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Acta Cryst. (2012). E68, o1024    [ doi:10.1107/S1600536812009361 ]

2-[(E)-(Naphthalen-2-ylimino)methyl]-4-(trifluoromethoxy)phenol

M. Pekdemir, Z. S. Sahin, S. Isik, A. Alaman Agar, S. Öztürk Yildirim and R. J. Butcher

Abstract top

In the title compound, C18H12F3NO2, the planes of the benzene ring and the naphthalene system form a dihedral angle of 47.21 (3)°. The hydroxy group is involved in an intramolecular O-H...N hydrogen bond. In the crystal, weak C-H...O and C-H...F interactions link the molecules related by translations along the c and a axes, respectively, into sheets.

Comment top

There are two characteristic properties of Schiff bases, viz. photochromism and thermochromism (Cohen et al., 1964). These properties result from proton transfer from the hydroxyl O atom to the imine N atom (Hadjoudis et al., 1987). There are two types of intramolecular hydrogen bonds in Schiff bases, which may be stabilized in keto-amine (N—H···O hydrogen bond) or phenol-imine (N···H—O hydrogen bond) tautomeric forms (Hadjoudis et al., 1987). Herewith we present the title compound (I), which exhibits the phenol-imine tautomeric form (Fig. 1).

In (I), the C1—N1 bond length of 1.417 (2) Å agrees with the matching distance in 1-{4-[2-hydroxy-benzylidene)amino]phenyl}ethanone [1.4138 (17) Å; Yüce et al., 2004]. The N1═C11 bond length of 1.284 (2) Å is typical of a double bond, like to the matching bond length in (E)-2-[(3-trifluoromenthylphenylimino)methyl]-4-methylphenol [1.280 (2) Å; Gül et al., 2007]. The O1—C17 distance of 1.349 (2) Å is similar to the worth of 1.352 (3) Å in (E)-2-[(3-trifluoromenthylphenylimino)methyl]-4-methylphenol (Gül et al., 2007). Fig.1 additionally shows a strong intramolecular hyrogen bond (O1—H1···N1) can be defined as an S(6) motif (Bernstein et al., 1995). The O1—N1 distance of 2.590 (2) Å is comparable to those observed for same hydrogen bonds in 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone [2.594 (2) Å; Yüce et al., 2004].

The molecules are linked into sheets by a combination of C—H···O and C—H···F interactions (Table 1). The atom C10 in the reference molecule at (x, y, z) acts as a hydrogen-bond donor, via H10, to atom O1 in the molecule at (x, y, z + 1), so forming a C(8) chain running parallel to the [001] direction. Similarly, atom C5 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H5, to atom F2 in the molecule at (x + 1, y, z), so forming a C(14) chain running parallel to the [100] direction. The combination of the C(8) and C(14) chains generates a chain edge-fused R55(36) rings running parallel to the ac plane (Fig.2)

Related literature top

For background to photochromic and thermochromic characteristics and tautomerism of Schiff bases, see: Cohen et al. (1964); Hadjoudis et al. (1987). For related structures, see: Gül et al. (2007); Yüce et al. (2004). For classification of hydrogen-bonding patterns, see: Bernstein et al. (1995).

Experimental top

The title compound, (I), was prepared by reflux a mixture of a solution containing 2-hydroxy-5-(trifluoromethoxy)benzaldehyde (0.045 g 0.23 mmol) in 20 ml e thanol and a solution containing 2-Naphthyamine (0.033 g 0.23 mmol) in 20 ml e thanol. The reaction mixture was stirred for 1 hunder reflux. The crystals of (I) suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield % 68; m.p.369–371 K).

