2-{(E)-[(3-Chloro-4-methyl­phen­yl)imino]­meth­yl}-4-(tri­fluoro­meth­oxy)phenol

Atalay, Ş.; Gerçeker, S.; Meral, S.; Bülbül, H.

doi:10.1107/S2414314617017254

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 12| December 2017| x171725

https://doi.org/10.1107/S2414314617017254

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2-{(E)-[(3-Chloro-4-methylphenyl)imino]methyl}-4-(trifluoromethoxy)phenol

Şehriman Atalay,^a ^* Semra Gerçeker,^a Seher Meral ^b and Hakan Bülbül ^a

^aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Kurupelit, 55139 Samsun, Turkey, and ^bDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayıs University, Kurupelit, 55139 Samsun, Turkey
^*Correspondence e-mail: atalays@omu.edu.tr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 29 November 2017; accepted 1 December 2017; online 12 December 2017)

In the title compound, C₁₅H₁₁ClF₃NO₂, the dihedral angle between the planes of the benzene rings is 8.3 (2)° and an intramolecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, weak C—H⋯O links connect the molecules into [-110] chains. The F atoms of the CF₃ group are disordered over two sets of sites with refined occupancies of 0.626 (11):0.374 (11).

Keywords: crystal structure; Schiff base; hydrogen bonding.

CCDC reference: 1517954

Structure description

We herein report the synthesis and structure of the new Schiff base (Fig. 1). The bond distances of the imino group atoms [N1–C9 = 1.423 (5); N1—C8 = 1.275 (5) Å] are consistent with those in the related structures 2-[(2- bromophenyl)iminomethyl]-6-methylphenol (Karadağ et al., 2010 ) and 2-amino-3-((E)-{[3-(trifluoromethyl)phenyl]imino}-methyl)-4H-chromen-4-one (Atalay et al., 2016 ). The dihedral angle between the benzene rings is 8.3 (2)° and an intramolecular O—H⋯N hydrogen bond (Table 1) closes an S(6) ring.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.88	2.609 (5)	148
C10—H10⋯O2ⁱ	0.93	2.52	3.277 (5)	139
Symmetry code: (i) x-1, y+1, z.

Figure 1
The molecular structure showing 30% probability displacement ellipsoids. Only the major-disorder component of the CF₃ group is shown.

In the crystal (Fig. 2), weak C—H⋯O links connect the molecules into [ $[\overline{1}]$ 10] chains.

Figure 2
The packing, viewed along [100] with hydrogen bonds shown as dashed lines..

Synthesis and crystallization

A mixture of 2-hydroxy-5-(trifluoromethoxy)benzaldehyde (0.19 g, 0.9 mol) in ethanol (20 ml) and 3-chloro-4-methyaniline (0.13 g, 0.9 mol) in ethanol (20 ml) were mixed and stirred for 5 h under reflux. Light-yellow plate-shaped crystals were obtained by slow evaporation of an ethanol solution (yield 67%; m.p. 361–363 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The F atoms of the CF₃ group are disordered over two sets of sites with refined occupancies of 0.626 (11):0.374 (11).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₁ClF₃NO₂
M_r	329.70
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	4.5971 (4), 6.4372 (7), 25.237 (2)
α, β, γ (°)	86.984 (8), 86.173 (7), 78.096 (8)
V (Å³)	728.57 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.42 × 0.24 × 0.05

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-AREA; Stoe & Cie, 2002 )
T_min, T_max	0.907, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	6174, 2581, 1173
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.181, 0.89
No. of reflections	2581
No. of parameters	228
No. of restraints	96
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.29
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2016 (Sheldrick, 2015 ), SHELXL2016 (Sheldrick, 2015 ) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Structural data

CCDC reference: 1517954

Crystal structure: contains datablocks seh25, I. DOI: https://doi.org/10.1107/S2414314617017254/hb4186sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017254/hb4186Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617017254/hb4186Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

2-{(E)-[(3-Chloro-4-methylphenyl)imino]methyl}-4-(trifluoromethoxy)phenol top

Crystal data top

C₁₅H₁₁ClF₃NO₂	Z = 2
M_r = 329.70	F(000) = 336
Triclinic, P1	D_x = 1.503 Mg m⁻³
a = 4.5971 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.4372 (7) Å	Cell parameters from 4834 reflections
c = 25.237 (2) Å	θ = 1.6–27.4°
α = 86.984 (8)°	µ = 0.30 mm⁻¹
β = 86.173 (7)°	T = 293 K
γ = 78.096 (8)°	Plate, light yellow
V = 728.57 (12) Å³	0.42 × 0.24 × 0.05 mm

