Acta Cryst. (2009). E65, o2319 [ doi:10.1107/S1600536809031444 ]
In the molecule of the title compound, C9H8ClNO4, an intramolecular C-H
O interaction results in the formation of a near-planar (r.m.s. deviation 0.002 Å) five-membered ring, which is oriented at a dihedral angle of 4.07 (4)° with respect to the adjacent aromatic ring. In the crystal structure, intermolecular C-HO interactions link the molecules into a two-dimensional network.
For the preparation of the title compound, chloroacetyl chloride (1.1 g) and 2-nitrobenzyl alcohol (1.53 g) were added into the mixture of pyridine (15 ml) and dichloromethane (30 ml) at 273–278 K. The gross products were extracted with n-hexane, washed with water and dried under vacuum, and then recrystallized from dichloromethane. Finally the title compound was obtained (yield; 0.61 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).
![[Figure 1]](./hk2752fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level. |
![[Figure 2]](./hk2752fig2thm.gif)
| Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C9H8ClNO4 | F(000) = 472 |
| Mr = 229.61 | Dx = 1.462 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 8.0270 (16) Å | θ = 9–13° |
| b = 6.7530 (14) Å | µ = 0.36 mm−1 |
| c = 19.266 (4) Å | T = 294 K |
| β = 92.52 (3)° | Block, yellow |
| V = 1043.3 (4) Å3 | 0.30 × 0.20 × 0.10 mm |
| Z = 4 |
| Enraf–Nonius CAD-4 diffractometer | 891 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.025 |
| graphite | θmax = 25.3°, θmin = 2.1° |
| ω/2θ scans | h = 0→9 |
| Absorption correction: ψ scan (North et al., 1968) | k = 0→8 |
| Tmin = 0.900, Tmax = 0.965 | l = −23→23 |
| 2036 measured reflections | 3 standard reflections every 120 min |
| 1893 independent reflections | intensity decay: 1% |
| 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)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.195 | w = 1/[σ2(Fo2) + (0.07P)2 + 0.84P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max < 0.001 |
| 1893 reflections | Δρmax = 0.28 e Å−3 |
| 137 parameters | Δρmin = −0.23 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: 0.031 (4) |
| C9H8ClNO4 | V = 1043.3 (4) Å3 |
| Mr = 229.61 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.0270 (16) Å | µ = 0.36 mm−1 |
| b = 6.7530 (14) Å | T = 294 K |
| c = 19.266 (4) Å | 0.30 × 0.20 × 0.10 mm |
| β = 92.52 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 891 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
| Tmin = 0.900, Tmax = 0.965 | θmax = 25.3° |
| 2036 measured reflections | 3 standard reflections every 120 min |
| 1893 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.195 | Δρmax = 0.28 e Å−3 |
| S = 1.00 | Δρmin = −0.23 e Å−3 |
| 1893 reflections | Absolute structure: ? |