Refinement top

The H1 atom was located in a difference map, and isotropically refined with restraint of O—H=0.82 (2) Å. All other H atoms were placed in calculated positions and constrained to ride on their parents atoms, with C—H=0.93 Å and Uiso(H)=1.2Ueq(C).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability. Dashed line denotes hydrogen bond.
[Figure 2] Fig. 2. A portion of the crystal packing showing hydrogen bonds as dashed lines.
2-[(E)-(Naphthalen-2-ylimino)methyl]-4-(trifluoromethoxy)phenol top
Crystal data top
C18H12F3NO2F(000) = 680
Mr = 331.29Dx = 1.495 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5076 reflections
a = 17.0813 (10) Åθ = 3.1–34.9°
b = 14.1248 (8) ŵ = 0.12 mm−1
c = 6.1900 (5) ÅT = 123 K
β = 99.669 (6)°Plate, yellow
V = 1472.25 (17) Å30.50 × 0.40 × 0.18 mm
Z = 4
Data collection top
Oxford Diffraction Gemini-R
diffractometer		2892 independent reflections
Radiation source: Enhance (Mo) X-ray Source2497 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 10.5081 pixels mm-1θmax = 26.0°, θmin = 3.1°
ω scansh = −20→21
Absorption correction: analytical
[CrysAlis RED (Oxford Diffraction, 2007) based on Clark & Reid (1995)		k = −17→17
Tmin = 0.941, Tmax = 0.978l = −7→6
15270 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.062P)2 + 0.5277P]
where P = (Fo2 + 2Fc2)/3
2892 reflections(Δ/σ)max < 0.001
221 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C18H12F3NO2V = 1472.25 (17) Å3
Mr = 331.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.0813 (10) ŵ = 0.12 mm−1
b = 14.1248 (8) ÅT = 123 K
c = 6.1900 (5) Å0.50 × 0.40 × 0.18 mm
β = 99.669 (6)°
Data collection top
Oxford Diffraction Gemini-R
diffractometer		2892 independent reflections
Absorption correction: analytical
[CrysAlis RED (Oxford Diffraction, 2007) based on Clark & Reid (1995)		2497 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.978Rint = 0.050
15270 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130Δρmax = 0.31 e Å−3
S = 1.09Δρmin = −0.22 e Å−3
2892 reflectionsAbsolute structure: ?
221 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.52707 (9)0.88417 (11)0.3403 (3)0.0225 (4)
C20.59465 (10)0.90836 (11)0.2604 (3)0.0225 (3)
H20.59030.93380.12030.027*
C30.67071 (9)0.89512 (10)0.3876 (3)0.0222 (3)
C40.74184 (10)0.91509 (11)0.3061 (3)0.0268 (4)
H40.73900.94130.16720.032*
C50.81420 (10)0.89635 (12)0.4287 (3)0.0313 (4)
H50.86010.91030.37290.038*
C60.82014 (11)0.85608 (12)0.6391 (3)0.0320 (4)
H60.86980.84240.72010.038*
C70.75296 (10)0.83705 (11)0.7244 (3)0.0275 (4)
H70.75730.81140.86420.033*
C80.67680 (10)0.85604 (11)0.6021 (3)0.0232 (4)
C90.60574 (10)0.83457 (11)0.6822 (3)0.0246 (4)
H90.60890.81100.82370.029*
C100.53290 (10)0.84767 (11)0.5564 (3)0.0244 (4)
H100.48710.83270.61210.029*
C110.38798 (10)0.90319 (11)0.2662 (3)0.0241 (4)
H110.38940.92150.41120.029*
C120.31186 (10)0.89349 (11)0.1221 (3)0.0236 (4)
C130.24206 (10)0.92206 (11)0.1940 (3)0.0246 (4)
H130.24430.94750.33340.030*
