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access4-Chloro-2,6-dinitrophenol
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The aromatic ring of the title compound, C6H3ClN2O5, is almost planar (r.m.s. deviation = 0.007 Å); one nitro substituent is nearly coplanar with the ring [dihedral angle = 3(1)°], whereas the other is twisted [dihedral angle = 36 (1)°]. The phenol OH group is intramolecularly hydrogen bonded to the nitro group that is coplanar with the ring, generating an S(6) graph-set motif.
Related literature
For the of picric acid, see: Duesler et al. (1978![[Duesler, E. N., Engelmann, J. H., Curtin, D. Y. & Paul, I. C. (1978). Cryst. Struct. Commun. 7, 449-453.]](../../../../../../logos/arrows/e_arr.gif "Duesler, E. N., Engelmann, J. H., Curtin, D. Y. & Paul, I. C. (1978). Cryst. Struct. Commun. 7, 449-453.")
); Soriano-Garcia et al. (1980).
![[Scheme 1]](hg2748scheme1.gif)
Experimental
Crystal data
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810046490/hg2748sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046490/hg2748Isup2.hkl
Commercially available 4-chloro-2,6-dinitrophenol was recrystallized from methanol to yield colorless prisms.
Hydrogen atoms were placed in calculated positions (C–H 0.93 Å) and were included in the in the riding model approximation, with U(H) set to 1.2Ueq(C). The hydroxy H-atom was located in a difference Fourier map, and was refined with a distance restraint of O–H 0.84±0.01 Å.
2,4,6-Trinitrophenol (picric acid) is a strong oxygen acid that dissociates in water. In the solid state, the molecule is nearly flat (Duesler et al., 1978; Soriano-Garcia et al., 1980). 4-Chloro-2,6-dinitrophenol (Scheme I) is also a similarly strong oxygen acid as it dissociates in water completely in water. In the the aromatic ring is nearly co-planar with one nitro substituent (dihedral angle 3(1) °) whereas it is twisted with respect to the other (dihedral angle 36 (1) °) (Fig. 1). The phenolic group is intra-molecularly hydrogen bonded to the nitro group that is co-planar with the ring.
For the of picric acid, see: Duesler et al. (1978); Soriano-Garcia et al. (1980).
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./hg2748fig1thm.gif) | Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 4-chloro-2,6-dinitrophenol at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
| C6H3ClN2O5 | F(000) = 220 |
| Mr = 218.55 | Dx = 1.761 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2yb | Cell parameters from 1662 reflections |
| a = 7.4700 (19) Å | θ = 4.1–27.4° |
| b = 5.8973 (15) Å | µ = 0.46 mm−1 |
| c = 9.952 (2) Å | T = 293 K |
| β = 109.939 (6)° | Prism, colorless |
| V = 412.13 (18) Å3 | 0.24 × 0.21 × 0.18 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID diffractometer | 1434 independent reflections |
| Radiation source: fine-focus sealed tube | 816 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.067 |
| Detector resolution: 10.000 pixels mm-1 | θmax = 25.0°, θmin = 4.1° |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −7→7 |
| Tmin = 0.897, Tmax = 0.922 | l = −11→11 |
| 3209 measured reflections |
