4-Meth­oxy-3-(trifluoro­meth­yl)aniline

He, J.-L.

doi:10.1107/S160053681200030X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o377

doi:10.1107/S160053681200030X

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4-Methoxy-3-(trifluoromethyl)aniline

Jian-Ling He ^a ^*

^aCollege of Chemical and Biological Engineering, Yancheng Institute of Technology, Yinbing Road No. 9 Yancheng, Yancheng 224051, People's Republic of China
^*Correspondence e-mail: jlheyc@163.com

(Received 21 December 2011; accepted 4 January 2012; online 14 January 2012)

In title compound, C₈H₈F₃NO, the methoxy group is inclined at 8.7 (4)° to the benzene ring plane. The crystal structure is stabilized by intermolecular N—H⋯F, N—H⋯N and C—H⋯F hydrogen-bonding interactions.

Related literature

The title compound is an intermediate in the synthesis of trifluoromethyl-containing phthalic acid diamides, which are effective pesticides. For the preparation, see: Feng & Li (2010 ). For the crystal structure of a closely related compound, see: Crampton et al. (2006 ).

Experimental

Crystal data

C₈H₈F₃NO
M_r = 191.15
Orthorhombic, P b c a
a = 5.4140 (11) Å
b = 14.880 (3) Å
c = 21.304 (4) Å
V = 1716.3 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.986, T_max = 0.986
1722 measured reflections
1722 independent reflections
1389 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.162
S = 1.13
1722 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1C⋯F2ⁱ	0.96	2.52	3.292 (3)	138
N—H0A⋯F1ⁱⁱ	0.86	2.44	3.242 (2)	155
N—H0B⋯Nⁱⁱⁱ	0.86	2.47	3.245 (3)	150
Symmetry codes: (i) x+1, y, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200030X/pv2499sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200030X/pv2499Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200030X/pv2499Isup3.cml

checkCIF report

Comment top

The tittle compound (Fig. 1) is used as an important intermediate in the synthesis of trifluoromethyl-containing phthalic acid compounds which are recognized as effective pesticides (Feng & Li, 2010). In the title molecule, the N, O and C8 atoms bonded to the central benzene ring (C2–C7) lie in its plane with methoxy group (O/C1) oriented at 8.7 (4) ° with respect to the benzene ring plane. There is an intramolecular interaction C6—H6A···F3 which stabilizes the molecular structure of the title compound. The crystal structure is stabilized by N—H0A···F1, N—H0B···N and C1—H1C···F2 intermolecular hydrogen bonding interactions. The bond distances and bond angles in the title compound agree with the corresponding bond distances and bond angles reported in a closely related compound (Crampton et al., 2006).

Related literature top

The title compound is an intermediate in the synthesis of trifluoromethyl-containing phthalic acid diamides, which are recognized as effective pesticides. For the preparation, see: Feng & Li (2010). For the crystal structure of a closely related compound, see: Crampton et al. (2006).

Experimental top

The title compound was prepared by a method reported in the literature (Feng & Li, 2010)). A solution of 4-amino-2-(trifluoromethyl)phenol (2 g, 11.3 mmol) in dichloromethane (20 ml) was added slowly to a solution of sodium hydride (0.33 g, 13.6 nmol) in an ice bath. After stirring for 6 h iodomethane (4.8 g, 33.9 mmol) was added slowly in 1 h. After stirring for 48 h at room tempeature, the solvent was evaporated on a rotary evaporator yielding the title compound. Colorless blocks of the title compound were grown in ethanol (20 ml) by slow evaporation of the solvent at room temperature in about 7 days.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound showing hydrogen bonds dashed lines.