C140.17025 (10)0.91238 (11)0.0580 (3)0.0265 (4)
C150.16428 (10)0.87238 (12)−0.1487 (3)0.0285 (4)
H150.11500.8661−0.23810.034*
C160.23260 (10)0.84183 (12)−0.2206 (3)0.0279 (4)
H160.22900.8130−0.35700.034*
C170.30663 (10)0.85398 (11)−0.0901 (3)0.0248 (4)
C180.05121 (10)0.89134 (14)0.1960 (3)0.0335 (4)
F10.08590 (7)0.83013 (9)0.3436 (2)0.0551 (4)
F2−0.00045 (7)0.94076 (10)0.2849 (2)0.0537 (4)
F30.01029 (7)0.84060 (11)0.0357 (2)0.0614 (4)
N10.45326 (8)0.88684 (9)0.1961 (2)0.0241 (3)
O10.37203 (7)0.82747 (9)−0.1701 (2)0.0301 (3)
O20.10202 (7)0.95092 (8)0.1277 (2)0.0328 (3)
H10.4140 (16)0.8422 (18)−0.067 (5)0.066 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0276 (8)0.0185 (8)0.0218 (8)0.0017 (6)0.0051 (7)−0.0016 (6)
C20.0325 (9)0.0176 (7)0.0184 (8)0.0003 (6)0.0072 (7)0.0002 (6)
C30.0282 (8)0.0162 (7)0.0228 (8)0.0003 (6)0.0060 (7)−0.0030 (6)
C40.0327 (9)0.0225 (8)0.0268 (9)−0.0017 (7)0.0095 (7)−0.0011 (7)
C50.0279 (9)0.0273 (9)0.0402 (10)−0.0031 (7)0.0102 (8)−0.0038 (8)
C60.0299 (9)0.0266 (9)0.0370 (10)0.0026 (7)−0.0018 (8)−0.0041 (8)
C70.0349 (9)0.0205 (8)0.0256 (9)0.0014 (6)0.0013 (7)−0.0025 (6)
C80.0317 (9)0.0158 (7)0.0220 (8)0.0005 (6)0.0043 (7)−0.0026 (6)
C90.0345 (9)0.0215 (8)0.0185 (8)0.0009 (6)0.0070 (7)0.0011 (6)
C100.0282 (8)0.0223 (8)0.0253 (9)−0.0004 (6)0.0118 (7)−0.0016 (6)
C110.0304 (9)0.0207 (8)0.0222 (8)0.0005 (6)0.0069 (7)−0.0012 (6)
C120.0292 (8)0.0191 (8)0.0231 (8)−0.0001 (6)0.0063 (7)0.0026 (6)
C130.0323 (9)0.0191 (8)0.0235 (8)0.0006 (6)0.0076 (7)−0.0003 (6)
C140.0277 (8)0.0224 (8)0.0303 (9)0.0020 (6)0.0080 (7)0.0031 (7)
C150.0291 (9)0.0270 (8)0.0282 (9)−0.0026 (7)0.0014 (7)0.0036 (7)
C160.0350 (9)0.0264 (8)0.0221 (8)−0.0016 (7)0.0041 (7)0.0003 (7)
C170.0303 (9)0.0213 (8)0.0245 (9)−0.0010 (6)0.0092 (7)0.0010 (6)
C180.0257 (9)0.0413 (11)0.0330 (10)0.0012 (7)0.0035 (8)−0.0022 (8)
F10.0503 (7)0.0630 (8)0.0554 (8)0.0110 (6)0.0188 (6)0.0264 (6)
F20.0386 (7)0.0587 (8)0.0701 (9)0.0065 (5)0.0274 (6)−0.0067 (6)
F30.0440 (7)0.0829 (10)0.0581 (8)−0.0267 (7)0.0108 (6)−0.0259 (7)
N10.0275 (7)0.0215 (7)0.0236 (7)−0.0009 (5)0.0052 (6)0.0006 (5)
O10.0299 (7)0.0375 (7)0.0244 (6)0.0001 (5)0.0085 (5)−0.0058 (5)
O20.0283 (6)0.0289 (7)0.0428 (8)0.0036 (5)0.0103 (5)−0.0008 (5)
Geometric parameters (Å, º) top
C1—C21.373 (2)C11—N11.284 (2)
C1—N11.417 (2)C11—C121.454 (2)
C1—C101.421 (2)C11—H110.9300
C2—C31.414 (2)C12—C131.400 (2)
C2—H20.9300C12—C171.416 (2)
C3—C41.420 (2)C13—C141.373 (2)
C3—C81.425 (2)C13—H130.9300
C4—C51.363 (2)C14—C151.387 (2)
C4—H40.9300C14—O21.4176 (19)
C5—C61.409 (3)C15—C161.386 (2)
C5—H50.9300C15—H150.9300
C6—C71.368 (3)C16—C171.392 (2)
C6—H60.9300C16—H160.9300
C7—C81.416 (2)C17—O11.349 (2)
C7—H70.9300C18—F21.316 (2)
C8—C91.419 (2)C18—F11.324 (2)
C9—C101.365 (2)C18—F31.324 (2)
C9—H90.9300C18—O21.328 (2)
C10—H100.9300O1—H10.90 (3)
C2—C1—N1118.63 (14)N1—C11—C12120.90 (15)
C2—C1—C10119.94 (15)N1—C11—H11119.5
N1—C1—C10121.10 (14)C12—C11—H11119.5
