2-{[2-Chloro-5-(trifluoro­meth­yl)phen­yl]imino­meth­yl]phenol

Yang, M.-H.; Zheng, Y.-F.

doi:10.1107/S1600536807057017

2-{[2-Chloro-5-(trifluoromethyl)phenyl]iminomethyl]phenol

M.-H. Yang and Y.-F. Zheng

In the title molecule, C₁₄H₁₉ClF₃NO, an intramolecular O—H

N hydrogen bond influences the molecular conformation; the two benzene rings make a dihedral angle of 47.7 (3)°. The crystal packing exhibits no classical intermolecular hydrogen bonds. One CF~3~ group is disordered over two positions; the site occupancy factors are 0.7 and 0.3.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057017/cv2348sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057017/cv2348Isup2.hkl Contains datablock I

CCDC reference: 672918

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.030
wR factor = 0.070
Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for       C13'

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT301_ALERT_3_C Main Residue  Disorder .........................      17.00 Perc.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         69

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes (Johnson et al., 1996; Alizadeh et al., 1999; Wang & Zheng, 2007). Schiff bases that have solvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (non-linear optically active) materials (Alemi & Shaabani, 2000). They are also useful in the asymmetric oxidation of methyl phenyl sulfide and are enantioselective (Kim & Shin, 1999). In this paper, we report the synthesis and crystal structure of the title compound, (I).

The molecular structure of the title compound is ramification of Schiff base (Fig. 1) The C7—N1 bond length is 1.283 (2) Å, indicative of a C═N double bond. The C—Cl, C—O and C—C distances are unremarkable. The dihedral angle between the two benzene rings is 47.7 (3) Å.

Related literature top

For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Johnson et al. (1996); Kim & Shin (1999); Wang & Zheng (2007).

Experimental top

Under nitrogen, a mixture of 2-chloro-5-(trifluoromethyl)aniline (1.95 g, 10 mmol), Na₂SO₄ (3.0 g) and 2-hydroxybenzaldehyde (1.22 g, 10 mmol) in absolute ethanol (20 ml) was refluxed for about 12 h to yield a yellow precipitate. The product was collected by vacuum filtration and washed with ethanol. The crude solid was redissolved in CH₂Cl₂ (100 ml) and washed with water (2 x 15 ml) and brine (8 ml). After drying over Na₂SO₄, the solvent was removed under vacuum, and a yellow solid was isolated in 90% yield (2.70 g). Colourless single crystals of the Schiff base, (I), suitable for X-ray analysis were grown from CH₂Cl₂ and absolute ethanol (4:1) by slow evaporation of the solvents at room temperature over a period of about three weeks.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top

Fig. 1. The molecular structure of (I), showing the atomic numbering scheme, disordered CF₃ group and 30% probability displacement ellipsoids.

2-{[2-Chloro-5-(trifluoromethyl)phenyl]iminomethyl]phenol top

Crystal data top

C₁₄H₉ClF₃NO	F(000) = 608
M_r = 299.67	D_x = 1.518 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2303 reflections
a = 12.979 (6) Å	θ = 3.0–25.2°
b = 7.418 (3) Å	µ = 0.32 mm⁻¹
c = 13.881 (6) Å	T = 298 K
β = 101.064 (7)°	Block, colourless
V = 1311.6 (10) Å³	0.28 × 0.22 × 0.15 mm
Z = 4

Data collection top

Bruker APEX-II area-detector diffractometer	2303 independent reflections
Radiation source: fine-focus sealed tube	1411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scan	θ_max = 25.2°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→14
T_min = 0.916, T_max = 0.954	k = −8→8
7694 measured reflections	l = −16→16

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 = 0.96	w = 1/[σ²(F_o²) + (0.0314P)²] where P = (F_o² + 2F_c²)/3
2303 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.12 e Å⁻³
69 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₄H₉ClF₃NO	V = 1311.6 (10) Å³
M_r = 299.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.979 (6) Å	µ = 0.32 mm⁻¹
b = 7.418 (3) Å	T = 298 K
c = 13.881 (6) Å	0.28 × 0.22 × 0.15 mm
β = 101.064 (7)°

