Acta Cryst. (2007). E63, o2918 [ doi:10.1107/S1600536807022404 ]
In the crystal structure of the title compound, C9H9Br3N2O3, molecules are linked by N-H
O hydrogen bonds to form centrosymmetric dimers of graph-set motif R22(10).
The hydrochloric acid salt of beta-alanine methyl ester (0.70 g, 5 mmol) and 3,4,5-tribromo-2-trichloroacetylpyrrole (2.25 g, 5 mmol) were added to acetonitrile (12 ml), followed by the dropwise addition of triethylamine (1.4 ml). The mixture was stirred at room temperature for 12 h and then poured into water. After filtration, the precipitate was collected as a yellow solid. The impure product was dissolved in EtOH at room temperature. Colourless monoclinic crystals suitable for X-ray analysis (m.p. 456 K, 90.3% yield) grew over a period of one week when the solution was exposed to the air. Analysis calculated for C9H9Br3N2O3: C 24.97, H 2.09, N 6.47%. Found: C 24.82, H 2.15, N 6.54%.
The H atoms were positioned geometrically [C—H = 0.99 Å for CH2, 0.98 Å for CH3, and N—H = 0.88 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq (1.5Ueq for the methyl group) of the parent atom.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./at2289fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./at2289fig2thm.gif)
| Fig. 2. Dimers formed by hydrogen bonds (dashed lines). |
| C9H9Br3N2O3 | F(000) = 824 |
| Mr = 432.91 | Dx = 2.265 Mg m−3 |
| Monoclinic, P21/c | Melting point: 456 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.7032 (12) Å | Cell parameters from 2696 reflections |
| b = 8.6376 (12) Å | θ = 2.6–22.7° |
| c = 16.962 (2) Å | µ = 9.53 mm−1 |
| β = 95.341 (2)° | T = 173 K |
| V = 1269.6 (3) Å3 | Prism, colourless |
| Z = 4 | 0.44 × 0.31 × 0.25 mm |
| Bruker SMART 1K CCD area-detector diffractometer | 2484 independent reflections |
| Radiation source: fine-focus sealed tube | 2097 reflections with I > 2σ(I) |
| graphite | Rint = 0.034 |
| φ and ω scans | θmax = 26.0°, θmin = 2.4° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.040, Tmax = 0.092 | k = −9→10 |
| 7442 measured reflections | l = −18→20 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.107 | H-atom parameters constrained |
| S = 1.14 | w = 1/[σ2(Fo2) + (0.0438P)2 + 6.1964P] where P = (Fo2 + 2Fc2)/3 |
| 2484 reflections | (Δ/σ)max = 0.001 |
| 155 parameters | Δρmax = 0.77 e Å−3 |
| 0 restraints | Δρmin = −1.86 e Å−3 |
| C9H9Br3N2O3 | V = 1269.6 (3) Å3 |
| Mr = 432.91 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.7032 (12) Å | µ = 9.53 mm−1 |
| b = 8.6376 (12) Å | T = 173 K |
| c = 16.962 (2) Å | 0.44 × 0.31 × 0.25 mm |
| β = 95.341 (2)° |
| Bruker SMART 1K CCD area-detector diffractometer | 2484 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2097 reflections with I > 2σ(I) |
| Tmin = 0.040, Tmax = 0.092 | Rint = 0.034 |
| 7442 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.107 | Δρmax = 0.77 e Å−3 |
| S = 1.14 | Δρmin = −1.86 e Å−3 |
| 2484 reflections | Absolute structure: ? |
| 155 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 | ||
| Br2 | 0.33602 (6) | 0.27122 (7) | 0.89835 (3) | 0.02380 (18) | |
| Br1 | 0.61311 (6) | 0.24109 (7) | 1.07246 (3) | 0.02411 (18) | |