| 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)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0358P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 1434 reflections | Δρmax = 0.24 e Å−3 |
| 131 parameters | Δρmin = −0.24 e Å−3 |
| 2 restraints | Absolute structure: Flack (1983), 640 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.14 (14) |
| C6H3ClN2O5 | V = 412.13 (18) Å3 |
| Mr = 218.55 | Z = 2 |
| Monoclinic, P21 | Mo Kα radiation |
| a = 7.4700 (19) Å | µ = 0.46 mm−1 |
| b = 5.8973 (15) Å | T = 293 K |
| c = 9.952 (2) Å | 0.24 × 0.21 × 0.18 mm |
| β = 109.939 (6)° |
| Rigaku R-AXIS RAPID diffractometer | 1434 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 816 reflections with I > 2σ(I) |
| Tmin = 0.897, Tmax = 0.922 | Rint = 0.067 |
| 3209 measured reflections |
| R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.098 | Δρmax = 0.24 e Å−3 |
| S = 1.01 | Δρmin = −0.24 e Å−3 |
| 1434 reflections | Absolute structure: Flack (1983), 640 Friedel pairs |
| 131 parameters | Absolute structure parameter: 0.14 (14) |
| 2 restraints |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.4887 (2) | 0.0000 (3) | 0.86383 (14) | 0.0688 (5) | |
| O1 | 0.3354 (6) | 0.5743 (6) | 0.4395 (4) | 0.0733 (13) | |
| O2 | 0.2527 (5) | 0.8807 (6) | 0.5218 (4) | 0.0721 (13) | |
| O3 | −0.0108 (6) | 0.7765 (6) | 0.6318 (4) | 0.0604 (12) | |
| H3 | −0.101 (7) | 0.774 (12) | 0.664 (7) | 0.10 (3)* | |
| O4 | −0.1986 (6) | 0.6424 (8) | 0.7898 (4) | 0.0729 (14) | |
| O5 | −0.1056 (7) | 0.3531 (8) | 0.9292 (5) | 0.0845 (14) | |
| N1 | 0.2807 (6) | 0.6773 (8) | 0.5258 (5) | 0.0497 (12) | |
| N2 | −0.0885 (7) | 0.4861 (11) | 0.8388 (5) | 0.0594 (13) | |
| C1 | 0.3379 (8) | 0.2247 (7) | 0.7937 (5) | 0.0383 (13) | |
| C2 | 0.3679 (7) | 0.3605 (9) | 0.6918 (6) | 0.0430 (13) | |
| H2 | 0.4672 | 0.3293 | 0.6582 | 0.052* | |
| C3 | 0.2500 (6) | 0.5442 (8) | 0.6390 (5) | 0.0376 (13) | |
| C4 | 0.0974 (7) | 0.5968 (8) | 0.6866 (6) | 0.0425 (13) | |
| C5 | 0.0733 (7) | 0.4491 (8) | 0.7875 (5) | 0.0387 (14) | |
| C6 | 0.1891 (8) | 0.2652 (9) | 0.8411 (6) | 0.0479 (15) | |
| H6 | 0.1666 | 0.1703 | 0.9083 | 0.057* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0706 (9) | 0.0606 (9) | 0.0678 (10) | 0.0225 (9) | 0.0142 (8) | 0.0110 (9) |
| O1 | 0.098 (3) | 0.069 (3) | 0.075 (3) | −0.012 (2) | 0.058 (3) | 0.002 (2) |
| O2 | 0.090 (3) | 0.050 (3) | 0.075 (3) | −0.002 (2) | 0.027 (3) | 0.018 (2) |
| O3 | 0.055 (3) | 0.048 (2) | 0.077 (3) | 0.011 (2) | 0.021 (3) | 0.008 (2) |
| O4 | 0.063 (3) | 0.083 (3) | 0.084 (3) | 0.023 (3) | 0.038 (3) | 0.001 (3) |
| O5 | 0.093 (3) | 0.093 (3) | 0.092 (4) | 0.009 (3) | 0.062 (3) | 0.012 (3) |
| N1 | 0.052 (3) | 0.055 (3) | 0.043 (3) | −0.011 (2) | 0.017 (3) | 0.003 (3) |
| N2 | 0.062 (4) | 0.065 (3) | 0.057 (3) | −0.005 (3) | 0.028 (3) | −0.019 (3) |
| C1 | 0.037 (3) | 0.027 (3) | 0.044 (3) | 0.011 (2) | 0.005 (3) | 0.003 (2) |
| C2 | 0.039 (3) | 0.047 (3) | 0.044 (3) | 0.000 (3) | 0.016 (3) | −0.001 (3) |
| C3 | 0.034 (3) | 0.042 (4) | 0.034 (3) | −0.009 (3) | 0.009 (2) | −0.002 (2) |
| C4 | 0.037 (3) | 0.042 (3) | 0.044 (3) | −0.001 (3) | 0.007 (3) | −0.003 (3) |
| C5 | 0.037 (3) | 0.041 (4) | 0.040 (3) | −0.002 (3) | 0.016 (3) | −0.005 (3) |
