-1,3-butadienes. In this paper, we report the crystal structure of the title compound, (I).
In the title compound (Fig. 1) only one intermolecular H-bond is formed between N3 and O6 of glide-related molecules (details are given in Table 1). Although the molecules of (I) are planar, the H-bonding chains are staggered as shown in Figure 2. The hydrogen bonding networks in (I) differs significantly from the hydrogen bonding in 4,5-dichloro (Parrish, Leuschner et al., 2009) and 4-bromo (Parrish, Tivitmahaisoon et al., 2009) derivatives.