4-(2-Hydroxy­benzyl­idene­amino)­benzonitrile

Abstract

The mol­ecule of the title compound, C₁₄H₁₀N₂O, is nearly planar. There is a strong intra­molecular O—H⋯N hydrogen bond between the imine and hydr­oxy groups. The configuration with respect to the C=N double bond is anti (1E).

Related literature

For related literature, see: Allen et al. (1987 ▶); Chen et al. (2008 ▶); Cheng et al. (2005 ▶, 2006 ▶); Elmah et al. (1999 ▶); May et al. (2004 ▶); Weber et al. (2007 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

• C₁₄H₁₀N₂O

• M _r = 222.24

• Monoclinic,

• a = 28.071 (6) Å

• b = 5.8471 (12) Å

• c = 14.687 (3) Å

• β = 109.91 (3)°

• V = 2266.6 (9) ų

• Z = 8

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 293 (2) K

• 0.12 × 0.11 × 0.03 mm

Data collection

• Rigaku Mercury2 diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.915, T _max = 1.00 (expected range = 0.913–0.997)

• 9782 measured reflections

• 2223 independent reflections

• 971 reflections with I > 2σ(I)

• R _int = 0.132

Refinement

• R[F ² > 2σ(F ²)] = 0.077

• wR(F ²) = 0.176

• S = 0.97

• 2223 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N1	0.82	1.88	2.609 (4)	147

supplementary crystallographic information

Comment

The Schiff base compounds have received considerable attention for several decades, 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). Recently, we have reported a Schiff base compound (Xu et al., 2008). As an extention of our work on the structural characterization of Schiff base compounds, the title compound has been synthesized.

The molecule of the title compound is nearly planar, the two aromatic rings are only twisted by a dihedral angle 3.28 (18) ° (Fig. 1), As expected, the molecule displays a trans configuration about the central C7=N1 imine double bond. Bond lengths and bond angles in the compound are within normal ranges (Allen et al., 1987). The C7=N1 bond length of 1.280 (4) Å indicates a high degree of double-bond character comparable with the corresponding bond lengths in other Schiff bases (1.280 (2) Å; Elmah et al., 1999).

A strong O–H···N intramolecular hydrogen-bond interaction is observed in the molecular structure (Table 1 ) as also found in previous reports (Xu et al., 2008; Cheng et al., 2006, 2005).

Experimental

All chemicals were obtained from commercial sources and used without further purification except for salicylaldehyde which is distilled under reduced pressure before use. 4-aminobenzonitrile (1.18 g, 10 mmol) and salicylaldehyde (1.22 g, 10 mmol) were dissolved in ethanol (20 ml). The mixture was heated to reflux for 4 h, then cooled to room temperature overnight then large amounts of a yellow precipitate were formed. Yellow crystals were obtained by recrystallization from ethyl alcohol(yield: 81%). ¹H-NMR(CDCl₃, 300 MHz): δ6.98 (t, 1 H), 7.04 (d, 1 H), 7.34(d, 2 H), 7.43 (t, 2 H), 7.72 (d, 2H), 8.61 (s, 1 H). ¹³C-NMR (CDCl₃)δ110.1, 117.4, 118.6, 118.7, 119.4, 122.1, 132.8, 133.5, 134.3, 152.4, 161.2, 165.0. Esi-MS: calcd for C₁₄H₉N₂O – H m/z 221.24, found 221.34. Suitable single crystals of the title compound were obtained after one week by slow evaporation from an ethyl alcohol solution.

Refinement

All H atoms attached to C atoms and O atom were fixed geometrically and treated as riding with C—H = 0.93 °H (C) and O-H= 0.82 (1)Å with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.