Data collection top

Bruker APEX-II area-detector diffractometer	2303 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1411 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.954	R_int = 0.029
7694 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	69 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 0.96	Δρ_max = 0.12 e Å⁻³
2303 reflections	Δρ_min = −0.16 e Å⁻³
210 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	Occ. (<1)
Cl1	0.63136 (4)	0.08790 (6)	0.59424 (3)	0.0854 (2)
O1	0.40859 (9)	0.40057 (17)	0.42934 (8)	0.0778 (3)
H1	0.4706	0.3721	0.4451	0.117*
N1	0.58895 (10)	0.27658 (15)	0.40482 (9)	0.0545 (3)
C8	0.69623 (12)	0.24343 (18)	0.44034 (10)	0.0519 (4)
C7	0.54804 (12)	0.24459 (18)	0.31476 (11)	0.0528 (4)
H7	0.5896	0.1956	0.2738	0.063*
C6	0.43864 (12)	0.28297 (19)	0.27537 (10)	0.0512 (4)
C5	0.39664 (14)	0.2422 (2)	0.17731 (11)	0.0652 (4)
H5	0.4397	0.1934	0.1376	0.078*
C1	0.37309 (13)	0.3581 (2)	0.33403 (12)	0.0592 (4)
C14	0.77401 (13)	0.29778 (19)	0.39131 (11)	0.0565 (4)
H14	0.7558	0.3553	0.3309	0.068*
C9	0.72630 (14)	0.15890 (19)	0.53128 (11)	0.0604 (4)
C12	0.87901 (13)	0.2676 (2)	0.43115 (12)	0.0614 (4)
C11	0.90654 (15)	0.1808 (2)	0.52090 (13)	0.0745 (5)
H11	0.9768	0.1594	0.5476	0.089*
C4	0.29257 (17)	0.2735 (2)	0.13898 (14)	0.0813 (5)
H4	0.2649	0.2448	0.0739	0.098*
C2	0.26852 (15)	0.3908 (2)	0.29453 (15)	0.0773 (5)
H2	0.2248	0.4415	0.3330	0.093*
C3	0.22978 (16)	0.3476 (2)	0.19782 (17)	0.0866 (6)
H3	0.1594	0.3691	0.1717	0.104*
C10	0.82995 (16)	0.1266 (2)	0.57015 (12)	0.0741 (5)
H10	0.8483	0.0678	0.6302	0.089*
C13	0.96069 (17)	0.3228 (3)	0.37635 (16)	0.0797 (5)	0.70 (3)
F3	0.9374 (6)	0.4774 (8)	0.3282 (6)	0.1087 (17)	0.70 (3)
F1	1.0542 (5)	0.3515 (13)	0.4326 (4)	0.1155 (19)	0.70 (3)
F2	0.9751 (7)	0.2058 (7)	0.3093 (5)	0.1148 (16)	0.70 (3)
C13'	0.96069 (17)	0.3228 (3)	0.37635 (16)	0.0797 (5)	0.30 (3)
F1'	1.0556 (10)	0.290 (4)	0.4232 (15)	0.146 (6)	0.30 (3)
