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access2,4-Dinitro-1-phenoxybenzene
aCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
*Correspondence e-mail: duzt@nwsuaf.edu.cn
The title compound, C12H8N2O5, was obtained by the reaction of 1-chloro-2,4-dinitrobenzene and phenol in the presence of potassium carbonate. The nitro-substituted benzene ring lies on a mirror plane, with one NO2 group in the same plane and the other disordered across this plane. The phenoxybenzene unit is placed perpendicular to this mirror, resulting in an exact orthogonal relationship between the phenyl and benzene rings in the molecule. The crystal packing exhibits no significantly short intermolecular contacts.
Related literature
For the synthesis of the title ether, see: Williamson (1852![[Williamson, W. A. (1852). J. Chem. Soc. pp. 229-239.]](../../../../../../logos/arrows/e_arr.gif "Williamson, W. A. (1852). J. Chem. Soc. pp. 229-239.")
); Paul & Gupta (2004). For a related structure, see: Gopal et al. (1980).
![[Scheme 1]](bh2266scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); data reduction: SAINT; 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.
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810001911/bh2266sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001911/bh2266Isup2.hkl
1-Chloro-2,4-dinitrobenzene (10 mmol), potassium carbonate (20 mmol), phenol (6 mmol), and 20 ml of acetone were mixed in a 50 ml flask. After stirring for 2 h. at 373 K, the crude product was obtained. Crystals were obtained by recrystallization from n-hexane/ethyl acetate. Elemental analysis: calculated for C12H8N2O5: C 55.39, H 3.10, N 10.77%; found: C 55.21, H 3.18, N 10.59%.
All H atoms were positioned geometrically, with C—H = 0.93 Å, and refined as riding, with Uiso(H) = 1.2Ueq(carrier C). The was carried-out using a model which includes 16 restraints: in order to converge to a sensible geometry for the phenyl ring mirrored in the symmetry plane, bond lengths C7—C8, C8—C9 and C9—C10 were restrained to 1.39 (1) Å. For the disordered nitro group, bond lengths N1—O2 and N1—O3 were averaged, and atoms N1, O2 and O3 were restrained to have similar displacement parameters.
One of the most common procedures for the synthesis of was originally introduced by Williamson, and involves the reaction of with alkyl halides (Williamson, 1852). This method has been known for nearly 170 years, and remains a very useful transformation in organic synthesis (Paul & Gupta, 2004).
In this paper, we present a new 2,4-dinitro-1-phenoxybenzene, (I), which was synthesized by the reaction of 1-chloro-2,4-dinitrobenzene and phenol, in the presence of potassium carbonate (see Experimental).
In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in related compounds (e.g. Gopal et al., 1980). The angle between the benzene and the phenyl rings is 90° by symmetry. In the no significantly short intermolecular contacts are observed.
For the synthesis of the title ether, see: Williamson (1852); Paul & Gupta (2004). For a related structure, see: Gopal et al. (1980).
Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 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]](./bh2266fig1thm.gif) | Fig. 1. ORTEP drawing of the title complex with atomic numbering scheme and thermal ellipsoids at 30% probability level. Disordered atoms O2 and O3 generated by symmetry x, 1/2-y, z (m plane) have been omitted. Unlabelled atoms in the phenyl ring are generated by symmetry x, 1/2-y, z. |
| C12H8N2O5 | F(000) = 536 |
| Mr = 260.20 | Dx = 1.448 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 1105 reflections |
| a = 21.012 (13) Å | θ = 2.7–21.4° |
| b = 6.917 (4) Å | µ = 0.12 mm−1 |
| c = 8.211 (5) Å | T = 298 K |
| V = 1193.4 (12) Å3 | Block, red |
| Z = 4 | 0.50 × 0.47 × 0.45 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 1150 independent reflections |