Data collection top

Stoe IPDS 2 diffractometer	1173 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.050
rotation method scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: integration (X-AREA; Stoe & Cie, 2002)	h = −5→5
T_min = 0.907, T_max = 0.986	k = −7→7
6174 measured reflections	l = −29→29
2581 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.181	w = 1/[σ²(F_o²) + (0.098P)²] where P = (F_o² + 2F_c²)/3
S = 0.89	(Δ/σ)_max < 0.001
2581 reflections	Δρ_max = 0.44 e Å⁻³
228 parameters	Δρ_min = −0.29 e Å⁻³
96 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The H atoms attached to C10 and C16 were placed in calculated positions and refined using a riding model, with C–H distances of 0.93 Å and methyl C–H distances 0.96 Å. All other H atoms were freely refined.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	1.2010 (15)	0.7569 (14)	0.5585 (3)	0.1286 (17)
C2	1.2114 (9)	0.5356 (8)	0.63470 (17)	0.0694 (12)
C3	0.9931 (9)	0.6027 (7)	0.67272 (17)	0.0691 (11)
H3	0.914764	0.747080	0.675766	0.083*
C4	0.8865 (8)	0.4547 (6)	0.70721 (15)	0.0595 (10)
C5	1.0128 (9)	0.2385 (7)	0.70263 (17)	0.0676 (11)
C6	1.2400 (11)	0.1773 (8)	0.6644 (2)	0.0847 (13)
H6	1.327412	0.034117	0.661899	0.102*
C7	1.3387 (10)	0.3233 (8)	0.63015 (19)	0.0795 (13)
H7	1.489359	0.279952	0.604209	0.095*
C8	0.6507 (9)	0.5284 (7)	0.74676 (16)	0.0647 (11)
H8	0.577359	0.673819	0.748866	0.078*
C9	0.3055 (8)	0.4808 (7)	0.81702 (15)	0.0609 (10)
C10	0.1480 (9)	0.6892 (7)	0.81789 (17)	0.0704 (12)
H10	0.190670	0.788803	0.792070	0.084*
C11	−0.0704 (9)	0.7473 (7)	0.85695 (18)	0.0736 (12)
H11	−0.171975	0.888128	0.856866	0.088*
C12	−0.1488 (9)	0.6093 (7)	0.89651 (16)	0.0658 (11)
C13	0.0067 (9)	0.4005 (7)	0.89411 (16)	0.0660 (11)
C14	0.2288 (9)	0.3368 (7)	0.85488 (17)	0.0663 (11)
H14	0.326900	0.195268	0.854176	0.080*
C15	−0.3891 (10)	0.6817 (8)	0.93910 (18)	0.0837 (13)
H15A	−0.467896	0.830850	0.933691	0.125*
H15B	−0.306594	0.655789	0.973358	0.125*
H15C	−0.545647	0.604398	0.937355	0.125*
Cl1	−0.0746 (3)	0.2116 (2)	0.94138 (5)	0.0940 (5)
F1A	1.229 (3)	0.6214 (16)	0.5215 (3)	0.150 (3)	0.374 (11)
F2A	1.287 (4)	0.918 (3)	0.5377 (6)	0.141 (3)	0.374 (11)
