7-Fluoro-4-oxochromene-3-carbaldehyde

Asad, M.; Oo, C.-W.; Osman, H.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811007045

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o766

doi:10.1107/S1600536811007045

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7-Fluoro-4-oxochromene-3-carbaldehyde

Mohammad Asad,^a Chuan-Wei Oo,^a ‡ Hasnah Osman,^a Madhukar Hemamalini ^b and Hoong-Kun Fun ^b ^*§

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 18 February 2011; accepted 24 February 2011; online 2 March 2011)

In the title compound, C₁₀H₅FO₃, the chromenone ring is essentially planar, with a maximum deviation of 0.039 (1) Å. The dihedral angle between the fluoro-subsituted benzene ring and the pyran ring is 1.92 (4)°. In the crystal, molecules are connected via weak intermolecular C—H⋯O hydrogen bonds, forming supramolecular ribbons along the b axis. These ribbons are stacked down the a axis.

Related literature

For the biological activity of chromones, see: Masami et al. (2007 ); Ellis et al. (1978 ); Raj et al. (2010 ); Nawrot-Modranka et al. (2006 ); Gomes et al. (2010 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₀H₅FO₃
M_r = 192.14
Monoclinic, P 2₁ /c
a = 3.7294 (1) Å
b = 6.2347 (2) Å
c = 34.6518 (11) Å
β = 90.740 (1)°
V = 805.65 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.52 × 0.20 × 0.08 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.935, T_max = 0.990
20369 measured reflections
2937 independent reflections
2622 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.125
S = 1.03
2937 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O3ⁱ	0.93	2.39	3.2147 (11)	148
C3—H3A⋯O2ⁱⁱ	0.93	2.29	3.1419 (12)	152
C10—H10A⋯O3ⁱⁱⁱ	0.93	2.58	3.3010 (14)	135
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x-1, y-1, z; (iii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007045/rz2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007045/rz2562Isup2.hkl

checkCIF report

Comment top

A large number of chromones and their derivatives possess a broad range of biological activities such as anti-HIV (Masami et al., 2007), antiallergic (Ellis et al., 1978), anticancer (Raj et al., 2010), antibacterial (Nawrot-Modranka et al., 2006), antiviral and antioxidant (Gomes et al., 2010) properties. We report here the structure of a newly synthesized chromone derivative, 7-fluoro-3-formylchromone. It was synthesized by own experimental process and structure elucidation was primarily carried out by elemental analysis, ¹H NMR and IR spectroscopic techniques.

The asymmetric unit of the title compound is shown in Fig. 1. The chromenone (O1/C1–C9) ring is essentially planar, with a maximum deviation of 0.039 (1) Å for atom C8. The dihedral angle between the fluoro-substituted benzene (C2–C7) ring and the pyran (O1/C1/C2/C7–C9) ring is 1.92 (4)°.

In the crystal structure (Fig. 2), adjacent molecules are connected via intermolecular C1—H1A···O3; C3—H3A···O2 and C10—H10A···O3 (Table 1) hydrogen bonds to form supramolecular ribbons along the b axis. These ribbons are stacked down the a axis.

Related literature top

For the biological activity of chromones, see: Masami et al. (2007); Ellis et al. (1978); Raj et al. (2010); Nawrot-Modranka et al. (2006); Gomes et al. (2010). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

To a well stirred solution of 4-fluoro-2-hydroxyacetophenone (6.5 mmol, 1.0 g) in DMF (4 ml), POCl₃ (26.1 mmol, 2.4 ml) was added dropwise with stirring in ice bath. After 15 minutes, the ice bath was removed and the reaction mixture was continued to be stirred at room temperature for overnight. The resultant reaction mixture was then decomposed by crushed ice and the final product was collected by filtration, washed with ethanol-water and recrystallized from acetone to afford the title compound in 75% yield.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of the title compound viewed along the a axis, showing a hydrogen-bonded (dashed lines) network.