4-Methoxy-3-(trifluoromethyl)aniline top

Crystal data top

C₈H₈F₃NO	F(000) = 784
M_r = 191.15	D_x = 1.480 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 5.4140 (11) Å	θ = 3.3–20.0°
b = 14.880 (3) Å	µ = 0.14 mm⁻¹
c = 21.304 (4) Å	T = 293 K
V = 1716.3 (6) Å³	Prism, colorless
Z = 8	0.10 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1722 independent reflections
Radiation source: fine-focus sealed tube	1389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
Detector resolution: 28.5714 pixels mm^-1	θ_max = 26.4°, θ_min = 3.3°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→18
T_min = 0.986, T_max = 0.986	l = 0→26
1722 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.074P)² + 0.3348P] where P = (F_o² + 2F_c²)/3
1722 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₈F₃NO	V = 1716.3 (6) Å³
M_r = 191.15	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 5.4140 (11) Å	µ = 0.14 mm⁻¹
b = 14.880 (3) Å	T = 293 K
c = 21.304 (4) Å	0.10 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1722 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1389 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.986	R_int = 0.000
1722 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.13	Δρ_max = 0.20 e Å⁻³
1722 reflections	Δρ_min = −0.19 e Å⁻³
118 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 > 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.

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

	x	y	z	U_iso*/U_eq
N	0.0910 (3)	0.09833 (11)	0.20799 (9)	0.0642 (5)
H0A	0.1826	0.0524	0.2003	0.077*
H0B	0.0020	0.0998	0.2414	0.077*
F3	−0.3126 (4)	0.39455 (11)	0.21116 (7)	0.1021 (6)
F2	−0.3656 (3)	0.42452 (10)	0.11387 (8)	0.0906 (5)
C7	−0.0486 (4)	0.32133 (13)	0.13969 (9)	0.0548 (5)
F1	−0.0537 (3)	0.47609 (9)	0.16277 (8)	0.0924 (6)
O	0.0805 (4)	0.39518 (12)	0.04733 (8)	0.0872 (6)
C6	−0.0515 (4)	0.24725 (13)	0.17919 (10)	0.0550 (5)
H6A	−0.1479	0.2487	0.2153	0.066*
C5	0.0868 (4)	0.17085 (13)	0.16592 (9)	0.0557 (5)
C8	−0.1937 (4)	0.40274 (15)	0.15659 (10)	0.0643 (6)
C2	0.0907 (4)	0.32022 (15)	0.08453 (10)	0.0653 (6)
C4	0.2268 (5)	0.17158 (16)	0.11146 (11)	0.0719 (7)
H4A	0.3216	0.1214	0.1016	0.086*
C3	0.2297 (5)	0.24452 (18)	0.07140 (11)	0.0767 (7)
H3A	0.3260	0.2427	0.0353	0.092*
C1	0.2463 (6)	0.4017 (2)	−0.00398 (11)	0.0865 (8)
H1A	0.2177	0.4570	−0.0260	0.130*
H1B	0.2203	0.3520	−0.0319	0.130*
H1C	0.4131	0.4005	0.0113	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0752 (12)	0.0474 (10)	0.0699 (11)	0.0025 (8)	0.0031 (9)	0.0081 (8)
F3	0.1383 (15)	0.0767 (10)	0.0912 (11)	0.0339 (10)	0.0413 (10)	0.0151 (8)
F2	0.0887 (10)	0.0811 (11)	0.1018 (11)	0.0177 (8)	−0.0227 (9)	0.0065 (8)
C7	0.0605 (11)	0.0477 (11)	0.0562 (11)	−0.0037 (9)	−0.0035 (10)	0.0018 (8)
F1	0.1106 (12)	0.0541 (8)	0.1124 (12)	−0.0104 (8)	−0.0073 (9)	−0.0123 (7)
O	0.1094 (14)	0.0758 (11)	0.0763 (11)	0.0142 (10)	0.0150 (10)	0.0304 (9)
C6	0.0620 (12)	0.0492 (11)	0.0539 (11)	−0.0033 (9)	0.0009 (10)	0.0014 (8)
C5	0.0625 (12)	0.0482 (11)	0.0563 (11)	−0.0046 (9)	−0.0058 (10)	0.0021 (8)
C8	0.0757 (15)	0.0539 (12)	0.0632 (12)	0.0042 (10)	0.0003 (11)	0.0069 (10)
C2	0.0782 (14)	0.0604 (13)	0.0572 (12)	0.0005 (11)	0.0006 (11)	0.0119 (10)
C4	0.0852 (16)	0.0629 (14)	0.0674 (13)	0.0141 (12)	0.0126 (13)	0.0032 (10)
C3	0.0922 (17)	0.0765 (16)	0.0614 (13)	0.0136 (13)	0.0179 (13)	0.0116 (11)
C1	0.0955 (18)	0.0942 (19)	0.0697 (15)	−0.0139 (15)	0.0077 (15)	0.0258 (14)

