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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1644.
Published online 2009 June 20. doi:  10.1107/S1600536809023174
PMCID: PMC2969199

(E)-3-(2-Hydr­oxy-4-methoxy­benzyl­idene­amino)benzonitrile

Abstract

In the mol­ecule of the title compound, C15H12N2O2, the aromatic rings are oriented at a dihedral angle of 28.11 (3)°. Intra­molecular O—H(...)N hydrogen bonding results in the formation of a planar six-membered ring, which is nearly coplanar with the adjacent ring at a dihedral angle of 1.53 (3)°. In the crystal structure, π–π contacts between the benzene rings [centroid–centroid distance = 3.841 (1) Å] may stabilize the structure.

Related literature

For general background, see: Chen et al. (2008 [triangle]); May et al. (2004 [triangle]); Weber et al. (2007 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1644-scheme1.jpg

Experimental

Crystal data

  • C15H12N2O2
  • M r = 252.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1644-efi1.jpg
  • a = 14.484 (3) Å
  • b = 6.6587 (13) Å
  • c = 26.461 (5) Å
  • β = 102.14 (3)°
  • V = 2494.9 (9) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 K
  • 0.2 × 0.2 × 0.2 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.982, T max = 0.982
  • 12044 measured reflections
  • 2861 independent reflections
  • 1608 reflections with I > 2σ(I)
  • R int = 0.062

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.142
  • S = 1.01
  • 2861 reflections
  • 176 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023174/hk2714sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023174/hk2714Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Schiff base compounds have received considerable attention for many years, primarily due to their importance in the development of coordination chemistry related to magnetism (Weber et al., 2007), catalysis (Chen et al., 2008) and biological process (May et al., 2004). Our group is interested in the syntheses and preparation of Schiff bases. We report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C9-C14) are, of course, planar and they are oriented at a dihedral angle of 28.11 (3)°. Atoms O1, O2, N1, C7 and C8 are 0.005 (3), 0.014 (3), 0.067 (3), 0.100 (3) and 0.054 (3) Å away from the plane of ring A, while atoms N1, N2 and C15 are 0.053 (3), 0.002 (3) and 0.002 (3) Å away from the plane of ring B, respectively. Intramolecular O-H···N hydrogen bond (Table 1) results in the formation of a planar six-membered ring C (O1/N1/C1/C2/C8/H1B), which is oriented with respect to rings A and B at dihedral angles of A/C = 1.53 (3) and B/C = 27.66 (3) °. So, rings A and C are nearly coplanar.

In the crystal structure, the π–π contact between the benzene rings, Cg1—Cg2i, [symmetry code: (i) -x, y, 1/2 - z, where Cg1 and Cg2 are centroids of the rings A (C1-C6) and B (C9-C14), respectively] may stabilize the structure, with centroid-centroid distance of 3.841 (1) Å.

Experimental

For the preparation of the title compound, 3-aminobenzonitrile (472 mg, 4 mmol) and 2-hydroxy-4-methoxybenzaldehyde (608 mg, 4 mmol) were dissolved in ethanol (20 ml). The mixture was heated to reflux for 5 h, and then cooled to room temperature. The solution was filtered and after two weeks, yellow crystals suitable for X-ray analysis were obtained (yield; 85%).

Refinement

H atom (for OH) was located in difference Fourier map and refined isotropically. The remaining H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as a dashed line.

Crystal data

C15H12N2O2F(000) = 1056
Mr = 252.27Dx = 1.343 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9417 reflections
a = 14.484 (3) Åθ = 3.1–27.7°
b = 6.6587 (13) ŵ = 0.09 mm1
c = 26.461 (5) ÅT = 294 K
β = 102.14 (3)°Prism, yellow
V = 2494.9 (9) Å30.2 × 0.2 × 0.2 mm
Z = 8

Data collection

Rigaku SCXmini diffractometer2861 independent reflections
Radiation source: fine-focus sealed tube1608 reflections with I > 2σ(I)
graphiteRint = 0.062
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scansh = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.982, Tmax = 0.982l = −34→34
12044 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0618P)2 + 0.0432P] where P = (Fo2 + 2Fc2)/3
2861 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

