Acta Cryst. (2009). E65, o1522 [ doi:10.1107/S1600536809021187 ]
In the molecule of the title compound, C9H8BrNO4, the acetate group is close to planar [maximum deviation = 0.042 (3) Å] and is oriented at a dihedral angle of 73.24 (3)° with respect to the aromatic ring. In the crystal structure, intermolecular C-H
O interactions link the molecules into a three-dimensional network, forming R22(10) ring motifs.
For the preparation of the title compound, bromoacetyl bromide (2.01 g) and p-nitrobenzyl alcohol (1.53 g) were added into dichloromethane (30 ml) in pyridine (15 ml) at 273-278 K. The gross products were extracted with n-hexane, washed with water, dried under vaccum, and then recrystallized from dichloromethane (yield; 0.503 g) (Pyun et al., 2001). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.
H atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./hk2706fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./hk2706fig2thm.gif)
| Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C9H8BrNO4 | F(000) = 1088 |
| Mr = 274.07 | Dx = 1.775 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 25 reflections |
| a = 13.851 (3) Å | θ = 10–14° |
| b = 8.1590 (16) Å | µ = 4.00 mm−1 |
| c = 19.201 (4) Å | T = 294 K |
| β = 109.08 (3)° | Block, colorless |
| V = 2050.7 (8) Å3 | 0.20 × 0.10 × 0.10 mm |
| Z = 8 |
| Enraf–Nonius CAD-4 diffractometer | 1055 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.043 |
| graphite | θmax = 25.3°, θmin = 2.2° |
| ω/2θ scans | h = 0→16 |
| Absorption correction: ψ scan (North et al., 1968) | k = −9→9 |
| Tmin = 0.502, Tmax = 0.690 | l = −23→21 |
| 3739 measured reflections | 3 standard reflections every 120 min |
| 1873 independent reflections | intensity decay: 1% |
| 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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.131 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.044P)2] where P = (Fo2 + 2Fc2)/3 |
| 1873 reflections | (Δ/σ)max < 0.001 |
| 136 parameters | Δρmax = 0.49 e Å−3 |
| 0 restraints | Δρmin = −0.46 e Å−3 |
| C9H8BrNO4 | V = 2050.7 (8) Å3 |
| Mr = 274.07 | Z = 8 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 13.851 (3) Å | µ = 4.00 mm−1 |
| b = 8.1590 (16) Å | T = 294 K |
| c = 19.201 (4) Å | 0.20 × 0.10 × 0.10 mm |
| β = 109.08 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 1055 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.043 |
| Tmin = 0.502, Tmax = 0.690 | θmax = 25.3° |
| 3739 measured reflections | 3 standard reflections every 120 min |
| 1873 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
| wR(F2) = 0.131 | Δρmax = 0.49 e Å−3 |
| S = 1.00 | Δρmin = −0.46 e Å−3 |
| 1873 reflections | Absolute structure: ? |
| 136 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 | ||
