Acta Cryst. (2009). E65, o2356 [ doi:10.1107/S1600536809034606 ]
In the title compound, C4HCl2NO3, the essentially planar (maximum deviation = 0.023 Å for the ring O atom) molecules form N-H
O hydrogen bonds between molecules lying about inversion centers, forming eight-membered rings with an R22(8) motif in graph-set notation.
Dichloromaleic anhydride (3,4-dichlorofuran-2,5-dione) and trimethylsilyl azide were treated analogously to the syntheses reported for the 4-methyl (Parrish, Leuschner et al., 2009) and 4-bromo derivatives. Crystals of the title compound were grown from a solution of acetone at room temperature by slow evaporation.
Hydrogen atom bonded to N3 was calculated and refined using a riding model using the N—H distance 0.88 Å with Uiso(H) = 1.2Ueq(N).
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]](./pv2198fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./pv2198fig2thm.gif)
| Fig. 2. The packing of the title compound viewed along the b axis and showing the H-bonded dimer formed by inversion related molecules. |
| C4HCl2NO3 | F(000) = 360 |
| Mr = 181.96 | Dx = 1.980 Mg m−3 Dm = 1.92 Mg m−3 Dm measured by floatation |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 20 reflections |
| a = 10.2290 (16) Å | θ = 10–12.5° |
| b = 5.2549 (8) Å | µ = 1.00 mm−1 |
| c = 12.2766 (16) Å | T = 293 K |
| β = 112.359 (11)° | Plates, colorless |
| V = 610.28 (16) Å3 | 0.38 × 0.33 × 0.15 mm |
| Z = 4 |
| Siemens R3m/V diffractometer | Rint = 0.053 |
| Radiation source: fine-focus sealed tube | θmax = 27.6°, θmin = 2.2° |
| graphite | h = 0→13 |
| θ–2θ scans | k = 0→6 |
| 1566 measured reflections | l = −15→14 |
| 1405 independent reflections | 3 standard reflections every 97 reflections |
| 1235 reflections with I > 2σ(I) | intensity decay: none |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0666P)2 + 0.3617P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.95 | (Δ/σ)max < 0.001 |
| 1405 reflections | Δρmax = 0.41 e Å−3 |
| 92 parameters | Δρmin = −0.38 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.042 (5) |
| C4HCl2NO3 | V = 610.28 (16) Å3 |
| Mr = 181.96 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.2290 (16) Å | µ = 1.00 mm−1 |
| b = 5.2549 (8) Å | T = 293 K |
| c = 12.2766 (16) Å | 0.38 × 0.33 × 0.15 mm |
| β = 112.359 (11)° |
| Siemens R3m/V diffractometer | Rint = 0.053 |
| 1566 measured reflections | θmax = 27.6° |
| 1405 independent reflections | 3 standard reflections every 97 reflections |
| 1235 reflections with I > 2σ(I) | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.100 | Δρmax = 0.41 e Å−3 |
| S = 0.95 | Δρmin = −0.38 e Å−3 |
| 1405 reflections | Absolute structure: ? |
| 92 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 | 0.89484 (14) | 0.7547 (3) | 0.20549 (12) | 0.0405 (4) | |
| C2 | 0.9358 (2) | 0.6588 (4) | 0.12050 (17) | 0.0362 (4) | |
| O2 | 1.03514 (16) | 0.7544 (3) | 0.10600 (14) | 0.0474 (4) | |
| N3 | 0.86084 (17) | 0.4586 (3) | 0.05845 (14) | 0.0363 (4) | |
| H3 | 0.8864 | 0.3892 | 0.0062 | 0.044* | |
| C4 | 0.74604 (19) | 0.3625 (3) | 0.07572 (15) | 0.0325 (4) | |
| Cl4 | 0.66660 (6) | 0.11274 (10) | −0.01234 (4) | 0.0453 (2) | |
| C5 | 0.7009 (2) | 0.4611 (4) | 0.15609 (16) | 0.0347 (4) | |
| Cl5 | 0.55557 (6) | 0.35198 (11) | 0.17764 (5) | 0.0491 (2) | |