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)

xyzUiso*/Ueq
O10.60788 (11)−0.3053 (2)0.21473 (6)0.0585 (4)
H1B0.602 (2)−0.228 (4)0.2426 (12)0.116 (11)*
O20.70583 (11)−0.2132 (2)0.05513 (6)0.0605 (4)
N10.61594 (10)0.0051 (2)0.27458 (6)0.0452 (4)
N20.56309 (17)−0.2127 (4)0.47862 (8)0.0890 (8)
C10.66562 (12)0.0183 (3)0.19441 (7)0.0415 (5)
C20.64330 (13)−0.1851 (3)0.18223 (7)0.0426 (5)
C30.65629 (13)−0.2662 (3)0.13598 (7)0.0458 (5)
H3A0.6414−0.40010.12820.055*
C40.69136 (13)−0.1477 (3)0.10142 (7)0.0456 (5)
C50.71476 (14)0.0530 (3)0.11294 (8)0.0537 (6)
H5A0.73870.13200.08970.064*
C60.70216 (14)0.1324 (3)0.15864 (8)0.0506 (5)
H6A0.71830.26580.16620.061*
C70.67817 (16)−0.4139 (4)0.03934 (8)0.0657 (7)
H7A0.6926−0.43980.00620.099*
H7B0.6115−0.42920.03710.099*
H7C0.7118−0.50720.06420.099*
C80.64973 (12)0.1077 (3)0.24112 (7)0.0459 (5)
H8A0.66410.24270.24750.055*
C90.59329 (12)0.0935 (3)0.31897 (7)0.0425 (5)
C100.59023 (13)−0.0336 (3)0.35993 (7)0.0465 (5)
H10A0.6050−0.16870.35750.056*
C110.56549 (13)0.0373 (3)0.40448 (7)0.0465 (5)
C120.54203 (14)0.2386 (3)0.40845 (8)0.0530 (6)
H12A0.52510.28690.43820.064*
C130.54431 (14)0.3653 (3)0.36748 (8)0.0553 (6)
H13A0.52880.50010.36970.066*
C140.56938 (14)0.2945 (3)0.32322 (8)0.0504 (5)
H14A0.57030.38200.29590.060*
C150.56360 (16)−0.1001 (4)0.44628 (9)0.0607 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0842 (11)0.0452 (9)0.0495 (9)−0.0166 (8)0.0219 (8)0.0008 (8)
O20.0731 (10)0.0597 (10)0.0543 (9)−0.0061 (8)0.0262 (8)−0.0050 (8)
N10.0460 (10)0.0446 (10)0.0429 (10)−0.0022 (8)0.0045 (8)−0.0012 (8)
N20.1156 (19)0.0890 (17)0.0664 (14)0.0167 (14)0.0283 (13)0.0222 (13)
C10.0390 (10)0.0397 (11)0.0441 (11)−0.0004 (9)0.0052 (8)0.0032 (9)
C20.0418 (11)0.0420 (12)0.0421 (11)−0.0008 (9)0.0043 (9)0.0072 (10)
C30.0477 (12)0.0408 (12)0.0488 (12)−0.0056 (9)0.0102 (9)−0.0002 (10)
C40.0418 (12)0.0491 (13)0.0467 (12)0.0012 (9)0.0110 (9)0.0026 (10)
C50.0596 (13)0.0461 (13)0.0598 (14)−0.0060 (10)0.0229 (11)0.0076 (11)
C60.0508 (13)0.0407 (12)0.0614 (14)−0.0057 (9)0.0139 (10)0.0008 (11)
C70.0796 (17)0.0624 (16)0.0582 (15)−0.0047 (13)0.0213 (12)−0.0105 (12)
C80.0399 (11)0.0435 (12)0.0511 (12)−0.0048 (9)0.0027 (9)−0.0005 (10)
C90.0373 (11)0.0436 (12)0.0441 (11)−0.0021 (9)0.0026 (8)−0.0008 (10)
C100.0465 (12)0.0403 (11)0.0510 (12)0.0030 (9)0.0068 (9)0.0018 (10)
C110.0416 (11)0.0531 (13)0.0439 (12)−0.0005 (9)0.0069 (9)0.0020 (10)
C120.0518 (13)0.0569 (14)0.0517 (13)−0.0007 (11)0.0144 (10)−0.0087 (11)
C130.0558 (14)0.0440 (13)0.0675 (15)0.0019 (10)0.0161 (11)−0.0056 (12)
C140.0500 (13)0.0450 (12)0.0542 (13)−0.0012 (10)0.0069 (10)0.0048 (11)
C150.0658 (15)0.0659 (16)0.0515 (14)0.0083 (12)0.0147 (11)0.0030 (13)