Geometric parameters (Å, º) top

N—C5	1.403 (3)	C6—C5	1.390 (3)
N—H0A	0.8600	C6—H6A	0.9300
N—H0B	0.8600	C5—C4	1.386 (3)
F3—C8	1.335 (3)	C2—C3	1.383 (3)
F2—C8	1.342 (3)	C4—C3	1.381 (3)
C7—C6	1.387 (3)	C4—H4A	0.9300
C7—C2	1.396 (3)	C3—H3A	0.9300
C7—C8	1.488 (3)	C1—H1A	0.9600
F1—C8	1.335 (3)	C1—H1B	0.9600
O—C2	1.369 (3)	C1—H1C	0.9600
O—C1	1.418 (3)

C5—N—H0A	120.0	F1—C8—C7	112.9 (2)
C5—N—H0B	120.0	F2—C8—C7	113.50 (19)
H0A—N—H0B	120.0	O—C2—C3	124.6 (2)
C6—C7—C2	120.48 (19)	O—C2—C7	117.1 (2)
C6—C7—C8	119.62 (19)	C3—C2—C7	118.27 (19)
C2—C7—C8	119.89 (18)	C3—C4—C5	122.0 (2)
C2—O—C1	118.4 (2)	C3—C4—H4A	119.0
C7—C6—C5	121.37 (19)	C5—C4—H4A	119.0
C7—C6—H6A	119.3	C4—C3—C2	120.6 (2)
C5—C6—H6A	119.3	C4—C3—H3A	119.7
C4—C5—C6	117.27 (18)	C2—C3—H3A	119.7
C4—C5—N	122.13 (19)	O—C1—H1A	109.5
C6—C5—N	120.53 (19)	O—C1—H1B	109.5
F3—C8—F1	105.23 (19)	H1A—C1—H1B	109.5
F3—C8—F2	106.14 (19)	O—C1—H1C	109.5
F1—C8—F2	105.25 (18)	H1A—C1—H1C	109.5
F3—C8—C7	113.03 (18)	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···F2ⁱ	0.96	2.52	3.292 (3)	138
C6—H6A···F3	0.93	2.35	2.696 (3)	102
N—H0A···F1ⁱⁱ	0.86	2.44	3.242 (2)	155
N—H0B···Nⁱⁱⁱ	0.86	2.47	3.245 (3)	150

Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y−1/2, z; (iii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈F₃NO
M_r	191.15
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	5.4140 (11), 14.880 (3), 21.304 (4)
V (Å³)	1716.3 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.986, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	1722, 1722, 1389
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.162, 1.13
No. of reflections	1722
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···F2ⁱ	0.96	2.52	3.292 (3)	138
N—H0A···F1ⁱⁱ	0.86	2.44	3.242 (2)	155
N—H0B···Nⁱⁱⁱ	0.86	2.47	3.245 (3)	150

Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y−1/2, z; (iii) x−1/2, y, −z+1/2.

Acknowledgements

The author thanks the Center of Testing and Analysis, Nanjing University, for the data collection.

References

Crampton, M. R., Emokpae, T. A., Isanbor, C., Batsanov, A. S., Howard, J. A. K. & Mondal, R. (2006). Eur. J. Org. Chem. pp. 1222–1230. Web of Science CSD CrossRef Google Scholar
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