| C6 | 0.7780 (2) | 0.6694 (4) | 0.22914 (17) | 0.0366 (4) | |
| O6 | 0.75456 (18) | 0.7746 (3) | 0.30575 (15) | 0.0533 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0479 (8) | 0.0401 (8) | 0.0369 (7) | −0.0084 (6) | 0.0199 (6) | −0.0094 (6) |
| C2 | 0.0401 (10) | 0.0363 (9) | 0.0321 (9) | −0.0007 (8) | 0.0138 (8) | 0.0003 (7) |
| O2 | 0.0479 (8) | 0.0484 (9) | 0.0515 (9) | −0.0126 (7) | 0.0251 (7) | −0.0079 (7) |
| N3 | 0.0405 (8) | 0.0411 (9) | 0.0317 (8) | −0.0050 (7) | 0.0188 (6) | −0.0060 (7) |
| C4 | 0.0366 (9) | 0.0333 (9) | 0.0256 (8) | −0.0020 (7) | 0.0097 (7) | 0.0002 (7) |
| Cl4 | 0.0530 (3) | 0.0453 (3) | 0.0375 (3) | −0.0132 (2) | 0.0172 (2) | −0.0125 (2) |
| C5 | 0.0387 (9) | 0.0387 (10) | 0.0286 (8) | −0.0019 (8) | 0.0148 (7) | 0.0005 (7) |
| Cl5 | 0.0526 (3) | 0.0587 (4) | 0.0464 (3) | −0.0136 (2) | 0.0303 (3) | −0.0082 (2) |
| C6 | 0.0442 (10) | 0.0362 (9) | 0.0317 (9) | −0.0008 (8) | 0.0171 (8) | −0.0007 (7) |
| O6 | 0.0691 (10) | 0.0521 (9) | 0.0484 (9) | −0.0073 (8) | 0.0334 (8) | −0.0166 (7) |
| O1—C2 | 1.360 (2) | C4—C5 | 1.342 (3) |
| O1—C6 | 1.406 (2) | C4—Cl4 | 1.698 (2) |
| C2—O2 | 1.206 (2) | C5—C6 | 1.444 (3) |
| C2—N3 | 1.353 (3) | C5—Cl5 | 1.706 (2) |
| N3—C4 | 1.367 (2) | C6—O6 | 1.192 (2) |
| N3—H3 | 0.8600 | ||
| C2—O1—C6 | 125.02 (15) | C5—C4—Cl4 | 123.46 (15) |
| O2—C2—N3 | 124.69 (18) | N3—C4—Cl4 | 114.72 (14) |
| O2—C2—O1 | 118.79 (18) | C4—C5—C6 | 119.33 (17) |
| N3—C2—O1 | 116.51 (16) | C4—C5—Cl5 | 123.23 (15) |
| C2—N3—C4 | 122.41 (16) | C6—C5—Cl5 | 117.44 (14) |
| C2—N3—H3 | 118.8 | O6—C6—O1 | 117.20 (18) |
| C4—N3—H3 | 118.8 | O6—C6—C5 | 127.99 (19) |
| C5—C4—N3 | 121.82 (17) | O1—C6—C5 | 114.81 (16) |
| C6—O1—C2—O2 | 177.41 (18) | N3—C4—C5—Cl5 | 178.26 (14) |
| C6—O1—C2—N3 | −3.1 (3) | Cl4—C4—C5—Cl5 | −1.5 (3) |
| O2—C2—N3—C4 | −177.81 (19) | C2—O1—C6—O6 | −179.15 (19) |
| O1—C2—N3—C4 | 2.7 (3) | C2—O1—C6—C5 | 1.0 (3) |
| C2—N3—C4—C5 | −0.3 (3) | C4—C5—C6—O6 | −178.2 (2) |
| C2—N3—C4—Cl4 | 179.47 (15) | Cl5—C5—C6—O6 | 1.5 (3) |
| N3—C4—C5—C6 | −2.0 (3) | C4—C5—C6—O1 | 1.6 (3) |
| Cl4—C4—C5—C6 | 178.29 (14) | Cl5—C5—C6—O1 | −178.62 (13) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3···O2i | 0.86 | 1.99 | 2.845 (2) | 174 |
| Symmetry codes: (i) −x+2, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3···O2i | 0.86 | 1.99 | 2.845 (2) | 174 |
| Symmetry codes: (i) −x+2, −y+1, −z. |
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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).
Unlike the hydrogen bonding observed in 4-methyl derivative (Parrish, Leuschner et al., 2009) resulting in staggered chains of molecules, in the crystal structure of of the title compound (Fig. 1), the molecules of (I) are held together by classical intermolecular hydrogen bonds of the type N—H···O resulting in dimeric units about inversion centers, forming eight membered ring systems which may be described in terms of graph set notation (Bernstein et al. 1994) as R22(8) ring motif (details have been given in Table 1 and Figure 2). The molecular dimensions in (I) agree well with the corresponding bond distances and angles reported for the above mentioned structures and 4-boromo derivative of 3-oxauracil (Parrish, Tivitmahaisoon et al., 2009).