1,3,5-Trichloro-2-methoxy­benzene

Telu, S.; Parkin, S.; Robertson, L.W.; Lehmler, H.-J.

doi:10.1107/S160053680800055X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o424

doi:10.1107/S160053680800055X

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1,3,5-Trichloro-2-methoxybenzene

Sanjay Telu,^a Sean Parkin,^b Larry W. Robertson ^a and Hans-Joachim Lehmler ^a ^*

^aDepartment of Occupational and Environmental Health, University of Iowa, 100 Oakdale Campus, 124 IREH, Iowa City, IA 52242-5000, USA, and ^bDepartment of Chemistry, University of Kentucky, Lexington, KY 40506-0055, USA
^*Correspondence e-mail: hans-joachim-lehmler@uiowa.edu

(Received 14 December 2007; accepted 7 January 2008; online 11 January 2008)

The methoxy group of the title compound, C₇H₅Cl₃O, is rotated out of the plane of the aromatic ring system, with a dihedral angle of 84.11 (13)°, due to the two bulky ortho-chloro substituents.

Related literature

For similar structures of anisoles with two ortho-chloro substituents, see: Rissanen et al. (1987 ); Weller & Gerstner (1995 ); Wieczorek (1980 ). For other related literature, see: Brownlee et al. (1993 ); Curtis et al. (1972 ); Iimura et al. (1984 ); Kolehmainen & Knuutinen (1983 ); Oswald et al. (2005 ); Pereira et al. (2000 ); Rissanen et al. (1988 ); Vlachos et al. (2007 ); Zhang et al. (2006 ).

Experimental

Crystal data

C₇H₅Cl₃O
M_r = 211.46
Monoclinic, P 2₁ /n
a = 14.7538 (5) Å
b = 3.9846 (2) Å
c = 15.4810 (7) Å
β = 115.5031 (19)°
V = 821.42 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 90.0 (2) K
0.25 × 0.25 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.780, T_max = 0.885
13489 measured reflections
1888 independent reflections
1558 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.070
S = 1.13
1888 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 1994 ); software used to prepare material for publication: SHELX97 and local procedures.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800055X/om2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800055X/om2200Isup2.hkl

checkCIF report

Comment top

Chlorinated anisoles are persistent environmental pollutants known for their toxicity and tendency to bioaccumulate (Brownlee et al., 1993). Especially anisoles with chlorine substitution in the 2- and 6- position are a well known cause for off-flavors in water, fish and chicken eggs (Brownlee et al., 1993; Curtis et al., 1972; Zhang et al., 2006). The title compound is a major contributor to "cork taint", a well known off-flavor in the wine industry (Pereira et al., 2000; Vlachos et al., 2007). We herin report the molecular structure of the title compound to aid in structure activity relationship (SAR) studies of the toxicity of chlorinated anisoles.

It has been reported that ortho-disubstitution causes drastic changes in the spatial arrangement of the methoxy group of chlorinated anisols, both in solution and in the solid state (Kolehmainen & Knuutinen, 1983; Rissanen et al., 1987). In the title compound, the methoxy group was rotated out of the plane of the phenyl ring with a dihedral angle of 84.11 (13)°. The angle was calculated between the plane of the benzene ring (C1 through C6) and the methoxy group (atoms C1,O1,C7). Comparable anisoles have similar dihedral angles ranging from 76.8 to 92.1° (Iimura et al., 1984; Rissanen et al., 1987; Rissanen et al., 1988; Weller & Gerstner, 1995; Wieczorek, 1980). In contrast, the methoxy group of non-ortho substituted anisoles lies within the plane of the phenyl ring.

The O—CH₃ bond length of the title compound (O1—C7: 1.446 (2) Å) was larger compared to non-ortho substituted anisoles, which have a mean bond length of 1.422 Å. Furthermore, the C_Ar—O—CH₃ bond angle of the title compound (C1—O1—C7: 114.60 (15)°) was smaller compared to non-ortho substituted anisoles, which is on average 117.73°. Chlorine disubstitution ortho to an aromatic methoxy group had a similar effect on the O—CH₃ bond length and the C_Ar—O—CH₃ bond angles in several structurally related compounds (Iimura et al., 1984; Rissanen et al., 1987; Rissanen et al., 1988; Weller & Gerstner, 1995; Wieczorek, 1980).

