Acta Cryst. (2007). E63, o3947 [ doi:10.1107/S1600536807042080 ]
In the title compound, C6H3Cl3O, the molecular geometry approximates C2v symmetry. The hydroxyl H atom lies in the plane of the ring; the closest approach between the centroids of aromatic rings of symmetry-related molecules exceeds 3.8 Å.
A sample of the title compound was donated by the Chemistry Stores at Universidad Autónoma de Nuevo León (UANL), and used without previous recrystallization.
All H atoms were found in a difference map, but their positions regularized in order to get an idealized geometry for C—H and O—H groups. Constrained bond lengths: 0.82 (hydroxyl OH) and 0.93 Å (aromatic CH). Isotropic displacement parameters for H atoms were fixed to Uiso(H1) = 1.5 Ueq(O1); Uiso(H3) = 1.2 Ueq(C3); Uiso(H5) = 1.2 Ueq(C5).
Data collection: XSCANS (Siemens, 1999); cell refinement: XSCANS (Siemens, 1999); data reduction: XSCANS (Siemens, 1999); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 1998); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 1998).
![[Figure 1]](./ng2314fig1thm.gif)
| Fig. 1. The structure of the title molecule, with displacement ellipsoids at the 50% probability level for non-H atoms. |
| C6H3Cl3O | F000 = 392 |
| Mr = 197.43 | Dx = 1.806 Mg m−3 |
| Monoclinic, P21/c | Melting point: 342 K |
| Hall symbol: -P 2ybc | Mo Kα radiation λ = 0.71073 Å |
| a = 3.8181 (18) Å | Cell parameters from 47 reflections |
| b = 15.742 (7) Å | θ = 6.0–12.4º |
| c = 12.127 (6) Å | µ = 1.18 mm−1 |
| β = 95.05 (4)º | T = 297 (1) K |
| V = 726.1 (6) Å3 | Plate, colourless |
| Z = 4 | 0.60 × 0.20 × 0.04 mm |
| Siemens P4 diffractometer | Rint = 0.089 |
| Monochromator: graphite | θmax = 26.0º |
| T = 297(1) K | θmin = 2.1º |
| 2θ/ω scans | h = −4→2 |
| Absorption correction: Gaussian (XSCANS; Siemens, 1999) | k = −19→1 |
| Tmin = 0.792, Tmax = 0.954 | l = −14→14 |
| 2445 measured reflections | 3 standard reflections |
| 1427 independent reflections | every 97 reflections |
| 1086 reflections with I > 2σ(I) | intensity decay: 1.5% |
| 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)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0372P)2 + 0.2366P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 1427 reflections | Δρmax = 0.28 e Å−3 |
| 91 parameters | Δρmin = −0.38 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C6H3Cl3O | V = 726.1 (6) Å3 |
| Mr = 197.43 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 3.8181 (18) Å | µ = 1.18 mm−1 |
| b = 15.742 (7) Å | T = 297 (1) K |
| c = 12.127 (6) Å | 0.60 × 0.20 × 0.04 mm |
| β = 95.05 (4)º |
| Siemens P4 diffractometer | 1086 reflections with I > 2σ(I) |
| Absorption correction: Gaussian (XSCANS; Siemens, 1999) | Rint = 0.089 |
| Tmin = 0.792, Tmax = 0.954 | 3 standard reflections |
| 2445 measured reflections | every 97 reflections |
| 1427 independent reflections | intensity decay: 1.5% |
| R[F2 > 2σ(F2)] = 0.040 | 91 parameters |
| wR(F2) = 0.109 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.28 e Å−3 |
| 1427 reflections | Δρmin = −0.38 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| Cl2 | 1.2802 (2) | 0.10705 (5) | 0.52181 (6) | 0.0599 (3) | |
| Cl4 | 0.6704 (3) | 0.06153 (5) | 0.11139 (7) | 0.0627 (3) | |
| Cl6 | 0.7136 (2) | 0.37081 (5) | 0.29722 (6) | 0.0587 (3) | |
| O1 | 1.1072 (7) | 0.28196 (14) | 0.48426 (17) | 0.0594 (6) | |
| H1 | 1.0670 | 0.3331 | 0.4822 | 0.089* | |
| C1 | 0.9955 (8) | 0.23290 (17) | 0.3971 (2) | 0.0414 (6) | |
| C2 | 1.0664 (7) | 0.14727 (19) | 0.4024 (2) | 0.0420 (6) | |
| C3 | 0.9675 (8) | 0.09404 (17) | 0.3154 (2) | 0.0445 (6) | |
| H3 | 1.0169 | 0.0362 | 0.3200 | 0.053* | |
| C4 | 0.7952 (8) | 0.12773 (17) | 0.2219 (2) | 0.0437 (6) | |
| C5 | 0.7129 (7) | 0.21246 (18) | 0.2133 (2) | 0.0413 (6) | |
| H5 | 0.5911 | 0.2343 | 0.1498 | 0.050* | |
| C6 | 0.8167 (8) | 0.26403 (17) | 0.3019 (2) | 0.0408 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl2 | 0.0671 (5) | 0.0637 (5) | 0.0464 (4) | 0.0052 (4) | −0.0082 (3) | 0.0143 (3) |
| Cl4 | 0.0876 (6) | 0.0460 (4) | 0.0519 (4) | −0.0112 (4) | −0.0086 (4) | −0.0119 (3) |