F3A	0.8893 (14)	0.837 (3)	0.5742 (4)	0.145 (3)	0.374 (11)
F1B	1.036 (2)	0.6539 (13)	0.5373 (3)	0.139 (2)	0.626 (11)
F2B	1.335 (2)	0.8762 (19)	0.5297 (4)	0.151 (3)	0.626 (11)
F3B	0.9360 (13)	0.9123 (13)	0.5759 (2)	0.142 (2)	0.626 (11)
N1	0.5390 (7)	0.4024 (5)	0.77887 (13)	0.0641 (9)
O1	1.3285 (6)	0.6855 (5)	0.60186 (13)	0.0859 (10)
O2	0.9184 (7)	0.0908 (5)	0.73535 (13)	0.0896 (10)
H2	0.783064	0.149011	0.755697	0.134*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.108 (3)	0.180 (4)	0.111 (4)	−0.070 (3)	−0.009 (3)	0.039 (3)
C2	0.059 (3)	0.083 (3)	0.069 (3)	−0.021 (2)	−0.005 (2)	−0.003 (2)
C3	0.062 (3)	0.069 (3)	0.076 (3)	−0.011 (2)	−0.008 (2)	−0.002 (2)
C4	0.058 (2)	0.055 (2)	0.064 (2)	−0.008 (2)	−0.009 (2)	−0.003 (2)
C5	0.068 (3)	0.057 (3)	0.075 (3)	−0.004 (2)	−0.007 (2)	−0.003 (2)
C6	0.083 (3)	0.070 (3)	0.096 (3)	−0.003 (3)	0.001 (3)	−0.013 (3)
C7	0.068 (3)	0.083 (4)	0.084 (3)	−0.007 (3)	0.003 (2)	−0.014 (3)
C8	0.060 (2)	0.057 (3)	0.074 (3)	−0.004 (2)	−0.008 (2)	−0.006 (2)
C9	0.056 (2)	0.066 (3)	0.061 (2)	−0.012 (2)	−0.010 (2)	−0.001 (2)
C10	0.074 (3)	0.063 (3)	0.070 (3)	−0.006 (2)	−0.003 (2)	0.003 (2)
C11	0.066 (3)	0.065 (3)	0.084 (3)	0.002 (2)	−0.003 (2)	−0.006 (2)
C12	0.064 (3)	0.072 (3)	0.064 (3)	−0.014 (2)	−0.012 (2)	−0.011 (2)
C13	0.066 (3)	0.070 (3)	0.064 (3)	−0.019 (2)	−0.008 (2)	0.000 (2)
C14	0.062 (3)	0.058 (3)	0.077 (3)	−0.006 (2)	−0.010 (2)	0.000 (2)
C15	0.077 (3)	0.092 (3)	0.081 (3)	−0.013 (3)	0.002 (3)	−0.016 (3)
Cl1	0.1027 (9)	0.0869 (9)	0.0912 (9)	−0.0253 (7)	0.0124 (7)	0.0085 (7)
F1A	0.155 (6)	0.217 (5)	0.097 (5)	−0.082 (5)	−0.017 (4)	0.019 (4)
F2A	0.113 (5)	0.177 (5)	0.134 (5)	−0.053 (5)	−0.002 (5)	0.062 (4)
F3A	0.104 (4)	0.189 (7)	0.145 (5)	−0.054 (4)	−0.019 (4)	0.064 (5)
F1B	0.134 (4)	0.203 (5)	0.096 (4)	−0.075 (3)	−0.024 (3)	0.023 (3)
F2B	0.125 (4)	0.204 (5)	0.128 (4)	−0.065 (4)	0.003 (3)	0.072 (4)
F3B	0.116 (3)	0.171 (5)	0.144 (4)	−0.050 (3)	−0.017 (3)	0.050 (3)
N1	0.061 (2)	0.065 (2)	0.065 (2)	−0.0095 (17)	−0.0083 (17)	0.0029 (17)
O1	0.0700 (19)	0.104 (3)	0.084 (2)	−0.0227 (18)	−0.0023 (16)	0.0140 (19)
O2	0.100 (2)	0.0600 (19)	0.098 (2)	0.0005 (17)	0.0112 (19)	0.0085 (17)