| Br | 0.14001 (5) | 0.10006 (10) | 0.25541 (4) | 0.0690 (3) | |
| O1 | 0.3414 (6) | −0.3704 (8) | −0.1100 (3) | 0.114 (2) | |
| O2 | 0.3855 (4) | −0.5164 (7) | −0.0136 (3) | 0.0823 (16) | |
| O3 | 0.3187 (3) | 0.2414 (5) | 0.1386 (2) | 0.0474 (10) | |
| O4 | 0.3549 (3) | 0.0826 (5) | 0.2389 (2) | 0.0550 (11) | |
| N | 0.3685 (4) | −0.3840 (8) | −0.0450 (4) | 0.0628 (16) | |
| C1 | 0.3826 (4) | −0.2328 (8) | 0.0002 (3) | 0.0436 (15) | |
| C2 | 0.4247 (4) | −0.2437 (8) | 0.0752 (3) | 0.0485 (16) | |
| H2A | 0.4448 | −0.3443 | 0.0980 | 0.058* | |
| C3 | 0.4364 (5) | −0.1024 (8) | 0.1156 (3) | 0.0508 (15) | |
| H3A | 0.4656 | −0.1081 | 0.1666 | 0.061* | |
| C4 | 0.4064 (4) | 0.0471 (8) | 0.0832 (3) | 0.0428 (15) | |
| C5 | 0.3638 (4) | 0.0536 (8) | 0.0067 (3) | 0.0482 (16) | |
| H5A | 0.3430 | 0.1538 | −0.0164 | 0.058* | |
| C6 | 0.3524 (4) | −0.0851 (8) | −0.0343 (3) | 0.0515 (17) | |
| H6A | 0.3243 | −0.0801 | −0.0854 | 0.062* | |
| C7 | 0.4165 (4) | 0.1993 (8) | 0.1284 (3) | 0.0483 (15) | |
| H7A | 0.4681 | 0.1828 | 0.1762 | 0.058* | |
| H7B | 0.4384 | 0.2893 | 0.1041 | 0.058* | |
| C8 | 0.2977 (4) | 0.1691 (8) | 0.1950 (3) | 0.0429 (14) | |
| C9 | 0.1933 (4) | 0.2229 (8) | 0.1920 (3) | 0.0540 (16) | |
| H9A | 0.1474 | 0.2124 | 0.1417 | 0.065* | |
| H9B | 0.1957 | 0.3377 | 0.2055 | 0.065* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.0593 (4) | 0.0744 (5) | 0.0828 (5) | 0.0128 (4) | 0.0362 (4) | 0.0107 (5) |
| O1 | 0.189 (6) | 0.076 (5) | 0.065 (3) | 0.000 (5) | 0.028 (4) | −0.022 (3) |
| O2 | 0.102 (4) | 0.036 (3) | 0.100 (4) | −0.008 (3) | 0.021 (3) | −0.004 (3) |
| O3 | 0.044 (2) | 0.045 (3) | 0.051 (2) | 0.010 (2) | 0.0132 (18) | 0.003 (2) |
| O4 | 0.044 (2) | 0.056 (3) | 0.061 (2) | 0.010 (2) | 0.012 (2) | 0.020 (3) |
| N | 0.059 (3) | 0.056 (5) | 0.070 (4) | −0.008 (3) | 0.018 (3) | −0.011 (4) |
| C1 | 0.033 (3) | 0.037 (4) | 0.060 (4) | 0.000 (3) | 0.015 (3) | −0.002 (3) |
| C2 | 0.049 (3) | 0.039 (4) | 0.055 (4) | 0.004 (3) | 0.014 (3) | 0.007 (3) |
| C3 | 0.057 (3) | 0.044 (4) | 0.047 (3) | 0.005 (4) | 0.011 (3) | 0.002 (4) |
| C4 | 0.029 (3) | 0.046 (4) | 0.054 (4) | −0.003 (3) | 0.015 (3) | −0.002 (3) |
| C5 | 0.054 (4) | 0.035 (4) | 0.052 (4) | 0.005 (3) | 0.012 (3) | 0.008 (3) |
| C6 | 0.049 (4) | 0.053 (4) | 0.047 (3) | 0.001 (3) | 0.008 (3) | 0.003 (4) |
| C7 | 0.040 (3) | 0.044 (4) | 0.060 (4) | −0.004 (3) | 0.017 (3) | 0.001 (4) |
| C8 | 0.032 (3) | 0.042 (4) | 0.050 (3) | −0.006 (3) | 0.008 (3) | −0.010 (3) |
| C9 | 0.046 (3) | 0.041 (4) | 0.075 (4) | 0.005 (3) | 0.019 (3) | 0.001 (4) |
| Br—C9 | 1.903 (6) | C3—H3A | 0.9300 |
| O3—C7 | 1.470 (6) | C4—C5 | 1.393 (8) |
| O3—C8 | 1.346 (7) | C4—C7 | 1.496 (8) |
| O4—C8 | 1.183 (7) | C5—C6 | 1.359 (8) |
| N—O1 | 1.185 (7) | C5—H5A | 0.9300 |
| N—O2 | 1.222 (7) | C6—H6A | 0.9300 |
