organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-[(E)-Benzyl­imino­meth­yl]-4-methyl­phenol

aDepartment of Chemistry, Jiaying University, Meizhou 514015, People's Republic of China, and bState Key Laboratory Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
*Correspondence e-mail: liangqifeng07@yahoo.com.cn

(Received 14 March 2008; accepted 14 April 2008; online 16 April 2008)

In the title Schiff base, C15H15NO, the benzene rings form a dihedral angle of 74.91 (1)°. There is a strong intra­molecular O—H⋯N hydrogen bond.

Related literature

For literature on photochromism and thermochromism of Schiff bases in the solid state, see: Cohen et al. (1964[Cohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964). J. Chem. Soc. pp. 2041-2043.]).

[Scheme 1]

Experimental

Crystal data
  • C15H15NO

  • Mr = 225.28

  • Monoclinic, P 21 /c

  • a = 14.248 (3) Å

  • b = 6.1724 (2) Å

  • c = 14.529 (3) Å

  • β = 102.79 (3)°

  • V = 1246.0 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 295 (2) K

  • 0.54 × 0.30 × 0.25 mm

Data collection
  • Rigaku R-AXIS RAPID IP diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.970, Tmax = 0.986

  • 11598 measured reflections

  • 2826 independent reflections

  • 1636 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.049

  • wR(F2) = 0.146

  • S = 1.03

  • 2826 reflections

  • 155 parameters

  • H-atom parameters constrained

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.14 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯N1 0.82 1.89 2.616 (2) 147

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: CrystalStructure; software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Compounds presenting photochromism, a reversible color change brought about in at least one direction by the action of electromagnetic radiation, attract considerable attention from various fields of chemistry, physics and material science as potential candidates for practical applications. For a long time, the Schiff bases of salicylaldehyde with aromatic amines (anils or N-salicylideneaniline derivatives) are recognized as such compounds, which undergo keto-enol tautomerism and present common features in their structures and reaction mechanisms (Cohen et al., 1964). The tautomerism involves proton transfer from the hydroxylic oxygen to the imino nitrogen atom that occurs intramolecularly via a six-membered ring, with the keto species showing bathochromically shifted spectra. Continuing our studies on the relation between the Schiff base geometry in the crystalline state and photochromism and/or thermochromism, we report here the crystal structure of 2-[(E)-(benzylimino)methyl]-4-methylphenol (I).

The molecular structure of (I) is illustrated in Fig. 1. Compound (I) is a typical Schiff base derived from salicylaldehyde with the C8—N1 bond length (Table 1) indicating double-bond character. The title molecule is not planar. The dihedral angle between the phenyl ring and salicylaldimine group is 74.91 (1)°. There is a strong intramolecular hydrogen bond between the phenolic group and the imine N atom (Table 1).

Related literature top

For literature on photochromism and thermochromism of Schiff bases in the solid state, see: Cohen et al. (1964).

Experimental top

1-Phenylmethanamine (0.02 mol, 2.14 g) and 5-methylsalicylaldehyde (0.02 mol, 2.76 g) were dissolved in ethanol and the solution was refluxed for 3 h. After evaporation, a crude product was recrystallized twice from ethanol to give a pure yellow product. Yield: 87.3%. Calcd. for C15H15NO: C, 79.97; H, 6.71; N, 6.22; Found: C, 79.53; H, 6.78; N, 6.02%.