Geometric parameters (Å, º) top

C1—F2B	1.255 (7)	C8—N1	1.275 (5)
C1—F2A	1.263 (7)	C8—H8	0.9300
C1—F1B	1.267 (8)	C9—C14	1.376 (5)
C1—O1	1.293 (7)	C9—C10	1.387 (6)
C1—F1A	1.293 (8)	C9—N1	1.423 (5)
C1—F3A	1.455 (9)	C10—C11	1.368 (6)
C1—F3B	1.466 (8)	C10—H10	0.9300
C2—C3	1.360 (6)	C11—C12	1.381 (6)
C2—C7	1.379 (6)	C11—H11	0.9300
C2—O1	1.406 (5)	C12—C13	1.388 (6)
C3—C4	1.398 (5)	C12—C15	1.508 (6)
C3—H3	0.9300	C13—C14	1.388 (6)
C4—C5	1.401 (6)	C13—Cl1	1.737 (4)
C4—C8	1.446 (5)	C14—H14	0.9300
C5—O2	1.347 (5)	C15—H15A	0.9600
C5—C6	1.383 (6)	C15—H15B	0.9600
C6—C7	1.369 (6)	C15—H15C	0.9600
C6—H6	0.9300	O2—H2	0.8200
C7—H7	0.9300

F2B—C1—F1B	119.1 (8)	N1—C8—C4	122.7 (4)
F2B—C1—O1	114.6 (6)	N1—C8—H8	118.6
F2A—C1—O1	113.5 (7)	C4—C8—H8	118.6
F1B—C1—O1	120.7 (7)	C14—C9—C10	118.4 (4)
F2A—C1—F1A	106.5 (12)	C14—C9—N1	116.9 (4)
O1—C1—F1A	115.4 (7)	C10—C9—N1	124.7 (4)
F2A—C1—F3A	103.6 (12)	C11—C10—C9	119.6 (4)
O1—C1—F3A	105.9 (6)	C11—C10—H10	120.2
F1A—C1—F3A	111.4 (10)	C9—C10—H10	120.2
F2B—C1—F3B	99.7 (9)	C10—C11—C12	123.9 (4)
F1B—C1—F3B	89.5 (6)	C10—C11—H11	118.1
O1—C1—F3B	104.8 (6)	C12—C11—H11	118.1
C3—C2—C7	121.5 (4)	C11—C12—C13	115.5 (4)
C3—C2—O1	119.8 (4)	C11—C12—C15	121.9 (4)
C7—C2—O1	118.5 (4)	C13—C12—C15	122.6 (4)
C2—C3—C4	120.0 (4)	C14—C13—C12	121.9 (4)
C2—C3—H3	120.0	C14—C13—Cl1	118.4 (3)
C4—C3—H3	120.0	C12—C13—Cl1	119.8 (3)
C3—C4—C5	118.9 (4)	C9—C14—C13	120.7 (4)
C3—C4—C8	119.3 (4)	C9—C14—H14	119.6
C5—C4—C8	121.8 (4)	C13—C14—H14	119.6
O2—C5—C6	119.9 (4)	C12—C15—H15A	109.5
O2—C5—C4	120.8 (4)	C12—C15—H15B	109.5
C6—C5—C4	119.3 (4)	H15A—C15—H15B	109.5
C7—C6—C5	121.3 (5)	C12—C15—H15C	109.5
C7—C6—H6	119.3	H15A—C15—H15C	109.5
C5—C6—H6	119.3	H15B—C15—H15C	109.5
C6—C7—C2	119.0 (5)	C8—N1—C9	121.1 (4)
C6—C7—H7	120.5	C1—O1—C2	119.2 (4)
C2—C7—H7	120.5	C5—O2—H2	109.5

C7—C2—C3—C4	−2.0 (6)	C11—C12—C13—C14	0.9 (6)
O1—C2—C3—C4	−176.8 (4)	C15—C12—C13—C14	−179.5 (4)
C2—C3—C4—C5	1.5 (6)	C11—C12—C13—Cl1	−179.4 (3)
C2—C3—C4—C8	−178.9 (4)	C15—C12—C13—Cl1	0.2 (6)
C3—C4—C5—O2	179.4 (4)	C10—C9—C14—C13	−2.3 (6)
C8—C4—C5—O2	−0.2 (6)	N1—C9—C14—C13	179.0 (3)
C3—C4—C5—C6	0.3 (6)	C12—C13—C14—C9	0.8 (6)
C8—C4—C5—C6	−179.3 (4)	Cl1—C13—C14—C9	−178.9 (3)
O2—C5—C6—C7	179.3 (4)	C4—C8—N1—C9	−179.5 (3)
C4—C5—C6—C7	−1.6 (7)	C14—C9—N1—C8	−170.8 (4)
C5—C6—C7—C2	1.1 (7)	C10—C9—N1—C8	10.6 (6)
C3—C2—C7—C6	0.7 (7)	F2B—C1—O1—C2	−174.4 (10)
O1—C2—C7—C6	175.6 (4)	F2A—C1—O1—C2	167.0 (13)
C3—C4—C8—N1	178.7 (4)	F1B—C1—O1—C2	−21.0 (11)
C5—C4—C8—N1	−1.6 (6)	F1A—C1—O1—C2	−69.7 (10)
C14—C9—C10—C11	2.1 (6)	F3A—C1—O1—C2	54.0 (11)
N1—C9—C10—C11	−179.2 (4)	F3B—C1—O1—C2	77.4 (7)
C9—C10—C11—C12	−0.4 (7)	C3—C2—O1—C1	−87.8 (6)
C10—C11—C12—C13	−1.1 (6)	C7—C2—O1—C1	97.2 (6)
C10—C11—C12—C15	179.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.88	2.609 (5)	148
C10—H10···O2ⁱ	0.93	2.52	3.277 (5)	139

Symmetry code: (i) x−1, y+1, z.

Funding information

The authors thank the Turkish Government and Ondokuz Mayıs University for research grant PYO·FEN.1904.16.005.

References

Atalay, Ş., Gerçeker, S., Meral, S. & Alaman Ağar, A. (2016). IUCrData, 1, x160797. Google Scholar
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