| Radiation source: fine-focus sealed tube | 639 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.069 |
| φ and ω scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→25 |
| Tmin = 0.945, Tmax = 0.950 | k = −8→8 |
| 5246 measured reflections | l = −5→9 |
| 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)] = 0.066 | H-atom parameters constrained |
| wR(F2) = 0.220 | w = 1/[σ2(Fo2) + (0.1048P)2 + 0.4983P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 1150 reflections | Δρmax = 0.30 e Å−3 |
| 117 parameters | Δρmin = −0.20 e Å−3 |
| 16 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 constraints | Extinction coefficient: 0.023 (6) |
| Primary atom site location: structure-invariant direct methods |
| C12H8N2O5 | V = 1193.4 (12) Å3 |
| Mr = 260.20 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 21.012 (13) Å | µ = 0.12 mm−1 |
| b = 6.917 (4) Å | T = 298 K |
| c = 8.211 (5) Å | 0.50 × 0.47 × 0.45 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 1150 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 639 reflections with I > 2σ(I) |
| Tmin = 0.945, Tmax = 0.950 | Rint = 0.069 |
| 5246 measured reflections |
| R[F2 > 2σ(F2)] = 0.066 | 16 restraints |
| wR(F2) = 0.220 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.30 e Å−3 |
| 1150 reflections | Δρmin = −0.20 e Å−3 |
| 117 parameters |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| N1 | 0.4600 (2) | 0.2500 | 0.9620 (5) | 0.0970 (18) | |
| N2 | 0.5869 (2) | 0.2500 | 0.4695 (6) | 0.0782 (13) | |
| O1 | 0.35033 (13) | 0.2500 | 0.7731 (4) | 0.0844 (13) | |
| O2 | 0.4181 (2) | 0.3065 (14) | 1.0352 (6) | 0.120 (3) | 0.50 |
| O3 | 0.5041 (3) | 0.1576 (11) | 1.0291 (7) | 0.146 (3) | 0.50 |
| O4 | 0.63351 (19) | 0.2500 | 0.5549 (6) | 0.1135 (17) | |
| O5 | 0.5895 (2) | 0.2500 | 0.3233 (6) | 0.1127 (16) | |
| C1 | 0.4064 (2) | 0.2500 | 0.6926 (6) | 0.0600 (13) | |
| C2 | 0.4620 (2) | 0.2500 | 0.7843 (5) | 0.0597 (13) | |
| C3 | 0.5208 (2) | 0.2500 | 0.7124 (6) | 0.0641 (13) | |
| H3 | 0.5577 | 0.2500 | 0.7752 | 0.077* | |
| C4 | 0.5240 (2) | 0.2500 | 0.5464 (6) | 0.0590 (12) | |
| C5 | 0.4704 (2) | 0.2500 | 0.4509 (6) | 0.0633 (13) | |
| H5 | 0.4738 | 0.2500 | 0.3380 | 0.076* | |
| C6 | 0.4115 (2) | 0.2500 | 0.5237 (6) | 0.0662 (14) | |
| H6 | 0.3750 | 0.2500 | 0.4598 | 0.079* | |
| C7 | 0.2935 (2) | 0.2500 | 0.6851 (6) | 0.0691 (15) | |
| C8 | 0.26597 (18) | 0.4227 (7) | 0.6495 (5) | 0.0960 (14) | |
| H8 | 0.2854 | 0.5386 | 0.6781 | 0.115* | |
| C9 | 0.2084 (2) | 0.4202 (10) | 0.5698 (6) | 0.130 (2) | |
| H9 | 0.1891 | 0.5362 | 0.5410 | 0.155* | |
| C10 | 0.1795 (3) | 0.2500 | 0.5328 (9) | 0.139 (4) | |
| H10 | 0.1400 | 0.2500 | 0.4820 | 0.167* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.055 (3) | 0.182 (5) | 0.054 (3) | 0.000 | −0.006 (2) | 0.000 |
| N2 | 0.071 (3) | 0.089 (3) | 0.074 (3) | 0.000 | 0.015 (3) | 0.000 |
| O1 | 0.053 (2) | 0.149 (4) | 0.0508 (19) | 0.000 | −0.0026 (16) | 0.000 |
| O2 | 0.089 (3) | 0.209 (10) | 0.062 (3) | 0.054 (4) | −0.001 (2) | −0.017 (4) |
| O3 | 0.146 (4) | 0.223 (8) | 0.070 (3) | 0.075 (5) | −0.013 (3) | 0.022 (4) |
| O4 | 0.061 (2) | 0.181 (5) | 0.099 (3) | 0.000 | 0.015 (2) | 0.000 |
| O5 | 0.100 (3) | 0.161 (4) | 0.077 (3) | 0.000 | 0.030 (2) | 0.000 |
| C1 | 0.052 (3) | 0.074 (3) | 0.054 (3) | 0.000 | 0.000 (2) | 0.000 |
| C2 | 0.053 (3) | 0.076 (3) | 0.050 (2) | 0.000 | −0.003 (2) | 0.000 |
| C3 | 0.055 (3) | 0.076 (3) | 0.061 (3) | 0.000 | −0.006 (2) | 0.000 |
| C4 | 0.055 (3) | 0.057 (3) | 0.065 (3) | 0.000 | 0.008 (2) | 0.000 |
| C5 | 0.074 (3) | 0.069 (3) | 0.047 (3) | 0.000 | 0.004 (2) | 0.000 |
| C6 | 0.062 (3) | 0.082 (3) | 0.054 (3) | 0.000 | −0.007 (2) | 0.000 |
| C7 | 0.049 (3) | 0.110 (4) | 0.048 (3) | 0.000 | 0.000 (2) | 0.000 |
| C8 | 0.085 (3) | 0.120 (4) | 0.083 (3) | 0.007 (3) | −0.004 (2) | 0.016 (3) |
| C9 | 0.089 (4) | 0.209 (7) | 0.091 (3) | 0.044 (4) | −0.003 (3) | 0.042 (4) |