F2'	0.951 (2)	0.231 (3)	0.2911 (15)	0.170 (7)	0.30 (3)
F3'	0.957 (2)	0.4929 (17)	0.350 (2)	0.131 (6)	0.30 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0968 (4)	0.0917 (4)	0.0741 (3)	0.0008 (3)	0.0328 (3)	0.0167 (2)
O1	0.0701 (8)	0.0978 (9)	0.0688 (7)	0.0127 (7)	0.0216 (6)	−0.0104 (6)
N1	0.0546 (9)	0.0567 (8)	0.0526 (8)	0.0022 (6)	0.0110 (6)	−0.0008 (6)
C8	0.0556 (11)	0.0490 (9)	0.0510 (9)	0.0032 (8)	0.0102 (8)	−0.0045 (7)
C7	0.0571 (11)	0.0469 (9)	0.0583 (10)	−0.0016 (8)	0.0209 (8)	−0.0001 (7)
C6	0.0509 (10)	0.0478 (9)	0.0552 (9)	−0.0044 (7)	0.0108 (8)	0.0043 (7)
C5	0.0714 (13)	0.0601 (11)	0.0624 (11)	−0.0095 (9)	0.0083 (9)	0.0014 (8)
C1	0.0545 (12)	0.0570 (10)	0.0674 (11)	0.0005 (8)	0.0147 (9)	0.0049 (8)
C14	0.0583 (12)	0.0579 (10)	0.0536 (9)	0.0036 (8)	0.0115 (8)	−0.0011 (7)
C9	0.0685 (12)	0.0595 (10)	0.0547 (10)	0.0027 (8)	0.0157 (8)	−0.0002 (8)
C12	0.0548 (11)	0.0659 (11)	0.0630 (10)	0.0009 (9)	0.0096 (8)	−0.0062 (8)
C11	0.0610 (12)	0.0867 (13)	0.0705 (11)	0.0109 (10)	−0.0006 (10)	−0.0023 (10)
C4	0.0799 (15)	0.0759 (13)	0.0779 (12)	−0.0108 (11)	−0.0101 (11)	0.0056 (10)
C2	0.0593 (13)	0.0732 (13)	0.1010 (15)	0.0071 (10)	0.0194 (10)	0.0066 (11)
C3	0.0573 (13)	0.0765 (13)	0.1162 (17)	−0.0031 (10)	−0.0077 (13)	0.0165 (12)
C10	0.0781 (14)	0.0836 (13)	0.0571 (10)	0.0129 (11)	0.0042 (10)	0.0082 (9)
C13	0.0599 (15)	0.0961 (18)	0.0825 (15)	−0.0006 (14)	0.0125 (12)	−0.0028 (14)
F3	0.079 (2)	0.129 (4)	0.126 (3)	−0.006 (2)	0.0405 (17)	0.032 (2)
F1	0.063 (3)	0.174 (4)	0.107 (3)	−0.030 (3)	0.0110 (19)	−0.017 (4)
F2	0.107 (3)	0.125 (4)	0.128 (3)	−0.0154 (18)	0.064 (2)	−0.0488 (19)
C13'	0.0599 (15)	0.0961 (18)	0.0825 (15)	−0.0006 (14)	0.0125 (12)	−0.0028 (14)
F1'	0.045 (6)	0.182 (12)	0.210 (14)	0.024 (7)	0.020 (7)	0.094 (9)
F2'	0.133 (10)	0.278 (18)	0.116 (7)	−0.051 (9)	0.070 (6)	−0.053 (7)
F3'	0.116 (10)	0.084 (7)	0.206 (13)	−0.007 (5)	0.061 (8)	0.036 (6)