| N—C1 | 1.485 (8) | C7—H7A | 0.9700 |
| C1—C2 | 1.367 (8) | C7—H7B | 0.9700 |
| C1—C6 | 1.373 (8) | C8—C9 | 1.494 (8) |
| C2—C3 | 1.370 (8) | C9—H9A | 0.9700 |
| C2—H2A | 0.9300 | C9—H9B | 0.9700 |
| C3—C4 | 1.371 (8) | ||
| C8—O3—C7 | 117.1 (5) | C5—C6—C1 | 119.4 (5) |
| O1—N—O2 | 123.1 (7) | C5—C6—H6A | 120.3 |
| O1—N—C1 | 118.3 (7) | C1—C6—H6A | 120.3 |
| O2—N—C1 | 118.6 (6) | O3—C7—C4 | 110.8 (4) |
| C2—C1—C6 | 121.6 (6) | O3—C7—H7A | 109.5 |
| C2—C1—N | 119.4 (6) | C4—C7—H7A | 109.5 |
| C6—C1—N | 119.0 (6) | O3—C7—H7B | 109.5 |
| C1—C2—C3 | 118.2 (6) | C4—C7—H7B | 109.5 |
| C1—C2—H2A | 120.9 | H7A—C7—H7B | 108.1 |
| C3—C2—H2A | 120.9 | O4—C8—O3 | 124.3 (5) |
| C2—C3—C4 | 121.9 (5) | O4—C8—C9 | 128.1 (6) |
| C2—C3—H3A | 119.0 | O3—C8—C9 | 107.5 (6) |
| C4—C3—H3A | 119.0 | C8—C9—Br | 113.2 (5) |
| C3—C4—C5 | 118.3 (6) | C8—C9—H9A | 108.9 |
| C3—C4—C7 | 121.2 (5) | Br—C9—H9A | 108.9 |
| C5—C4—C7 | 120.5 (6) | C8—C9—H9B | 108.9 |
| C6—C5—C4 | 120.6 (6) | Br—C9—H9B | 108.9 |
| C6—C5—H5A | 119.7 | H9A—C9—H9B | 107.8 |
| C4—C5—H5A | 119.7 | ||
| O1—N—C1—C2 | −172.7 (6) | C4—C5—C6—C1 | 0.5 (9) |
| O2—N—C1—C2 | 7.3 (8) | C2—C1—C6—C5 | −0.5 (9) |
| O1—N—C1—C6 | 7.6 (9) | N—C1—C6—C5 | 179.2 (5) |
| O2—N—C1—C6 | −172.4 (6) | C8—O3—C7—C4 | 85.8 (6) |
| C6—C1—C2—C3 | −0.1 (8) | C3—C4—C7—O3 | −98.5 (6) |
| N—C1—C2—C3 | −179.8 (5) | C5—C4—C7—O3 | 79.9 (6) |
| C1—C2—C3—C4 | 0.6 (9) | C7—O3—C8—O4 | 4.6 (8) |
| C2—C3—C4—C5 | −0.6 (9) | C7—O3—C8—C9 | −177.1 (5) |
| C2—C3—C4—C7 | 177.8 (5) | O4—C8—C9—Br | −13.4 (8) |
| C3—C4—C5—C6 | 0.1 (8) | O3—C8—C9—Br | 168.3 (4) |
| C7—C4—C5—C6 | −178.4 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C7—H7A···O4i | 0.97 | 2.59 | 3.486 (7) | 153 |
| C9—H9B···O4ii | 0.97 | 2.47 | 3.376 (8) | 155 |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C7—H7A···O4i | 0.97 | 2.59 | 3.486 (7) | 153 |
| C9—H9B···O4ii | 0.97 | 2.47 | 3.376 (8) | 155 |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Pyun, D. K., Jeong, W. J., Jung, H. J., Kim, J. H., Lee, J. S., Lee, C. H. & Kim, B. J. (2001). Synlett, 12, 1950–1952.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Some derivatives of p-nitrobenzyl alcohol are important chemical materials. We report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. Atoms O1, O2, N, and C7 are 0.119 (3), -0.161 (3), -0.015 (3) and -0.042 (3) Å away from the plane of ring A, respectively. The moiety (O3/O4/C7-C9) is planar with a maximum deviation of -0.042 (3) Å for atom C7, and it is oriented with respect to ring A at a dihedral angle of 73.24 (3)°.
In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a three-dimensional network forming R22(10) ring motifs (Bernstein et al., 1995) (Fig. 2), in which they may be effective in the stabilization of the structure.