| Cl6 | 0.0812 (6) | 0.0372 (4) | 0.0559 (5) | 0.0080 (4) | −0.0031 (4) | −0.0018 (3) |
| O1 | 0.0813 (15) | 0.0537 (12) | 0.0406 (11) | 0.0020 (11) | −0.0093 (10) | −0.0117 (9) |
| C1 | 0.0489 (16) | 0.0407 (14) | 0.0347 (12) | −0.0026 (13) | 0.0049 (12) | −0.0037 (11) |
| C2 | 0.0429 (15) | 0.0453 (14) | 0.0374 (13) | 0.0012 (12) | 0.0023 (11) | 0.0040 (11) |
| C3 | 0.0533 (17) | 0.0355 (13) | 0.0447 (15) | 0.0015 (13) | 0.0033 (13) | 0.0034 (11) |
| C4 | 0.0529 (16) | 0.0389 (14) | 0.0396 (14) | −0.0059 (13) | 0.0059 (12) | −0.0031 (11) |
| C5 | 0.0465 (16) | 0.0427 (14) | 0.0338 (13) | −0.0015 (12) | −0.0010 (11) | 0.0009 (10) |
| C6 | 0.0466 (15) | 0.0337 (13) | 0.0419 (13) | 0.0032 (12) | 0.0032 (12) | 0.0016 (11) |
| Cl2—C2 | 1.719 (3) | C2—C3 | 1.374 (4) |
| Cl4—C4 | 1.731 (3) | C3—C4 | 1.366 (4) |
| Cl6—C6 | 1.726 (3) | C3—H3 | 0.9300 |
| O1—C1 | 1.347 (3) | C4—C5 | 1.372 (4) |
| O1—H1 | 0.8200 | C5—C6 | 1.377 (4) |
| C1—C2 | 1.375 (4) | C5—H5 | 0.9300 |
| C1—C6 | 1.379 (4) | ||
| C1—O1—H1 | 119.6 | C3—C4—C5 | 122.1 (3) |
| O1—C1—C2 | 118.5 (3) | C3—C4—Cl4 | 119.2 (2) |
| O1—C1—C6 | 123.5 (3) | C5—C4—Cl4 | 118.7 (2) |
| C2—C1—C6 | 117.9 (2) | C4—C5—C6 | 117.7 (3) |
| C3—C2—C1 | 121.5 (3) | C4—C5—H5 | 121.1 |
| C3—C2—Cl2 | 120.0 (2) | C6—C5—H5 | 121.1 |
| C1—C2—Cl2 | 118.5 (2) | C5—C6—C1 | 122.1 (2) |
| C4—C3—C2 | 118.7 (3) | C5—C6—Cl6 | 120.0 (2) |
| C4—C3—H3 | 120.7 | C1—C6—Cl6 | 117.9 (2) |
| C2—C3—H3 | 120.7 | ||
| O1—C1—C2—C3 | −178.4 (3) | C3—C4—C5—C6 | 1.4 (4) |
| C6—C1—C2—C3 | 0.9 (4) | Cl4—C4—C5—C6 | −179.6 (2) |
| O1—C1—C2—Cl2 | 2.2 (4) | C4—C5—C6—C1 | −0.4 (4) |
| C6—C1—C2—Cl2 | −178.5 (2) | C4—C5—C6—Cl6 | −178.7 (2) |
| C1—C2—C3—C4 | 0.0 (4) | O1—C1—C6—C5 | 178.5 (3) |
| Cl2—C2—C3—C4 | 179.4 (2) | C2—C1—C6—C5 | −0.7 (4) |
| C2—C3—C4—C5 | −1.2 (4) | O1—C1—C6—Cl6 | −3.1 (4) |
| C2—C3—C4—Cl4 | 179.8 (2) | C2—C1—C6—Cl6 | 177.7 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···Cl6 | 0.82 | 2.58 | 2.960 (3) | 110 |
| O1—H1···Cl4i | 0.82 | 2.81 | 3.418 (3) | 132 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
Support by PROVERICyT (IX Verano de la Investigación Científica y Tecnológica UANL) is acknowledged.
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The title molecule has been used in the past as an antiseptic, a pesticide for wood, leather and glue preservation, and also as an antimildew treatment for textiles. However, production was discontinued in the 1980 s and the molecule is no longer used in the USA, mainly because its production process systematically affords small quantities of dioxins and dibenzofurans. This molecule is currently listed as "reasonably anticipated to be a human carcinogen" (US Department of Health and Human Services, 2005). The corresponding phenolate has been used as a ligand for transition and non-transition metal ions, e.g. CuII (Gökaugaç et al., 1999), MnIII (Wesolek et al., 1994), or MgII (Zechmann et al., 2000).
The molecular structure (Fig. 1) approximates a C2v symmetry. However, the molecule is placed on a general position. The hydroxyl H atom lies in the plane of the aromatic ring and is oriented toward Cl6. The corresponding site oriented toward Cl2 is not available for hydroxyl H atom, as, due to crystal symmetry, it would give a short intermolecular H···H contact.
Interestingly, two polymorphs of pentafluorophenol have been reported (Das et al., 2006). For the Z' = 1 polymorph, hydroxyl H atom is placed 0.36 Å above the aromatic ring. A second polymorph, with Z' = 3, shows a variety of hydroxyl conformations. Two molecules are almost planar, with H deviations of 0.10 and 0.04 Å, while the third one has O—H bond almost normal to the aromatic ring, with the H atom placed 0.66 Å out of the benzene mean plane. In the same way, the title compound could present a degree of free rotation about the C—O bond, allowing the stabilization of polymorphic phases.
Regarding the crystal structure, no significant π···π interactions are observed. The closest approach between centroids of aromatic rings of symmetry-related molecules is 3.818 Å.