7-Fluoro-4-oxochromene-3-carbaldehyde top

Crystal data top

C₁₀H₅FO₃	F(000) = 392
M_r = 192.14	D_x = 1.584 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9357 reflections
a = 3.7294 (1) Å	θ = 3.3–32.6°
b = 6.2347 (2) Å	µ = 0.13 mm⁻¹
c = 34.6518 (11) Å	T = 100 K
β = 90.740 (1)°	Plate, yellow
V = 805.65 (4) Å³	0.52 × 0.20 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	2937 independent reflections
Radiation source: fine-focus sealed tube	2622 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 32.6°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.935, T_max = 0.990	k = −9→9
20369 measured reflections	l = −51→52

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0705P)² + 0.3007P] where P = (F_o² + 2F_c²)/3
2937 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₅FO₃	V = 805.65 (4) Å³
M_r = 192.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.7294 (1) Å	µ = 0.13 mm⁻¹
b = 6.2347 (2) Å	T = 100 K
c = 34.6518 (11) Å	0.52 × 0.20 × 0.08 mm
β = 90.740 (1)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	2937 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2622 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.990	R_int = 0.022
20369 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.03	Δρ_max = 0.68 e Å⁻³
2937 reflections	Δρ_min = −0.18 e Å⁻³
127 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
F1	0.11979 (18)	0.11518 (12)	0.279011 (18)	0.02856 (16)
O1	0.12537 (18)	0.31079 (11)	0.409211 (19)	0.01826 (15)
O2	0.6366 (2)	0.87750 (12)	0.38719 (2)	0.02381 (17)
O3	0.2976 (2)	0.75507 (14)	0.49717 (2)	0.02861 (18)
C1	0.1927 (2)	0.45457 (15)	0.43718 (2)	0.01768 (17)
H1A	0.1255	0.4194	0.4621	0.021*
C2	0.2137 (2)	0.36246 (14)	0.37194 (2)	0.01554 (16)
C3	0.1252 (2)	0.20906 (15)	0.34431 (3)	0.01823 (17)
H3A	0.0180	0.0796	0.3508	0.022*
C4	0.2053 (2)	0.25964 (16)	0.30674 (3)	0.01986 (18)
C5	0.3659 (2)	0.45082 (17)	0.29548 (3)	0.02122 (19)
H5A	0.4134	0.4783	0.2697	0.025*
C6	0.4525 (2)	0.59831 (16)	0.32376 (3)	0.01913 (18)
H6A	0.5617	0.7268	0.3170	0.023*
C7	0.3775 (2)	0.55659 (14)	0.36268 (2)	0.01570 (16)
C8	0.4695 (2)	0.71039 (14)	0.39326 (3)	0.01698 (17)
C9	0.3518 (2)	0.64737 (15)	0.43164 (3)	0.01704 (17)
C10	0.4046 (3)	0.79260 (17)	0.46468 (3)	0.02236 (19)
H10A	0.5266	0.9205	0.4606	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0312 (3)	0.0358 (4)	0.0187 (3)	−0.0032 (3)	0.0015 (2)	−0.0083 (2)
O1	0.0214 (3)	0.0184 (3)	0.0151 (3)	−0.0049 (2)	0.0026 (2)	0.0025 (2)
O2	0.0249 (3)	0.0205 (3)	0.0260 (3)	−0.0073 (3)	0.0031 (3)	0.0042 (3)
O3	0.0367 (4)	0.0295 (4)	0.0198 (3)	−0.0090 (3)	0.0056 (3)	−0.0039 (3)
C1	0.0181 (4)	0.0201 (4)	0.0149 (3)	−0.0024 (3)	0.0014 (3)	0.0023 (3)
C2	0.0140 (3)	0.0185 (4)	0.0141 (3)	−0.0006 (3)	0.0022 (3)	0.0030 (3)
C3	0.0164 (4)	0.0203 (4)	0.0180 (4)	−0.0014 (3)	0.0014 (3)	0.0008 (3)
C4	0.0169 (4)	0.0264 (4)	0.0162 (4)	0.0007 (3)	0.0000 (3)	−0.0022 (3)
C5	0.0182 (4)	0.0300 (5)	0.0155 (4)	0.0007 (3)	0.0024 (3)	0.0044 (3)
C6	0.0162 (4)	0.0233 (4)	0.0179 (4)	−0.0007 (3)	0.0025 (3)	0.0064 (3)
C7	0.0133 (3)	0.0178 (4)	0.0160 (3)	−0.0004 (3)	0.0012 (3)	0.0037 (3)
C8	0.0145 (3)	0.0178 (4)	0.0187 (4)	−0.0007 (3)	0.0016 (3)	0.0043 (3)
C9	0.0164 (3)	0.0185 (4)	0.0162 (3)	−0.0023 (3)	0.0006 (3)	0.0013 (3)
C10	0.0244 (4)	0.0230 (4)	0.0198 (4)	−0.0041 (3)	0.0010 (3)	−0.0013 (3)