| C9 | 1.1909 (7) | 0.4604 (9) | 0.5581 (4) | 0.0341 (15) | |
| H9A | 1.1514 | 0.5392 | 0.5199 | 0.051* | |
| H9B | 1.1172 | 0.3746 | 0.5579 | 0.051* | |
| H9C | 1.2902 | 0.4215 | 0.5434 | 0.051* | |
| C4 | 0.7555 (6) | 0.4767 (6) | 0.8898 (3) | 0.0157 (10) | |
| C3 | 0.6101 (6) | 0.4372 (7) | 0.8553 (3) | 0.0164 (11) | |
| O1 | 1.0017 (4) | 0.5867 (5) | 0.9124 (2) | 0.0272 (10) | |
| N2 | 0.8719 (5) | 0.6408 (5) | 0.7957 (3) | 0.0176 (9) | |
| H2 | 0.7916 | 0.6209 | 0.7618 | 0.021* | |
| N1 | 0.7698 (5) | 0.4137 (5) | 0.9641 (3) | 0.0168 (9) | |
| H1 | 0.8523 | 0.4207 | 0.9981 | 0.020* | |
| O3 | 1.2117 (4) | 0.5281 (5) | 0.6367 (2) | 0.0260 (9) | |
| C6 | 0.9914 (6) | 0.7501 (6) | 0.7736 (3) | 0.0188 (11) | |
| H6A | 1.0287 | 0.8119 | 0.8207 | 0.023* | |
| H6B | 0.9446 | 0.8224 | 0.7329 | 0.023* | |
| O2 | 0.9712 (4) | 0.6185 (5) | 0.6209 (2) | 0.0293 (10) | |
| C1 | 0.6386 (6) | 0.3391 (6) | 0.9774 (3) | 0.0156 (11) | |
| C7 | 1.1278 (6) | 0.6691 (6) | 0.7418 (3) | 0.0170 (11) | |
| H7A | 1.2142 | 0.7435 | 0.7411 | 0.020* | |
| H7B | 1.1623 | 0.5836 | 0.7781 | 0.020* | |
| C2 | 0.5355 (6) | 0.3512 (6) | 0.9103 (3) | 0.0157 (11) | |
| C8 | 1.0915 (6) | 0.6051 (6) | 0.6604 (3) | 0.0174 (11) | |
| C5 | 0.8841 (6) | 0.5724 (6) | 0.8659 (3) | 0.0170 (11) | |
| Br3 | 0.51990 (6) | 0.48619 (7) | 0.75407 (3) | 0.02589 (18) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br2 | 0.0114 (3) | 0.0376 (4) | 0.0222 (3) | −0.0095 (2) | 0.0003 (2) | −0.0027 (2) |
| Br1 | 0.0206 (3) | 0.0334 (4) | 0.0184 (3) | −0.0073 (2) | 0.0021 (2) | 0.0047 (2) |
| C9 | 0.028 (3) | 0.050 (4) | 0.025 (3) | 0.007 (3) | 0.004 (3) | −0.017 (3) |
| C4 | 0.011 (2) | 0.022 (3) | 0.014 (2) | 0.001 (2) | 0.0006 (18) | 0.002 (2) |
| C3 | 0.010 (2) | 0.027 (3) | 0.011 (2) | 0.003 (2) | −0.0012 (19) | −0.001 (2) |
| O1 | 0.0143 (19) | 0.044 (3) | 0.022 (2) | −0.0086 (18) | −0.0054 (16) | 0.0083 (19) |
| N2 | 0.011 (2) | 0.026 (3) | 0.015 (2) | −0.0033 (18) | 0.0004 (17) | 0.0028 (19) |
| N1 | 0.009 (2) | 0.021 (2) | 0.019 (2) | −0.0011 (17) | −0.0033 (17) | −0.0017 (19) |
| O3 | 0.0174 (19) | 0.041 (3) | 0.019 (2) | 0.0071 (18) | 0.0013 (15) | −0.0054 (18) |
| C6 | 0.016 (3) | 0.020 (3) | 0.021 (3) | −0.004 (2) | 0.003 (2) | 0.003 (2) |
| O2 | 0.019 (2) | 0.045 (3) | 0.022 (2) | 0.0105 (19) | −0.0062 (16) | −0.0085 (19) |
| C1 | 0.011 (2) | 0.020 (3) | 0.015 (3) | −0.002 (2) | 0.0006 (19) | −0.001 (2) |
| C7 | 0.012 (2) | 0.019 (3) | 0.021 (3) | −0.001 (2) | 0.003 (2) | 0.001 (2) |
| C2 | 0.008 (2) | 0.021 (3) | 0.018 (3) | −0.002 (2) | 0.0002 (19) | −0.003 (2) |
| C8 | 0.014 (3) | 0.021 (3) | 0.018 (3) | −0.001 (2) | 0.004 (2) | 0.005 (2) |
| C5 | 0.008 (2) | 0.021 (3) | 0.022 (3) | −0.002 (2) | 0.002 (2) | −0.003 (2) |
| Br3 | 0.0185 (3) | 0.0375 (4) | 0.0206 (3) | 0.0007 (2) | −0.0034 (2) | 0.0017 (2) |
| Br2—C2 | 1.862 (5) | N2—C6 | 1.479 (7) |
| Br1—C1 | 1.852 (5) | N2—H2 | 0.8800 |
| C9—O3 | 1.453 (7) | N1—C1 | 1.349 (7) |
| C9—H9A | 0.9800 | N1—H1 | 0.8800 |
| C9—H9B | 0.9800 | O3—C8 | 1.332 (6) |
| C9—H9C | 0.9800 | C6—C7 | 1.520 (7) |
| C4—N1 | 1.368 (7) | C6—H6A | 0.9900 |
| C4—C3 | 1.386 (7) | C6—H6B | 0.9900 |