Geometric parameters (Å, °)

O1—C21.352 (2)C7—H7B0.9600
O1—H1B0.92 (3)C7—H7C0.9600
O2—C41.357 (2)C8—C11.434 (3)
O2—C71.432 (3)C8—H8A0.9300
N1—C81.293 (2)C9—C101.383 (3)
N1—C91.413 (2)C9—C141.393 (3)
C1—C61.402 (2)C10—C111.385 (3)
C2—C11.414 (3)C10—H10A0.9300
C3—C21.386 (3)C11—C121.392 (3)
C3—C41.383 (3)C11—C151.440 (3)
C3—H3A0.9300C12—C131.380 (3)
C4—C51.397 (3)C12—H12A0.9300
C5—H5A0.9300C13—H13A0.9300
C6—C51.367 (3)C14—C131.380 (3)
C6—H6A0.9300C14—H14A0.9300
C7—H7A0.9600C15—N21.139 (3)
C2—O1—H1B107.1 (18)H7A—C7—H7C109.5
C4—O2—C7118.43 (16)H7B—C7—H7C109.5
C8—N1—C9122.42 (18)N1—C8—C1121.54 (19)
C2—C1—C8121.61 (17)N1—C8—H8A119.2
C6—C1—C2117.77 (17)C1—C8—H8A119.2
C6—C1—C8120.60 (19)C10—C9—N1116.60 (18)
O1—C2—C1121.40 (17)C10—C9—C14118.36 (18)
O1—C2—C3118.10 (18)C14—C9—N1124.96 (18)
C3—C2—C1120.50 (17)C9—C10—H10A119.5
C2—C3—H3A120.0C11—C10—C9121.01 (19)
C4—C3—C2119.91 (19)C11—C10—H10A119.5
C4—C3—H3A120.0C10—C11—C12120.22 (19)
O2—C4—C3124.17 (19)C10—C11—C15119.15 (19)
O2—C4—C5115.32 (18)C12—C11—C15120.63 (19)
C3—C4—C5120.51 (19)C11—C12—H12A120.6
C4—C5—H5A120.3C13—C12—C11118.87 (19)
C6—C5—C4119.45 (19)C13—C12—H12A120.6
C6—C5—H5A120.3C12—C13—C14120.8 (2)
C1—C6—H6A119.1C12—C13—H13A119.6
C5—C6—C1121.8 (2)C14—C13—H13A119.6
C5—C6—H6A119.1C9—C14—H14A119.6
O2—C7—H7A109.5C13—C14—C9120.7 (2)
O2—C7—H7B109.5C13—C14—H14A119.6
O2—C7—H7C109.5N2—C15—C11178.2 (3)
H7A—C7—H7B109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1B···N10.92 (3)1.76 (3)2.592 (3)149 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2714).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Chen, Z. H., Morimoto, H., Matsunaga, S. & Shibasaki, M. (2008). J. Am. Chem. Soc.130, 2170–2171. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • May, J. P., Ting, R., Lermer, L., Thomas, J. M., Roupioz, Y. & Perrin, D. M. (2004). J. Am. Chem. Soc.126, 4145–4156. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Weber, B., Tandon, R. & Himsl, D. (2007). Z. Anorg. Allg. Chem.633, 1159–1162.

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