Ortho disubstitution forced the methoxy group out of the plane of the aromatic ring, so that the CH₃ group (C7) of the title compound was located 1.192 (4) Å above and the O1 atom -0.079 (3)Å below the calculated least-squares plane of the benzene ring. In other, structurally related compounds with ortho dichloro substitution, the O atoms are positioned 0.030 to 0.133 Å below and the methoxy C atoms 1.119 to 1.252 Å above the calculated last-squares plane (Iimura et al., 1984; Rissanen et al., 1987; Rissanen et al., 1988; Weller & Gerstner, 1995; Wieczorek, 1980). Overall, this difference in the spatial arrangement of the methoxy group is thought to explain the off-flavor of anisoles with ortho disubstitution.

Related literature top

For similar structures of anisoles with two ortho-chlorine substituents, see: Rissanen et al. (1987); Weller & Gerstner (1995); Wieczorek (1980). For other related literature, see: Brownlee et al. (1993); Curtis et al. (1972); Iimura et al. (1984); Kolehmainen & Knuutinen (1983); Oswald et al. (2005); Pereira et al. (2000); Rissanen et al. (1988); Vlachos et al. (2007); Zhang et al. (2006).

Experimental top

Crystals of the title compound suitable for crystal structure analysis were obtained from TCI America (Portland, Oregon, USA.).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELX97 (Sheldrick, 2008) and local procedures.

Figures top

Fig. 1. View of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

1,3,5-Trichloro-2-methoxybenzene top

Crystal data top

C₇H₅Cl₃O	F(000) = 424
M_r = 211.46	D_x = 1.710 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2156 reflections
a = 14.7538 (5) Å	θ = 1.0–27.5°
b = 3.9846 (2) Å	µ = 1.05 mm⁻¹
c = 15.4810 (7) Å	T = 90 K
β = 115.5031 (19)°	Block, colourless
V = 821.42 (6) Å³	0.25 × 0.25 × 0.12 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	1888 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 18 pixels mm^-1	θ_max = 27.5°, θ_min = 1.6°
ω scans at fixed χ = 55°	h = −18→19
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −5→5
T_min = 0.780, T_max = 0.885	l = −20→19
13489 measured reflections

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0244P)² + 0.6499P] where P = (F_o² + 2F_c²)/3
1888 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₇H₅Cl₃O	V = 821.42 (6) Å³
M_r = 211.46	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.7538 (5) Å	µ = 1.05 mm⁻¹
b = 3.9846 (2) Å	T = 90 K
c = 15.4810 (7) Å	0.25 × 0.25 × 0.12 mm
β = 115.5031 (19)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1888 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1558 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.885	R_int = 0.020
13489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.13	Δρ_max = 0.35 e Å⁻³
1888 reflections	Δρ_min = −0.31 e Å⁻³
101 parameters

Special details top

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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.65436 (3)	0.31728 (13)	0.83292 (3)	0.02202 (13)
Cl2	0.36963 (3)	0.90882 (13)	0.91077 (3)	0.01965 (12)
Cl3	0.32350 (3)	0.84337 (13)	0.54775 (3)	0.02053 (13)
O1	0.51708 (9)	0.4751 (4)	0.63059 (9)	0.0189 (3)
C1	0.48575 (13)	0.5887 (5)	0.69659 (13)	0.0161 (4)
C2	0.54027 (13)	0.5242 (5)	0.79404 (13)	0.0161 (4)
C3	0.50643 (13)	0.6209 (5)	0.86111 (13)	0.0162 (4)
H3	0.5447	0.5753	0.9273	0.019*
C4	0.41531 (14)	0.7858 (5)	0.82874 (13)	0.0164 (4)
C5	0.35818 (13)	0.8564 (5)	0.73309 (13)	0.0158 (4)
H5	0.2958	0.9705	0.7126	0.019*
C6	0.39426 (13)	0.7561 (5)	0.66748 (12)	0.0147 (4)
C7	0.58710 (16)	0.6940 (6)	0.61549 (15)	0.0253 (5)
H7A	0.5565	0.9156	0.5951	0.038*
H7B	0.6039	0.5988	0.5659	0.038*
H7C	0.6483	0.7159	0.6753	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0146 (2)	0.0252 (3)	0.0231 (2)	0.00407 (19)	0.00509 (19)	−0.0021 (2)
Cl2	0.0178 (2)	0.0266 (3)	0.0163 (2)	0.00018 (18)	0.00906 (18)	−0.00204 (18)
Cl3	0.0190 (2)	0.0279 (3)	0.0139 (2)	0.00294 (19)	0.00632 (18)	0.00251 (18)
O1	0.0171 (7)	0.0230 (8)	0.0205 (7)	−0.0022 (6)	0.0119 (6)	−0.0046 (6)
C1	0.0160 (9)	0.0152 (10)	0.0188 (9)	−0.0037 (7)	0.0092 (7)	−0.0036 (7)
C2	0.0123 (8)	0.0142 (10)	0.0208 (9)	−0.0003 (7)	0.0061 (7)	−0.0008 (7)
C3	0.0152 (9)	0.0177 (10)	0.0129 (8)	−0.0030 (7)	0.0035 (7)	−0.0009 (7)
C4	0.0177 (9)	0.0160 (10)	0.0184 (9)	−0.0037 (7)	0.0106 (8)	−0.0031 (7)
C5	0.0128 (8)	0.0155 (10)	0.0192 (9)	−0.0002 (7)	0.0069 (7)	0.0005 (7)
C6	0.0138 (9)	0.0168 (10)	0.0120 (8)	−0.0023 (7)	0.0040 (7)	0.0002 (7)
C7	0.0273 (11)	0.0255 (11)	0.0310 (11)	−0.0054 (9)	0.0201 (9)	−0.0052 (9)