| 137 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 | ||
| Cl | −0.3781 (2) | 0.3294 (4) | 0.19943 (9) | 0.1458 (10) | |
| O1 | −0.0286 (4) | 0.3868 (6) | 0.25207 (18) | 0.0985 (12) | |
| O2 | −0.0679 (3) | 0.2382 (5) | 0.35365 (15) | 0.0743 (9) | |
| O3 | 0.4281 (5) | 0.3113 (9) | 0.3977 (2) | 0.151 (2) | |
| O4 | 0.5546 (5) | 0.2492 (8) | 0.4935 (3) | 0.161 (2) | |
| N | 0.4264 (5) | 0.2744 (8) | 0.4576 (3) | 0.1028 (16) | |
| C1 | −0.2908 (6) | 0.2341 (10) | 0.2755 (2) | 0.1002 (18) | |
| H1A | −0.3577 | 0.2745 | 0.3137 | 0.120* | |
| H1B | −0.2939 | 0.0906 | 0.2730 | 0.120* | |
| C2 | −0.1141 (6) | 0.2988 (7) | 0.2904 (2) | 0.0722 (13) | |
| C3 | 0.1048 (5) | 0.2696 (7) | 0.3759 (2) | 0.0722 (13) | |
| H3A | 0.1424 | 0.3976 | 0.3600 | 0.087* | |
| H3B | 0.1746 | 0.1680 | 0.3566 | 0.087* | |
| C4 | 0.1165 (5) | 0.2610 (6) | 0.4535 (2) | 0.0559 (10) | |
| C5 | 0.2673 (5) | 0.2629 (7) | 0.4927 (2) | 0.0706 (13) | |
| C6 | 0.2753 (7) | 0.2548 (8) | 0.5642 (3) | 0.0889 (15) | |
| H6A | 0.3780 | 0.2567 | 0.5885 | 0.107* | |
| C7 | 0.1300 (8) | 0.2440 (7) | 0.5994 (3) | 0.0874 (15) | |
| H7A | 0.1332 | 0.2379 | 0.6477 | 0.105* | |
| C8 | −0.0187 (6) | 0.2423 (7) | 0.5624 (2) | 0.0735 (13) | |
| H8A | −0.1173 | 0.2364 | 0.5859 | 0.088* | |
| C9 | −0.0259 (5) | 0.2491 (6) | 0.4913 (2) | 0.0599 (11) | |
| H9A | −0.1294 | 0.2456 | 0.4677 | 0.072* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl | 0.1014 (12) | 0.224 (2) | 0.1105 (13) | 0.0086 (13) | −0.0150 (9) | 0.0395 (14) |
| O1 | 0.101 (3) | 0.116 (3) | 0.080 (2) | −0.014 (2) | 0.0205 (19) | 0.024 (2) |
| O2 | 0.0632 (18) | 0.096 (2) | 0.0641 (19) | −0.0135 (17) | 0.0092 (14) | 0.0080 (17) |
| O3 | 0.074 (2) | 0.267 (7) | 0.115 (3) | −0.035 (3) | 0.041 (2) | −0.036 (4) |
| O4 | 0.055 (2) | 0.222 (6) | 0.205 (5) | 0.002 (3) | 0.001 (3) | 0.003 (4) |
| N | 0.049 (3) | 0.122 (4) | 0.138 (4) | −0.010 (3) | 0.013 (3) | −0.032 (4) |
| C1 | 0.077 (3) | 0.148 (5) | 0.076 (3) | −0.006 (4) | 0.004 (2) | 0.008 (3) |
| C2 | 0.080 (3) | 0.075 (3) | 0.064 (3) | 0.004 (3) | 0.018 (2) | 0.000 (3) |
| C3 | 0.062 (3) | 0.080 (3) | 0.076 (3) | −0.008 (2) | 0.021 (2) | −0.005 (3) |
| C4 | 0.051 (2) | 0.050 (2) | 0.068 (2) | 0.000 (2) | 0.0161 (19) | −0.005 (2) |
| C5 | 0.057 (2) | 0.071 (3) | 0.086 (3) | −0.005 (2) | 0.016 (2) | −0.007 (3) |
| C6 | 0.081 (3) | 0.091 (4) | 0.093 (4) | 0.003 (3) | −0.015 (3) | 0.004 (3) |
| C7 | 0.114 (4) | 0.080 (4) | 0.069 (3) | −0.001 (4) | 0.015 (3) | 0.001 (3) |
| C8 | 0.078 (3) | 0.064 (3) | 0.080 (3) | −0.003 (3) | 0.028 (3) | 0.001 (3) |
| C9 | 0.056 (2) | 0.056 (3) | 0.070 (3) | −0.001 (2) | 0.0164 (19) | −0.001 (2) |
| Cl—C1 | 1.721 (5) | C3—H3B | 0.9700 |
| O1—C2 | 1.189 (5) | C4—C9 | 1.385 (5) |
| O2—C2 | 1.324 (5) | C4—C5 | 1.398 (6) |
