4-Fluoro-2-[(E)-2-pyridyliminomethyl]phenol

Abstract

In the title compound, C₁₂H₉FN₂O, the dihedral angle between the benzene ring and the pyridine ring is 4.35 (16)°. The mol­ecular conformation is stabilized by an intra­molecular O—H⋯N hydrogen bond.

Related literature

For a related structure, see: Li et al. (2006 ▶). For reference strutural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₂H₉FN₂O

• M _r = 216.21

• Monoclinic,

• a = 13.1635 (11) Å

• b = 6.2252 (6) Å

• c = 13.8235 (17) Å

• β = 113.33 (3)°

• V = 1040.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.40 × 0.25 × 0.15 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.960, T _max = 0.985

• 1907 measured reflections

• 1825 independent reflections

• 1210 reflections with I > 2σ(I)

• R _int = 0.064

Refinement

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.145

• S = 1.05

• 1825 reflections

• 147 parameters

• H-atom parameters constrained

• Δρ_max = 0.16 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: SHELXL97.

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—H1⋯N1	0.82	1.86	2.588 (2)	147

supplementary crystallographic information

Comment

Recently, we have reported the structural characterization of one Schiff base compound derived from the condensation of 5-chloro-salicylaldehyde and primary amines (Li et al., 2006). As an extension of this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). There is an intramolecular O—H···N hydrogen bond in (I). The dihedral angle between the two aromatic rings is 4.35(0.16)°.

Experimental

Pyridin-2-amine (94 mg, 1 mmol) and 5-fluoro-salicylaldehyde (140 mg, 1 mmol) were dissolved in methanol (10 ml) at 323 K. The mixture was stirred for 2 h to give a clear yellow solution. After keeping the solution in air for 7 d by slow evaporation of the solvent, yellow blocks of (I) were formed at the bottom of the vessel, with 80% yield. The crystals were isolated, washed three times with methanol and dried in a vacuum desiccator containing anhydrous CaCl₂.

Refinement

All H atoms were positioned geometrically (C—H = 0.93–0.96 Å, O—H = 0.82Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier).

Figures

Fig. 1.

The molecular structure of (I) showing 30% probability displacement ellipsoids.

Crystal data

C12H9FN2O	F(000) = 448
Mr = 216.21	Dx = 1.381 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 13.1635 (11) Å	θ = 9–12°
b = 6.2252 (6) Å	µ = 0.10 mm−1
c = 13.8235 (17) Å	T = 293 K
β = 113.33 (3)°	Block, yellow
V = 1040.1 (3) Å3	0.40 × 0.25 × 0.15 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1825 independent reflections
Radiation source: fine-focus sealed tube	1210 reflections with I > 2σ(I)
graphite	Rint = 0.064
ω/2θ scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: ψ scan (North et al., 1968)	h = 0→15
Tmin = 0.960, Tmax = 0.985	k = 0→7
1907 measured reflections	l = −16→15

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)] = 0.053	H-atom parameters constrained
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0657P)2 + 0.1652P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1825 reflections	Δρmax = 0.16 e Å−3
147 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.089 (10)

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
C1	0.96836 (16)	0.2734 (3)	0.23488 (17)	0.0457 (6)
C2	1.06679 (18)	0.2492 (4)	0.21918 (18)	0.0529 (6)
C3	1.1349 (2)	0.0730 (4)	0.2622 (2)	0.0633 (7)
H3	1.1996	0.0568	0.2510	0.076*
C4	1.1080 (2)	−0.0767 (4)	0.3207 (2)	0.0658 (7)
H4	1.1540	−0.1936	0.3496	0.079*
C5	1.0116 (2)	−0.0506 (4)	0.3357 (2)	0.0619 (7)
C6	0.94233 (19)	0.1189 (3)	0.29492 (19)	0.0548 (6)
H6	0.8779	0.1318	0.3069	0.066*
C7	0.89393 (17)	0.4506 (3)	0.18913 (17)	0.0484 (6)
H7	0.8301	0.4632	0.2022	0.058*
C8	0.83993 (18)	0.7650 (3)	0.08721 (17)	0.0488 (6)
C9	0.8652 (2)	0.9050 (4)	0.02246 (19)	0.0591 (7)
H9	0.9269	0.8816	0.0070	0.071*
C10	0.7981 (2)	1.0788 (4)	−0.01873 (19)	0.0673 (7)
H10	0.8141	1.1762	−0.0618	0.081*
C11	0.7071 (2)	1.1067 (4)	0.0045 (2)	0.0677 (7)
H11	0.6600	1.2231	−0.0223	0.081*
C12	0.6870 (2)	0.9583 (4)	0.0684 (2)	0.0660 (7)
H12	0.6247	0.9772	0.0835	0.079*
F1	0.98419 (14)	−0.2003 (2)	0.39318 (14)	0.0938 (6)
N1	0.91366 (15)	0.5906 (3)	0.13106 (15)	0.0514 (5)
N2	0.75169 (16)	0.7888 (3)	0.11012 (15)	0.0582 (6)
O1	1.09729 (14)	0.3937 (3)	0.16264 (16)	0.0721 (6)
H1	1.0476	0.4818	0.1364	0.108*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0411 (11)	0.0435 (12)	0.0504 (13)	−0.0015 (10)	0.0159 (10)	−0.0095 (10)
C2	0.0488 (13)	0.0527 (13)	0.0569 (14)	−0.0022 (11)	0.0206 (11)	−0.0129 (12)
C3	0.0499 (14)	0.0678 (17)	0.0690 (16)	0.0094 (13)	0.0201 (13)	−0.0160 (14)
C4	0.0655 (17)	0.0503 (15)	0.0676 (17)	0.0120 (13)	0.0116 (13)	−0.0067 (13)
C5	0.0649 (16)	0.0453 (13)	0.0677 (16)	−0.0035 (12)	0.0181 (13)	0.0006 (12)
C6	0.0502 (13)	0.0500 (14)	0.0638 (15)	−0.0036 (11)	0.0221 (11)	−0.0062 (12)
C7	0.0439 (12)	0.0493 (13)	0.0539 (14)	−0.0027 (10)	0.0216 (11)	−0.0089 (11)
C8	0.0513 (13)	0.0479 (13)	0.0462 (13)	−0.0020 (11)	0.0181 (11)	−0.0058 (11)
C9	0.0651 (16)	0.0579 (15)	0.0577 (15)	−0.0051 (12)	0.0280 (13)	−0.0030 (12)
C10	0.0829 (19)	0.0613 (16)	0.0551 (15)	−0.0051 (15)	0.0248 (14)	0.0088 (13)
C11	0.0761 (18)	0.0572 (16)	0.0582 (15)	0.0115 (14)	0.0143 (14)	0.0083 (13)
C12	0.0631 (16)	0.0661 (16)	0.0678 (16)	0.0146 (13)	0.0249 (13)	0.0088 (14)
F1	0.1042 (13)	0.0645 (10)	0.1094 (13)	0.0031 (9)	0.0390 (10)	0.0279 (9)
N1	0.0525 (11)	0.0486 (11)	0.0553 (12)	−0.0021 (9)	0.0237 (9)	−0.0043 (10)
N2	0.0564 (12)	0.0585 (12)	0.0618 (13)	0.0107 (10)	0.0257 (10)	0.0087 (10)
O1	0.0616 (11)	0.0784 (13)	0.0899 (14)	0.0050 (9)	0.0444 (10)	0.0052 (11)