Refinement top

All H atoms were located from difference Fourier syntheses. H atoms from the C—H groups and O—H group were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93–0.97%A; O—H = 0.82 Å). and Uiso(H) values equal to 1.2 Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku/MSC, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
2-[(E)-Benzyliminomethyl]-4-methylphenol top
Crystal data top
C15H15NOF(000) = 480
Mr = 225.28Dx = 1.201 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6530 reflections
a = 14.248 (3) Åθ = 1.0–27.5°
b = 6.1724 (2) ŵ = 0.08 mm1
c = 14.529 (3) ÅT = 295 K
β = 102.79 (3)°Block, yellow
V = 1246.0 (4) Å30.54 × 0.30 × 0.25 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
2826 independent reflections
Radiation source: fine-focus sealed tube1636 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 0 pixels mm-1θmax = 27.5°, θmin = 3.5°
ω scansh = 1818
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 77
Tmin = 0.970, Tmax = 0.986l = 1818
11598 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) = 0.146H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0657P)2 + 0.0924P]
where P = (Fo2 + 2Fc2)/3
2826 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C15H15NOV = 1246.0 (4) Å3
Mr = 225.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.248 (3) ŵ = 0.08 mm1
b = 6.1724 (2) ÅT = 295 K
c = 14.529 (3) Å0.54 × 0.30 × 0.25 mm
β = 102.79 (3)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
2826 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1636 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.986Rint = 0.036
11598 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 1.03Δρmax = 0.15 e Å3
2826 reflectionsΔρmin = 0.14 e Å3
155 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
xyzUiso*/Ueq
O10.60971 (8)0.30589 (18)0.62915 (9)0.0799 (4)
H1A0.65390.23260.65950.120*
N10.69322 (11)0.0362 (3)0.71735 (10)0.0756 (4)
C10.90441 (17)0.3943 (4)0.58653 (16)0.0962 (7)
H1C0.90180.51850.54980.115*
C20.96894 (15)0.2373 (4)0.58075 (16)0.0989 (7)
H2A1.01040.25360.54000.119*
C30.97336 (16)0.0579 (4)0.63369 (17)0.0958 (7)
H3A1.01820.04940.62990.115*
C40.84281 (13)0.3717 (3)0.64613 (14)0.0820 (5)
H4A0.79880.48090.64950.098*
C50.91196 (15)0.0324 (3)0.69338 (14)0.0833 (6)
H5A0.91540.09310.72940.100*
C60.84528 (12)0.1892 (3)0.70109 (12)0.0672 (5)
C70.77651 (14)0.1640 (4)0.76503 (14)0.0978 (7)
H7A0.80850.09190.82280.117*
H7B0.75540.30550.78130.117*
C80.61136 (13)0.1263 (3)0.70132 (11)0.0661 (5)
H8A0.60680.26720.72250.079*
C90.52454 (11)0.0188 (2)0.65129 (10)0.0535 (4)
C100.43697 (12)0.1266 (2)0.63498 (11)0.0616 (4)
H10A0.43510.26560.65920.074*
C110.25972 (15)0.1615 (4)0.56557 (16)0.1024 (7)
H12A0.27260.31310.56010.154*
H12B0.22780.13930.61650.154*
H12C0.21920.11090.50770.154*
C120.35323 (12)0.0375 (3)0.58492 (11)0.0657 (4)
C130.35819 (13)0.1710 (3)0.55086 (11)0.0694 (5)
H14A0.30230.23570.51670.083*
C140.44260 (13)0.2846 (3)0.56589 (12)0.0671 (5)
H15A0.44330.42450.54230.081*
C150.52682 (11)0.1926 (2)0.61595 (11)0.0572 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0798 (8)0.0663 (7)0.1004 (10)0.0110 (6)0.0346 (7)0.0035 (6)
N10.0683 (10)0.0952 (11)0.0659 (9)0.0153 (8)0.0206 (8)0.0023 (8)
C10.0927 (15)0.0946 (15)0.1008 (16)0.0124 (12)0.0202 (13)0.0275 (12)
C20.0763 (14)0.135 (2)0.0896 (15)0.0130 (14)0.0268 (12)0.0031 (15)
C30.0789 (14)0.1082 (17)0.0998 (16)0.0156 (12)0.0189 (12)0.0135 (14)
C40.0696 (12)0.0780 (12)0.0946 (14)0.0086 (9)0.0096 (10)0.0031 (11)