Geometric parameters (Å, º) top

C1—O1	1.367 (2)	Cl3—C6	1.7264 (18)
C1—C2	1.394 (3)	C4—C5	1.381 (3)
C1—C6	1.395 (3)	C5—C6	1.393 (3)
C2—C3	1.386 (3)	C5—H5	0.9500
C2—Cl1	1.7329 (19)	O1—C7	1.446 (2)
C3—C4	1.382 (3)	C7—H7A	0.9800
C3—H3	0.9500	C7—H7B	0.9800
Cl2—C4	1.7447 (18)	C7—H7C	0.9800

O1—C1—C2	121.63 (16)	C4—C5—H5	120.8
O1—C1—C6	120.55 (16)	C6—C5—H5	120.8
C2—C1—C6	117.70 (16)	C5—C6—C1	121.46 (16)
C3—C2—C1	122.21 (17)	C5—C6—Cl3	118.74 (14)
C3—C2—Cl1	118.77 (14)	C1—C6—Cl3	119.79 (14)
C1—C2—Cl1	119.02 (14)	C1—O1—C7	114.60 (15)
C4—C3—C2	117.92 (17)	O1—C7—H7A	109.5
C4—C3—H3	121.0	O1—C7—H7B	109.5
C2—C3—H3	121.0	H7A—C7—H7B	109.5
C5—C4—C3	122.34 (17)	O1—C7—H7C	109.5
C5—C4—Cl2	118.33 (14)	H7A—C7—H7C	109.5
C3—C4—Cl2	119.33 (14)	H7B—C7—H7C	109.5
C4—C5—C6	118.36 (17)

O1—C1—C2—C3	−176.17 (17)	Cl2—C4—C5—C6	−179.55 (14)
C6—C1—C2—C3	−0.1 (3)	C4—C5—C6—C1	−0.1 (3)
O1—C1—C2—Cl1	4.0 (3)	C4—C5—C6—Cl3	−179.94 (14)
C6—C1—C2—Cl1	−179.91 (14)	O1—C1—C6—C5	176.18 (17)
C1—C2—C3—C4	0.1 (3)	C2—C1—C6—C5	0.1 (3)
Cl1—C2—C3—C4	179.96 (15)	O1—C1—C6—Cl3	−4.0 (3)
C2—C3—C4—C5	−0.2 (3)	C2—C1—C6—Cl3	179.92 (14)
C2—C3—C4—Cl2	179.51 (15)	C2—C1—O1—C7	−86.2 (2)
C3—C4—C5—C6	0.1 (3)	C6—C1—O1—C7	97.9 (2)

Experimental details

Crystal data
Chemical formula	C₇H₅Cl₃O
M_r	211.46
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	90
a, b, c (Å)	14.7538 (5), 3.9846 (2), 15.4810 (7)
β (°)	115.5031 (19)
V (Å³)	821.42 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.05
Crystal size (mm)	0.25 × 0.25 × 0.12

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.780, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	13489, 1888, 1558
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.070, 1.13
No. of reflections	1888
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.31

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 1994), SHELX97 (Sheldrick, 2008) and local procedures.

Acknowledgements

This research was supported by grant Nos. ES05605, ES012475 and ES013661 from the National Institute of Environmental Health Sciences, NIH.

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