Geometric parameters (Å, °)

C1—C6	1.399 (3)	C7—H7	0.9300
C1—C2	1.404 (3)	C8—N2	1.328 (3)
C1—C7	1.444 (3)	C8—C9	1.381 (3)
C2—O1	1.353 (3)	C8—N1	1.422 (3)
C2—C3	1.392 (3)	C9—C10	1.370 (3)
C3—C4	1.369 (3)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.368 (4)
C4—C5	1.375 (3)	C10—H10	0.9300
C4—H4	0.9300	C11—C12	1.375 (3)
C5—C6	1.362 (3)	C11—H11	0.9300
C5—F1	1.363 (3)	C12—N2	1.335 (3)
C6—H6	0.9300	C12—H12	0.9300
C7—N1	1.279 (3)	O1—H1	0.8200
C6—C1—C2	118.4 (2)	C1—C7—H7	119.2
C6—C1—C7	120.12 (19)	N2—C8—C9	122.8 (2)
C2—C1—C7	121.5 (2)	N2—C8—N1	119.8 (2)
O1—C2—C3	118.8 (2)	C9—C8—N1	117.3 (2)
O1—C2—C1	121.4 (2)	C10—C9—C8	119.1 (2)
C3—C2—C1	119.7 (2)	C10—C9—H9	120.4
C4—C3—C2	121.0 (2)	C8—C9—H9	120.4
C4—C3—H3	119.5	C11—C10—C9	118.9 (2)
C2—C3—H3	119.5	C11—C10—H10	120.6
C3—C4—C5	118.6 (2)	C9—C10—H10	120.6
C3—C4—H4	120.7	C10—C11—C12	118.4 (2)
C5—C4—H4	120.7	C10—C11—H11	120.8
C6—C5—F1	118.9 (2)	C12—C11—H11	120.8
C6—C5—C4	122.4 (2)	N2—C12—C11	123.8 (2)
F1—C5—C4	118.8 (2)	N2—C12—H12	118.1
C5—C6—C1	119.8 (2)	C11—C12—H12	118.1
C5—C6—H6	120.1	C7—N1—C8	120.91 (19)
C1—C6—H6	120.1	C8—N2—C12	117.0 (2)
N1—C7—C1	121.6 (2)	C2—O1—H1	109.5
N1—C7—H7	119.2
C6—C1—C2—O1	−179.5 (2)	C6—C1—C7—N1	−177.70 (19)
C7—C1—C2—O1	1.6 (3)	C2—C1—C7—N1	1.2 (3)
C6—C1—C2—C3	0.7 (3)	N2—C8—C9—C10	1.3 (3)
C7—C1—C2—C3	−178.2 (2)	N1—C8—C9—C10	−178.0 (2)
O1—C2—C3—C4	179.5 (2)	C8—C9—C10—C11	−0.9 (4)
C1—C2—C3—C4	−0.6 (3)	C9—C10—C11—C12	0.0 (4)
C2—C3—C4—C5	0.4 (4)	C10—C11—C12—N2	0.6 (4)
C3—C4—C5—C6	−0.2 (4)	C1—C7—N1—C8	−179.53 (19)
C3—C4—C5—F1	179.5 (2)	N2—C8—N1—C7	2.8 (3)
F1—C5—C6—C1	−179.4 (2)	C9—C8—N1—C7	−177.8 (2)
C4—C5—C6—C1	0.3 (4)	C9—C8—N2—C12	−0.8 (3)
C2—C1—C6—C5	−0.5 (3)	N1—C8—N2—C12	178.5 (2)
C7—C1—C6—C5	178.4 (2)	C11—C12—N2—C8	−0.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.588 (2)	147