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

Cui, P.; Shi, L.

doi:10.1107/S1600536809017280

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1282

doi:10.1107/S1600536809017280

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

Ping Cui ^a and Lei Shi ^a ^*

^aKey Laboratory of Anhui Educational Department, Anhui University of Technology, Maanshan 243002, People's Republic of China, and State Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: shilei0828@gmail.com

(Received 7 May 2009; accepted 8 May 2009; online 14 May 2009)

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, P 2₁ /n
a = 13.1635 (11) Å
b = 6.2252 (6) Å
c = 13.8235 (17) Å
β = 113.33 (3)°
V = 1040.1 (3) Å³
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[F² > 2σ(F²)] = 0.053
wR(F²) = 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

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

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017280/hb2968sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017280/hb2968Isup2.hkl

checkCIF report

Comment top

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)°.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.

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

Crystal data top

C₁₂H₉FN₂O	F(000) = 448
M_r = 216.21	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0657P)² + 0.1652P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1825 reflections	Δρ_max = 0.16 e Å⁻³
147 parameters	Δρ_min = −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)

Crystal data top

C₁₂H₉FN₂O	V = 1040.1 (3) Å³
M_r = 216.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.1635 (11) Å	µ = 0.10 mm⁻¹
b = 6.2252 (6) Å	T = 293 K
c = 13.8235 (17) Å	0.40 × 0.25 × 0.15 mm
β = 113.33 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1825 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1210 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.985	R_int = 0.064
1907 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
1825 reflections	Δρ_min = −0.17 e Å⁻³
147 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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉FN₂O
M_r	216.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.1635 (11), 6.2252 (6), 13.8235 (17)
β (°)	113.33 (3)
V (Å³)	1040.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.960, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	1907, 1825, 1210
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.145, 1.05
No. of reflections	1825
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

We thank the Measurement Foundation of Nanjing University, and Dr Rui-Qin Fang for her support.

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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, Y.-G., Huang, K.-X., Ai, L. & Zhu, H.-L. (2006). Acta Cryst. E62, o2219–o2220. Web of Science CSD CrossRef IUCr Journals Google Scholar
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