C50.0920 (14)0.0717 (11)0.0777 (13)0.0020 (11)0.0007 (11)0.0079 (9)
C60.0584 (10)0.0795 (11)0.0601 (10)0.0123 (9)0.0053 (8)0.0041 (8)
C70.0822 (13)0.143 (2)0.0699 (12)0.0370 (13)0.0208 (10)0.0184 (12)
C80.0832 (12)0.0665 (10)0.0539 (9)0.0141 (9)0.0265 (9)0.0049 (8)
C90.0675 (10)0.0496 (8)0.0470 (8)0.0047 (7)0.0206 (7)0.0014 (6)
C100.0832 (12)0.0492 (8)0.0563 (9)0.0028 (8)0.0239 (9)0.0022 (7)
C110.0860 (14)0.1106 (17)0.1066 (17)0.0238 (13)0.0126 (12)0.0172 (13)
C120.0722 (11)0.0711 (10)0.0555 (9)0.0062 (9)0.0179 (8)0.0090 (8)
C130.0746 (12)0.0814 (12)0.0543 (10)0.0160 (10)0.0184 (8)0.0064 (8)
C140.0848 (12)0.0565 (9)0.0675 (10)0.0122 (9)0.0331 (9)0.0132 (8)
C150.0705 (10)0.0517 (8)0.0566 (9)0.0021 (8)0.0297 (8)0.0034 (7)
Geometric parameters (Å, º) top
O1—C151.3493 (18)C7—H7B0.9700
O1—H1A0.8200C8—C91.449 (2)
N1—C81.266 (2)C8—H8A0.9300
N1—C71.465 (2)C9—C101.387 (2)
C1—C21.351 (3)C9—C151.405 (2)
C1—C41.370 (3)C10—C121.368 (2)
C1—H1C0.9300C10—H10A0.9300
C2—C31.342 (3)C11—C121.508 (2)
C2—H2A0.9300C11—H12A0.9600
C3—C51.370 (3)C11—H12B0.9600
C3—H3A0.9300C11—H12C0.9600
C4—C61.376 (3)C12—C131.386 (2)
C4—H4A0.9300C13—C141.367 (2)
C5—C61.378 (3)C13—H14A0.9300
C5—H5A0.9300C14—C151.380 (2)
C6—C71.500 (2)C14—H15A0.9300
C7—H7A0.9700
C15—O1—H1A109.5N1—C8—H8A118.6
C8—N1—C7117.85 (18)C9—C8—H8A118.6
C2—C1—C4120.4 (2)C10—C9—C15118.39 (15)
C2—C1—H1C119.8C10—C9—C8120.12 (14)
C4—C1—H1C119.8C15—C9—C8121.47 (15)
C3—C2—C1120.2 (2)C12—C10—C9122.94 (15)
C3—C2—H2A119.9C12—C10—H10A118.5
C1—C2—H2A119.9C9—C10—H10A118.5
C2—C3—C5120.1 (2)C12—C11—H12A109.5
C2—C3—H3A119.9C12—C11—H12B109.5
C5—C3—H3A119.9H12A—C11—H12B109.5
C1—C4—C6120.83 (19)C12—C11—H12C109.5
C1—C4—H4A119.6H12A—C11—H12C109.5
C6—C4—H4A119.6H12B—C11—H12C109.5
C3—C5—C6121.27 (19)C10—C12—C13117.10 (16)
C3—C5—H5A119.4C10—C12—C11121.73 (17)
C6—C5—H5A119.4C13—C12—C11121.15 (18)
C4—C6—C5117.19 (17)C14—C13—C12122.12 (16)
C4—C6—C7120.53 (18)C14—C13—H14A118.9
C5—C6—C7122.28 (18)C12—C13—H14A118.9
N1—C7—C6109.57 (15)C13—C14—C15120.28 (15)
N1—C7—H7A109.8C13—C14—H15A119.9
C6—C7—H7A109.8C15—C14—H15A119.9
N1—C7—H7B109.8O1—C15—C14119.53 (14)
C6—C7—H7B109.8O1—C15—C9121.32 (15)
H7A—C7—H7B108.2C14—C15—C9119.15 (15)
N1—C8—C9122.71 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.821.892.616 (2)147

Experimental details

Crystal data
Chemical formulaC15H15NO
Mr225.28
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)14.248 (3), 6.1724 (2), 14.529 (3)
β (°) 102.79 (3)
V3)1246.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.54 × 0.30 × 0.25
Data collection
DiffractometerRigaku R-AXIS RAPID IP
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.970, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
11598, 2826, 1636
Rint0.036
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.146, 1.03
No. of reflections2826
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.14

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Selected bond lengths (Å) top
O1—C151.3493 (18)N1—C71.465 (2)
N1—C81.266 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N10.821.892.616 (2)147
 

Acknowledgements

This project was supported by the Talent Fund of Ningbo University (grant No. 2006668).

References

First citationCohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964). J. Chem. Soc. pp. 2041–2043.  CrossRef Web of Science Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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