| C6 | 0.055 (4) | 0.048 (3) | 0.037 (3) | −0.004 (3) | 0.012 (3) | −0.002 (3) |
| Cl1—C1 | 1.725 (4) | C1—C6 | 1.369 (7) |
| O1—N1 | 1.230 (5) | C1—C2 | 1.369 (6) |
| O2—N1 | 1.216 (5) | C2—C3 | 1.382 (7) |
| O3—C4 | 1.332 (6) | C2—H2 | 0.9300 |
| O3—H3 | 0.84 (6) | C3—C4 | 1.410 (6) |
| O4—N2 | 1.221 (6) | C4—C5 | 1.387 (6) |
| O5—N2 | 1.233 (6) | C5—C6 | 1.376 (7) |
| N1—C3 | 1.454 (6) | C6—H6 | 0.9300 |
| N2—C5 | 1.480 (6) | ||
| C4—O3—H3 | 107 (5) | C2—C3—C4 | 121.9 (5) |
| O2—N1—O1 | 124.0 (5) | C2—C3—N1 | 118.0 (4) |
| O2—N1—C3 | 119.2 (5) | C4—C3—N1 | 120.1 (5) |
| O1—N1—C3 | 116.9 (5) | O3—C4—C5 | 125.9 (5) |
| O4—N2—O5 | 123.3 (5) | O3—C4—C3 | 119.0 (5) |
| O4—N2—C5 | 119.5 (5) | C5—C4—C3 | 115.1 (4) |
| O5—N2—C5 | 117.3 (6) | C6—C5—C4 | 123.8 (4) |
| C6—C1—C2 | 120.7 (5) | C6—C5—N2 | 117.5 (5) |
| C6—C1—Cl1 | 119.3 (4) | C4—C5—N2 | 118.7 (5) |
| C2—C1—Cl1 | 120.0 (4) | C1—C6—C5 | 118.7 (5) |
| C1—C2—C3 | 119.7 (4) | C1—C6—H6 | 120.6 |
| C1—C2—H2 | 120.1 | C5—C6—H6 | 120.6 |
| C3—C2—H2 | 120.1 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O4 | 0.84 (6) | 1.82 (4) | 2.563 (6) | 146 (7) |
Experimental details
| Crystal data | |
| Chemical formula | C6H3ClN2O5 |
| Mr | 218.55 |
| Crystal system, space group | Monoclinic, P21 |
| Temperature (K) | 293 |
| a, b, c (Å) | 7.4700 (19), 5.8973 (15), 9.952 (2) |
| β (°) | 109.939 (6) |
| V (Å3) | 412.13 (18) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.46 |
| Crystal size (mm) | 0.24 × 0.21 × 0.18 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.897, 0.922 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3209, 1434, 816 |
| Rint | 0.067 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.098, 1.01 |
| No. of reflections | 1434 |
| No. of parameters | 131 |
| No. of restraints | 2 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.24, −0.24 |
| Absolute structure | Flack (1983), 640 Friedel pairs |
| Absolute structure parameter | 0.14 (14) |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O4 | 0.84 (6) | 1.82 (4) | 2.563 (6) | 146 (7) |
Acknowledgements
I thank Professor Shan Gao of Heilongjiang University for the diffraction measurements, and the University of Malaya for supporting this study.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Duesler, E. N., Engelmann, J. H., Curtin, D. Y. & Paul, I. C. (1978). Cryst. Struct. Commun. 7, 449–453. CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Soriano-Garcia, M., Srikrishnan, T. & Parthasarathy, R. (1980). Z. Kristallogr. 151, 317–323. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
2,4,6-Trinitrophenol (picric acid) is a strong oxygen acid that dissociates in water. In the solid state, the molecule is nearly flat (Duesler et al., 1978; Soriano-Garcia et al., 1980). 4-Chloro-2,6-dinitrophenol (Scheme I) is also a similarly strong oxygen acid as it dissociates in water completely in water. In the crystal structure, the aromatic ring is nearly co-planar with one nitro substituent (dihedral angle 3(1) °) whereas it is twisted with respect to the other (dihedral angle 36 (1) °) (Fig. 1). The phenolic group is intra-molecularly hydrogen bonded to the nitro group that is co-planar with the ring.