Crystal data

C14H10N2O	F000 = 928
Mr = 222.24	Dx = 1.303 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7031 reflections
a = 28.071 (6) Å	θ = 3.1–29.0º
b = 5.8471 (12) Å	µ = 0.08 mm−1
c = 14.687 (3) Å	T = 293 (2) K
β = 109.91 (3)º	Block, yellow
V = 2266.6 (9) Å3	0.12 × 0.11 × 0.03 mm
Z = 8

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer	2223 independent reflections
Radiation source: fine-focus sealed tube	971 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.132
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0º
T = 293(2) K	θmin = 3.5º
ω scans	h = −34→34
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)	k = −7→7
Tmin = 0.915, Tmax = 1.00	l = −18→18
9782 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.077	H-atom parameters constrained
wR(F2) = 0.176	w = 1/[σ2(Fo2) + (0.0584P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max < 0.001
2223 reflections	Δρmax = 0.18 e Å−3
154 parameters	Δρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 (Ų)

	x	y	z	Uiso*/Ueq
C13	0.34671 (13)	0.0317 (6)	0.9348 (3)	0.0487 (10)
H14A	0.3362	−0.0983	0.9592	0.058*
C7	0.22581 (13)	0.3041 (6)	0.8582 (2)	0.0466 (10)
H13A	0.2331	0.4471	0.8385	0.056*
N1	0.26153 (10)	0.1571 (4)	0.8889 (2)	0.0443 (8)
C3	0.11223 (12)	0.0032 (6)	0.8792 (3)	0.0504 (10)
H12A	0.1038	−0.1343	0.9017	0.061*
C10	0.37793 (13)	0.4177 (6)	0.8639 (3)	0.0527 (11)
H11A	0.3889	0.5492	0.8414	0.063*
C11	0.41195 (13)	0.2453 (7)	0.9055 (3)	0.0479 (10)
C8	0.31195 (12)	0.1997 (6)	0.8920 (2)	0.0396 (9)
C9	0.32765 (13)	0.3953 (6)	0.8557 (3)	0.0485 (10)
H8A	0.3045	0.5095	0.8262	0.058*
O1	0.19746 (9)	−0.1128 (4)	0.92932 (18)	0.0630 (8)
H1B	0.2253	−0.0677	0.9302	0.095*
C2	0.16187 (13)	0.0481 (6)	0.8873 (3)	0.0439 (9)
C1	0.17471 (12)	0.2547 (6)	0.8532 (2)	0.0384 (9)
C6	0.13639 (13)	0.4125 (6)	0.8116 (3)	0.0497 (10)
H5A	0.1444	0.5505	0.7888	0.060*
C14	0.46381 (14)	0.2676 (6)	0.9108 (3)	0.0591 (12)
C12	0.39627 (13)	0.0523 (6)	0.9420 (3)	0.0522 (10)
H3A	0.4193	−0.0625	0.9713	0.063*
C4	0.07550 (14)	0.1627 (7)	0.8377 (3)	0.0545 (11)
H2A	0.0422	0.1319	0.8323	0.065*
C5	0.08702 (14)	0.3697 (7)	0.8034 (3)	0.0602 (12)
H1A	0.0618	0.4769	0.7754	0.072*
N2	0.50503 (13)	0.2785 (6)	0.9144 (3)	0.0899 (13)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C13	0.052 (2)	0.041 (2)	0.055 (3)	0.0006 (19)	0.020 (2)	0.0061 (19)
C7	0.058 (3)	0.045 (2)	0.038 (2)	−0.009 (2)	0.0190 (19)	0.0019 (18)
N1	0.0419 (17)	0.0436 (18)	0.048 (2)	−0.0016 (15)	0.0161 (15)	0.0017 (15)
C3	0.051 (2)	0.051 (2)	0.051 (3)	−0.007 (2)	0.019 (2)	0.003 (2)
C10	0.055 (2)	0.052 (2)	0.056 (3)	−0.011 (2)	0.026 (2)	0.001 (2)
C11	0.042 (2)	0.055 (2)	0.049 (2)	−0.005 (2)	0.0189 (19)	0.001 (2)
C8	0.038 (2)	0.046 (2)	0.036 (2)	−0.0043 (18)	0.0143 (17)	−0.0006 (18)
C9	0.049 (2)	0.046 (2)	0.051 (3)	0.0014 (19)	0.0181 (19)	0.0106 (19)
O1	0.0538 (17)	0.0503 (16)	0.087 (2)	0.0003 (13)	0.0273 (15)	0.0197 (14)
C2	0.042 (2)	0.045 (2)	0.044 (2)	0.0030 (19)	0.0135 (19)	0.0047 (18)
C1	0.038 (2)	0.042 (2)	0.035 (2)	−0.0046 (18)	0.0124 (17)	−0.0021 (17)
C6	0.049 (2)	0.050 (2)	0.053 (3)	−0.001 (2)	0.0212 (19)	0.009 (2)
C14	0.045 (3)	0.061 (3)	0.070 (3)	0.002 (2)	0.017 (2)	0.009 (2)
C12	0.044 (2)	0.050 (2)	0.062 (3)	0.0027 (19)	0.017 (2)	0.005 (2)
C4	0.042 (2)	0.069 (3)	0.056 (3)	−0.003 (2)	0.021 (2)	0.003 (2)
C5	0.054 (3)	0.065 (3)	0.063 (3)	0.014 (2)	0.021 (2)	0.010 (2)
N2	0.050 (2)	0.097 (3)	0.124 (4)	0.002 (2)	0.033 (2)	0.029 (3)