C1—C2—C3121.05 (15)C13—C12—C17118.92 (15)
C1—C2—H2119.5C13—C12—C11119.96 (15)
C3—C2—H2119.5C17—C12—C11121.11 (15)
C2—C3—C4122.47 (15)C14—C13—C12119.83 (15)
C2—C3—C8119.10 (14)C14—C13—H13120.1
C4—C3—C8118.35 (15)C12—C13—H13120.1
C5—C4—C3120.90 (16)C13—C14—C15121.73 (15)
C5—C4—H4119.6C13—C14—O2118.08 (15)
C3—C4—H4119.6C15—C14—O2120.04 (15)
C4—C5—C6120.71 (16)C16—C15—C14119.18 (16)
C4—C5—H5119.6C16—C15—H15120.4
C6—C5—H5119.6C14—C15—H15120.4
C7—C6—C5120.07 (16)C15—C16—C17120.49 (16)
C7—C6—H6120.0C15—C16—H16119.8
C5—C6—H6120.0C17—C16—H16119.8
C6—C7—C8120.76 (16)O1—C17—C16118.72 (15)
C6—C7—H7119.6O1—C17—C12121.51 (15)
C8—C7—H7119.6C16—C17—C12119.77 (15)
C7—C8—C9122.39 (15)F2—C18—F1108.15 (15)
C7—C8—C3119.20 (15)F2—C18—F3107.09 (14)
C9—C8—C3118.38 (15)F1—C18—F3106.41 (17)
C10—C9—C8121.55 (15)F2—C18—O2108.49 (16)
C10—C9—H9119.2F1—C18—O2113.14 (14)
C8—C9—H9119.2F3—C18—O2113.28 (15)
C9—C10—C1119.93 (15)C11—N1—C1121.55 (14)
C9—C10—H10120.0C17—O1—H1106.7 (17)
C1—C10—H10120.0C18—O2—C14117.93 (13)
N1—C1—C2—C3−171.57 (13)C17—C12—C13—C14−0.7 (2)
C10—C1—C2—C31.8 (2)C11—C12—C13—C14−179.68 (14)
C1—C2—C3—C4176.90 (14)C12—C13—C14—C151.8 (2)
C1—C2—C3—C80.0 (2)C12—C13—C14—O2−173.65 (14)
C2—C3—C4—C5−176.17 (15)C13—C14—C15—C16−0.4 (2)
C8—C3—C4—C50.8 (2)O2—C14—C15—C16174.97 (14)
C3—C4—C5—C60.4 (3)C14—C15—C16—C17−2.1 (2)
C4—C5—C6—C7−1.3 (3)C15—C16—C17—O1−176.85 (14)
C5—C6—C7—C81.0 (3)C15—C16—C17—C123.2 (2)
C6—C7—C8—C9178.00 (15)C13—C12—C17—O1178.27 (14)
C6—C7—C8—C30.2 (2)C11—C12—C17—O1−2.7 (2)
C2—C3—C8—C7175.98 (14)C13—C12—C17—C16−1.8 (2)
C4—C3—C8—C7−1.1 (2)C11—C12—C17—C16177.22 (14)
C2—C3—C8—C9−1.9 (2)C12—C11—N1—C1−171.85 (13)
C4—C3—C8—C9−178.95 (14)C2—C1—N1—C11−151.42 (15)
C7—C8—C9—C10−175.68 (15)C10—C1—N1—C1135.3 (2)
C3—C8—C9—C102.1 (2)F2—C18—O2—C14170.19 (14)
C8—C9—C10—C1−0.4 (2)F1—C18—O2—C1450.2 (2)
C2—C1—C10—C9−1.6 (2)F3—C18—O2—C14−71.0 (2)
N1—C1—C10—C9171.60 (14)C13—C14—O2—C18−105.77 (18)
N1—C11—C12—C13−172.63 (14)C15—C14—O2—C1878.7 (2)
N1—C11—C12—C178.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.90 (3)1.77 (3)2.5904 (18)150 (2)
C10—H10···O1i0.932.573.473 (2)165
C5—H5···F2ii0.932.573.487 (2)170
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.90 (3)1.77 (3)2.5904 (18)150 (2)
C10—H10···O1i0.932.573.473 (2)165.4
C5—H5···F2ii0.932.573.487 (2)170.1
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z.
references
References top

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Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.

Cohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964). J. Chem. Soc. pp. 2041–2051.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Gül, Z. S., Erşahin, F., Ağar, E. & Işık, Ş. (2007). Acta Cryst. E63, o2902.

Hadjoudis, E., Vitterakis, M., Moustakali, I. & Mavridis, I. (1987). Tetrahedron, 43, 1345–1360.

Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yüce, S., Özek, A., Albayrak, Ç., Odabaşoğlu, M. & Büyükgüngör, O. (2004). Acta Cryst. E60, o718–o719.