| C4—C5 | 1.478 (7) | O2—C8 | 1.196 (6) |
| C3—C2 | 1.398 (7) | C1—C2 | 1.387 (7) |
| C3—Br3 | 1.869 (5) | C7—C8 | 1.493 (7) |
| O1—C5 | 1.239 (6) | C7—H7A | 0.9900 |
| N2—C5 | 1.324 (7) | C7—H7B | 0.9900 |
| O3—C9—H9A | 109.5 | N2—C6—H6B | 109.0 |
| O3—C9—H9B | 109.5 | C7—C6—H6B | 109.0 |
| H9A—C9—H9B | 109.5 | H6A—C6—H6B | 107.8 |
| O3—C9—H9C | 109.5 | N1—C1—C2 | 108.6 (5) |
| H9A—C9—H9C | 109.5 | N1—C1—Br1 | 122.5 (4) |
| H9B—C9—H9C | 109.5 | C2—C1—Br1 | 128.9 (4) |
| N1—C4—C3 | 107.0 (4) | C8—C7—C6 | 113.2 (4) |
| N1—C4—C5 | 117.9 (4) | C8—C7—H7A | 108.9 |
| C3—C4—C5 | 135.0 (5) | C6—C7—H7A | 108.9 |
| C4—C3—C2 | 108.2 (4) | C8—C7—H7B | 108.9 |
| C4—C3—Br3 | 128.4 (4) | C6—C7—H7B | 108.9 |
| C2—C3—Br3 | 123.5 (4) | H7A—C7—H7B | 107.7 |
| C5—N2—C6 | 120.9 (4) | C1—C2—C3 | 106.4 (4) |
| C5—N2—H2 | 119.6 | C1—C2—Br2 | 125.9 (4) |
| C6—N2—H2 | 119.6 | C3—C2—Br2 | 127.7 (4) |
| C1—N1—C4 | 109.8 (4) | O2—C8—O3 | 123.4 (5) |
| C1—N1—H1 | 125.1 | O2—C8—C7 | 125.5 (5) |
| C4—N1—H1 | 125.1 | O3—C8—C7 | 111.1 (4) |
| C8—O3—C9 | 116.4 (4) | O1—C5—N2 | 121.3 (5) |
| N2—C6—C7 | 112.8 (4) | O1—C5—C4 | 118.9 (5) |
| N2—C6—H6A | 109.0 | N2—C5—C4 | 119.8 (4) |
| C7—C6—H6A | 109.0 | ||
| N1—C4—C3—C2 | 0.9 (6) | C4—C3—C2—C1 | −0.4 (6) |
| C5—C4—C3—C2 | −175.4 (6) | Br3—C3—C2—C1 | 179.9 (4) |
| N1—C4—C3—Br3 | −179.5 (4) | C4—C3—C2—Br2 | 178.3 (4) |
| C5—C4—C3—Br3 | 4.3 (10) | Br3—C3—C2—Br2 | −1.4 (7) |
| C3—C4—N1—C1 | −1.0 (6) | C9—O3—C8—O2 | 0.7 (8) |
| C5—C4—N1—C1 | 176.0 (5) | C9—O3—C8—C7 | −179.9 (5) |
| C5—N2—C6—C7 | 83.9 (6) | C6—C7—C8—O2 | 2.8 (8) |
| C4—N1—C1—C2 | 0.7 (6) | C6—C7—C8—O3 | −176.7 (4) |
| C4—N1—C1—Br1 | −179.1 (4) | C6—N2—C5—O1 | −6.5 (8) |
| N2—C6—C7—C8 | 73.0 (6) | C6—N2—C5—C4 | 173.5 (5) |
| N1—C1—C2—C3 | −0.2 (6) | N1—C4—C5—O1 | 2.9 (8) |
| Br1—C1—C2—C3 | 179.7 (4) | C3—C4—C5—O1 | 178.8 (6) |
| N1—C1—C2—Br2 | −178.9 (4) | N1—C4—C5—N2 | −177.2 (5) |
| Br1—C1—C2—Br2 | 1.0 (8) | C3—C4—C5—N2 | −1.2 (10) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.88 | 1.89 | 2.751 (6) | 166 |
| Symmetry codes: (i) −x+2, −y+1, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.88 | 1.89 | 2.751 (6) | 166 |
| Symmetry codes: (i) −x+2, −y+1, −z+2. |
We thank the Natural Science Foundation of Guangdong Province, China (No. 06300581), and the Student Science and Technology Program of Jinan University for generously supporting this study.
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Pyrrole derivatives are well known in many marine organisms (Faulkner, 2002), some show important bioactivities, such as antitumor activity (Banwell et al., 2006) and protein kinase inhibiting activity (Sosa et al., 2002). This is the reason why they have attracted our interest. This study follows our previous studies on 3-[(3,4,5-tribromo-1H-pyrrol-2-ylcarbonyl)amino]propanoic acid (Zeng et al., 2006) and 3-bromo-1-methyl-6,7-dihydropyrrolo[2,3-c]azepine-4,8(1H,5H)-dione (Zeng, 2006).
In the crystal structure, molecules of the title compound are linked through N—H···O hydrogen bonds (Table 1) to form centrosymmetric dimers (Fig. 2) of graph-set motif R22(10) (Bernstein et al., 1995). Bond lengths and angles are unexceptional.