Geometric parameters (Å, º) top

Cl1—C9	1.7242 (17)	C14—H14	0.9300
O1—C1	1.3520 (18)	C9—C10	1.371 (2)
O1—H1	0.8200	C12—C11	1.387 (2)
N1—C7	1.2831 (18)	C12—C13	1.477 (2)
N1—C8	1.4068 (19)	C11—C10	1.370 (2)
C8—C14	1.382 (2)	C11—H11	0.9300
C8—C9	1.396 (2)	C4—C3	1.374 (3)
C7—C6	1.449 (2)	C4—H4	0.9300
C7—H7	0.9300	C2—C3	1.378 (2)
C6—C5	1.399 (2)	C2—H2	0.9300
C6—C1	1.401 (2)	C3—H3	0.9300
C5—C4	1.373 (2)	C10—H10	0.9300
C5—H5	0.9300	C13—F2	1.312 (5)
C1—C2	1.384 (2)	C13—F1	1.329 (5)
C14—C12	1.387 (2)	C13—F3	1.333 (5)

C7—N1—C8	120.38 (13)	C11—C12—C13	120.32 (18)
C14—C8—C9	118.20 (15)	C14—C12—C13	119.83 (17)
C14—C8—N1	122.96 (13)	C10—C11—C12	119.86 (17)
C9—C8—N1	118.78 (14)	C10—C11—H11	120.1
N1—C7—C6	121.59 (14)	C12—C11—H11	120.1
N1—C7—H7	119.2	C5—C4—C3	119.25 (18)
C6—C7—H7	119.2	C5—C4—H4	120.4
C5—C6—C1	119.00 (15)	C3—C4—H4	120.4
C5—C6—C7	119.71 (15)	C3—C2—C1	119.47 (18)
C1—C6—C7	121.28 (14)	C3—C2—H2	120.3
C4—C5—C6	120.75 (18)	C1—C2—H2	120.3
C4—C5—H5	119.6	C4—C3—C2	121.66 (18)
C6—C5—H5	119.6	C4—C3—H3	119.2
O1—C1—C2	118.10 (15)	C2—C3—H3	119.2
O1—C1—C6	122.03 (15)	C11—C10—C9	120.22 (16)
C2—C1—C6	119.86 (16)	C11—C10—H10	119.9
C8—C14—C12	120.75 (15)	C9—C10—H10	119.9
C8—C14—H14	119.6	F2—C13—F1	106.5 (4)
C12—C14—H14	119.6	F2—C13—F3	105.3 (4)
C10—C9—C8	121.14 (15)	F1—C13—F3	104.5 (4)
C10—C9—Cl1	119.33 (13)	F2—C13—C12	113.4 (3)
C8—C9—Cl1	119.50 (13)	F1—C13—C12	114.0 (3)
C11—C12—C14	119.81 (16)	F3—C13—C12	112.4 (4)

C7—N1—C8—C14	46.70 (19)	C8—C14—C12—C13	178.50 (16)
C7—N1—C8—C9	−136.21 (14)	C14—C12—C11—C10	−0.5 (2)
C8—N1—C7—C6	−177.93 (12)	C13—C12—C11—C10	−178.58 (17)
N1—C7—C6—C5	−178.56 (13)	C6—C5—C4—C3	0.7 (3)
N1—C7—C6—C1	0.5 (2)	O1—C1—C2—C3	−179.45 (15)
C1—C6—C5—C4	−0.6 (2)	C6—C1—C2—C3	0.5 (2)
C7—C6—C5—C4	178.46 (14)	C5—C4—C3—C2	−0.2 (3)
C5—C6—C1—O1	179.94 (13)	C1—C2—C3—C4	−0.4 (3)
C7—C6—C1—O1	0.9 (2)	C12—C11—C10—C9	−0.4 (3)
C5—C6—C1—C2	0.0 (2)	C8—C9—C10—C11	1.4 (2)
C7—C6—C1—C2	−179.07 (13)	Cl1—C9—C10—C11	179.52 (13)
C9—C8—C14—C12	0.5 (2)	C11—C12—C13—F2	96.0 (5)
N1—C8—C14—C12	177.65 (13)	C14—C12—C13—F2	−82.1 (5)
C14—C8—C9—C10	−1.5 (2)	C11—C12—C13—F1	−26.1 (5)
N1—C8—C9—C10	−178.71 (13)	C14—C12—C13—F1	155.8 (5)
C14—C8—C9—Cl1	−179.58 (11)	C11—C12—C13—F3	−144.8 (4)
N1—C8—C9—Cl1	3.19 (18)	C14—C12—C13—F3	37.1 (5)
C8—C14—C12—C11	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.5975 (19)	147

Experimental details

Crystal data
Chemical formula	C₁₄H₉ClF₃NO
M_r	299.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.979 (6), 7.418 (3), 13.881 (6)
β (°)	101.064 (7)
V (Å³)	1311.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.28 × 0.22 × 0.15

Data collection
Diffractometer	Bruker APEX-II area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.916, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	7694, 2303, 1411
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.070, 0.96
No. of reflections	2303
No. of parameters	210
No. of restraints	69
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004).