Geometric parameters (Å, °)

C13—C12	1.364 (4)	C11—C14	1.437 (5)
C13—C8	1.376 (4)	C8—C9	1.395 (4)
C13—H14A	0.9300	C9—H8A	0.9300
C7—N1	1.280 (4)	O1—C2	1.358 (4)
C7—C1	1.440 (4)	O1—H1B	0.8200
C7—H13A	0.9300	C2—C1	1.401 (4)
N1—C8	1.422 (4)	C1—C6	1.391 (4)
C3—C4	1.370 (4)	C6—C5	1.373 (4)
C3—C2	1.383 (4)	C6—H5A	0.9300
C3—H12A	0.9300	C14—N2	1.142 (4)
C10—C11	1.380 (5)	C12—H3A	0.9300
C10—C9	1.381 (4)	C4—C5	1.391 (5)
C10—H11A	0.9300	C4—H2A	0.9300
C11—C12	1.384 (4)	C5—H1A	0.9300
C12—C13—C8	121.2 (3)	C8—C9—H8A	120.3
C12—C13—H14A	119.4	C2—O1—H1B	109.5
C8—C13—H14A	119.4	O1—C2—C3	118.1 (3)
N1—C7—C1	122.0 (3)	O1—C2—C1	121.4 (3)
N1—C7—H13A	119.0	C3—C2—C1	120.5 (3)
C1—C7—H13A	119.0	C6—C1—C2	118.3 (3)
C7—N1—C8	123.0 (3)	C6—C1—C7	119.8 (3)
C4—C3—C2	119.5 (3)	C2—C1—C7	121.8 (3)
C4—C3—H12A	120.2	C5—C6—C1	121.6 (3)
C2—C3—H12A	120.2	C5—C6—H5A	119.2
C11—C10—C9	120.1 (3)	C1—C6—H5A	119.2
C11—C10—H11A	119.9	N2—C14—C11	178.0 (5)
C9—C10—H11A	119.9	C13—C12—C11	119.5 (3)
C10—C11—C12	120.2 (3)	C13—C12—H3A	120.3
C10—C11—C14	119.5 (3)	C11—C12—H3A	120.3
C12—C11—C14	120.2 (4)	C3—C4—C5	121.4 (3)
C13—C8—C9	119.5 (3)	C3—C4—H2A	119.3
C13—C8—N1	115.6 (3)	C5—C4—H2A	119.3
C9—C8—N1	124.9 (3)	C6—C5—C4	118.6 (3)
C10—C9—C8	119.4 (3)	C6—C5—H1A	120.7
C10—C9—H8A	120.3	C4—C5—H1A	120.7

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N1	0.82	1.88	2.609 (4)	147