| O2—C3 | 1.448 (5) | C5—C6 | 1.378 (6) |
| N—O3 | 1.181 (6) | C6—C7 | 1.377 (7) |
| N—O4 | 1.227 (6) | C6—H6A | 0.9300 |
| N—C5 | 1.472 (6) | C7—C8 | 1.363 (7) |
| C1—C2 | 1.499 (7) | C7—H7A | 0.9300 |
| C1—H1A | 0.9700 | C8—C9 | 1.369 (6) |
| C1—H1B | 0.9700 | C8—H8A | 0.9300 |
| C3—C4 | 1.494 (6) | C9—H9A | 0.9300 |
| C3—H3A | 0.9700 | ||
| C2—O2—C3 | 117.0 (3) | C9—C4—C5 | 115.6 (4) |
| O3—N—O4 | 122.3 (5) | C9—C4—C3 | 120.8 (4) |
| O3—N—C5 | 120.5 (5) | C5—C4—C3 | 123.7 (4) |
| O4—N—C5 | 117.2 (6) | C6—C5—C4 | 122.7 (4) |
| C2—C1—Cl | 113.6 (4) | C6—C5—N | 117.2 (5) |
| C2—C1—H1A | 108.8 | C4—C5—N | 120.0 (4) |
| Cl—C1—H1A | 108.8 | C7—C6—C5 | 119.5 (5) |
| C2—C1—H1B | 108.8 | C7—C6—H6A | 120.3 |
| Cl—C1—H1B | 108.8 | C5—C6—H6A | 120.3 |
| H1A—C1—H1B | 107.7 | C8—C7—C6 | 119.0 (5) |
| O1—C2—O2 | 125.4 (5) | C8—C7—H7A | 120.5 |
| O1—C2—C1 | 126.5 (5) | C6—C7—H7A | 120.5 |
| O2—C2—C1 | 108.1 (4) | C7—C8—C9 | 121.4 (4) |
| O2—C3—C4 | 107.9 (3) | C7—C8—H8A | 119.3 |
| O2—C3—H3A | 110.1 | C9—C8—H8A | 119.3 |
| C4—C3—H3A | 110.1 | C8—C9—C4 | 121.9 (4) |
| O2—C3—H3B | 110.1 | C8—C9—H9A | 119.0 |
| C4—C3—H3B | 110.1 | C4—C9—H9A | 119.0 |
| H3A—C3—H3B | 108.4 | ||
| C3—O2—C2—O1 | −4.6 (7) | O3—N—C5—C6 | −168.6 (6) |
| C3—O2—C2—C1 | 174.4 (4) | O4—N—C5—C6 | 9.6 (8) |
| Cl—C1—C2—O1 | −9.0 (8) | O3—N—C5—C4 | 11.2 (8) |
| Cl—C1—C2—O2 | 172.1 (3) | O4—N—C5—C4 | −170.6 (5) |
| C2—O2—C3—C4 | 159.9 (4) | C4—C5—C6—C7 | 0.2 (8) |
| O2—C3—C4—C9 | −7.0 (6) | N—C5—C6—C7 | 180.0 (5) |
| O2—C3—C4—C5 | 172.5 (4) | C5—C6—C7—C8 | −0.3 (8) |
| C9—C4—C5—C6 | −0.4 (7) | C6—C7—C8—C9 | 0.7 (8) |
| C3—C4—C5—C6 | −180.0 (5) | C7—C8—C9—C4 | −1.0 (7) |
| C9—C4—C5—N | 179.8 (4) | C5—C4—C9—C8 | 0.8 (6) |
| C3—C4—C5—N | 0.2 (7) | C3—C4—C9—C8 | −179.6 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···O3i | 0.97 | 2.43 | 3.372 (6) | 166 |
| C7—H7A···O1ii | 0.93 | 2.58 | 3.374 (6) | 143 |
| C9—H9A···O2 | 0.93 | 2.27 | 2.660 (5) | 104 |
| Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···O3i | 0.97 | 2.43 | 3.372 (6) | 166 |
| C7—H7A···O1ii | 0.93 | 2.58 | 3.374 (6) | 143 |
| C9—H9A···O2 | 0.93 | 2.27 | 2.660 (5) | 104 |
| Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z+1/2. |
The authors thank the Innovation Fund for doctoral theses (BSCX200811), Nanjing University of Technology, for support.
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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 (C4-C9) is, of course, planar. Intramolecular C-H···O interaction (Table 1) results in the formation of a planar five-membered ring B (O2/C3/C4/C9/H9A), which is oriented with respect to the adjacent ring A at a dihedral angle of A/B = 4.07 (4)°.
In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a two dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.