| C10 | 0.055 (4) | 0.299 (14) | 0.063 (4) | 0.000 | −0.006 (3) | 0.000 |
| N1—O2i | 1.137 (6) | C3—C4 | 1.365 (6) |
| N1—O2 | 1.137 (6) | C3—H3 | 0.9300 |
| N1—O3 | 1.253 (6) | C4—C5 | 1.373 (6) |
| N1—O3i | 1.253 (6) | C5—C6 | 1.373 (6) |
| N1—C2 | 1.459 (6) | C5—H5 | 0.9300 |
| N2—O5 | 1.202 (6) | C6—H6 | 0.9300 |
| N2—O4 | 1.204 (6) | C7—C8i | 1.358 (5) |
| N2—C4 | 1.465 (6) | C7—C8 | 1.358 (5) |
| O1—C1 | 1.351 (5) | C8—C9 | 1.375 (5) |
| O1—C7 | 1.397 (5) | C8—H8 | 0.9300 |
| O2—O2i | 0.78 (2) | C9—C10 | 1.360 (6) |
| O3—O3i | 1.278 (15) | C9—H9 | 0.9300 |
| C1—C2 | 1.389 (6) | C10—C9i | 1.360 (6) |
| C1—C6 | 1.391 (6) | C10—H10 | 0.9300 |
| C2—C3 | 1.371 (6) | ||
| O2i—N1—O3 | 99.5 (6) | C3—C4—C5 | 122.0 (4) |
| O2—N1—O3 | 121.1 (6) | C3—C4—N2 | 118.3 (4) |
| O2i—N1—O3i | 121.1 (6) | C5—C4—N2 | 119.6 (4) |
| O2—N1—O3i | 99.5 (6) | C6—C5—C4 | 119.4 (4) |
| O2i—N1—C2 | 123.4 (4) | C6—C5—H5 | 120.3 |
| O2—N1—C2 | 123.4 (4) | C4—C5—H5 | 120.3 |
| O3—N1—C2 | 114.8 (4) | C5—C6—C1 | 120.2 (4) |
| O3i—N1—C2 | 114.8 (4) | C5—C6—H6 | 119.9 |
| O5—N2—O4 | 123.1 (5) | C1—C6—H6 | 119.9 |
| O5—N2—C4 | 118.1 (5) | C8i—C7—C8 | 123.1 (5) |
| O4—N2—C4 | 118.8 (5) | C8i—C7—O1 | 118.4 (3) |
| C1—O1—C7 | 119.5 (4) | C8—C7—O1 | 118.4 (3) |
| O1—C1—C2 | 117.9 (4) | C7—C8—C9 | 117.7 (5) |
| O1—C1—C6 | 123.7 (4) | C7—C8—H8 | 121.1 |
| C2—C1—C6 | 118.4 (4) | C9—C8—H8 | 121.1 |
| C3—C2—C1 | 121.6 (4) | C10—C9—C8 | 120.7 (6) |
| C3—C2—N1 | 117.1 (4) | C10—C9—H9 | 119.7 |
| C1—C2—N1 | 121.3 (4) | C8—C9—H9 | 119.7 |
| C4—C3—C2 | 118.3 (4) | C9—C10—C9i | 120.0 (7) |
| C4—C3—H3 | 120.9 | C9—C10—H10 | 120.0 |
| C2—C3—H3 | 120.9 | C9i—C10—H10 | 120.0 |
| Symmetry code: (i) x, −y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C5—H5···O3ii | 0.93 | 2.69 | 3.593 (8) | 163 |
| C9—H9···O2iii | 0.93 | 2.50 | 3.274 (8) | 141 |
| Symmetry codes: (ii) x, y, z−1; (iii) −x+1/2, −y+1, z−1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C12H8N2O5 |
| Mr | 260.20 |
| Crystal system, space group | Orthorhombic, Pnma |
| Temperature (K) | 298 |
| a, b, c (Å) | 21.012 (13), 6.917 (4), 8.211 (5) |
| V (Å3) | 1193.4 (12) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.12 |
| Crystal size (mm) | 0.50 × 0.47 × 0.45 |
| Data collection | |
| Diffractometer | Bruker SMART APEX CCD area-detector |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.945, 0.950 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5246, 1150, 639 |
| Rint | 0.069 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.220, 1.03 |
| No. of reflections | 1150 |
| No. of parameters | 117 |
| No. of restraints | 16 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.30, −0.20 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge the support of the Foundation of Northwest A&F University.
References
Gopal, R., Chandler, W. D. & Robertson, B. E. (1980). Can. J. Chem. 58, 658–663. CrossRef CAS Web of Science Google Scholar
Paul, S. & Gupta, M. (2004). Tetrahedron Lett. 45, 8825–8829. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Williamson, W. A. (1852). J. Chem. Soc. pp. 229–239. Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
One of the most common procedures for the synthesis of ethers was originally introduced by Williamson, and involves the reaction of alkoxides with alkyl halides (Williamson, 1852). This method has been known for nearly 170 years, and remains a very useful transformation in organic synthesis (Paul & Gupta, 2004).
In this paper, we present a new crystal structure, 2,4-dinitro-1-phenoxybenzene, (I), which was synthesized by the reaction of 1-chloro-2,4-dinitrobenzene and phenol, in the presence of potassium carbonate (see Experimental).
In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in related compounds (e.g. Gopal et al., 1980). The angle between the benzene and the phenyl rings is 90° by symmetry. In the crystal structure, no significantly short intermolecular contacts are observed.