Geometric parameters (Å, º) top

F1—C4	1.3521 (11)	C3—H3A	0.9300
O1—C1	1.3414 (11)	C4—C5	1.3921 (14)
O1—C2	1.3751 (10)	C5—C6	1.3791 (14)
O2—C8	1.2334 (11)	C5—H5A	0.9300
O3—C10	1.2218 (12)	C6—C7	1.4052 (12)
C1—C9	1.3551 (12)	C6—H6A	0.9300
C1—H1A	0.9300	C7—C8	1.4664 (13)
C2—C3	1.3902 (12)	C8—C9	1.4599 (12)
C2—C7	1.3950 (12)	C9—C10	1.4711 (13)
C3—C4	1.3759 (12)	C10—H10A	0.9300

C1—O1—C2	118.49 (7)	C5—C6—C7	120.72 (9)
O1—C1—C9	124.66 (8)	C5—C6—H6A	119.6
O1—C1—H1A	117.7	C7—C6—H6A	119.6
C9—C1—H1A	117.7	C2—C7—C6	118.33 (8)
O1—C2—C3	115.35 (8)	C2—C7—C8	120.02 (8)
O1—C2—C7	122.02 (8)	C6—C7—C8	121.65 (8)
C3—C2—C7	122.63 (8)	O2—C8—C9	122.77 (9)
C4—C3—C2	116.20 (9)	O2—C8—C7	122.90 (8)
C4—C3—H3A	121.9	C9—C8—C7	114.32 (8)
C2—C3—H3A	121.9	C1—C9—C8	120.34 (8)
F1—C4—C3	117.88 (9)	C1—C9—C10	119.36 (8)
F1—C4—C5	118.01 (8)	C8—C9—C10	120.30 (8)
C3—C4—C5	124.11 (9)	O3—C10—C9	123.87 (9)
C6—C5—C4	118.01 (8)	O3—C10—H10A	118.1
C6—C5—H5A	121.0	C9—C10—H10A	118.1
C4—C5—H5A	121.0

C2—O1—C1—C9	−1.81 (13)	C5—C6—C7—C2	0.03 (13)
C1—O1—C2—C3	−177.90 (8)	C5—C6—C7—C8	179.56 (8)
C1—O1—C2—C7	1.50 (12)	C2—C7—C8—O2	174.82 (8)
O1—C2—C3—C4	178.80 (8)	C6—C7—C8—O2	−4.70 (14)
C7—C2—C3—C4	−0.59 (13)	C2—C7—C8—C9	−4.23 (12)
C2—C3—C4—F1	−179.36 (8)	C6—C7—C8—C9	176.24 (8)
C2—C3—C4—C5	0.09 (14)	O1—C1—C9—C8	−1.12 (14)
F1—C4—C5—C6	179.89 (8)	O1—C1—C9—C10	178.88 (9)
C3—C4—C5—C6	0.45 (15)	O2—C8—C9—C1	−175.04 (9)
C4—C5—C6—C7	−0.49 (14)	C7—C8—C9—C1	4.01 (12)
O1—C2—C7—C6	−178.81 (8)	O2—C8—C9—C10	4.95 (14)
C3—C2—C7—C6	0.54 (13)	C7—C8—C9—C10	−175.99 (8)
O1—C2—C7—C8	1.65 (13)	C1—C9—C10—O3	−3.67 (15)
C3—C2—C7—C8	−178.99 (8)	C8—C9—C10—O3	176.33 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3ⁱ	0.93	2.39	3.2147 (11)	148
C3—H3A···O2ⁱⁱ	0.93	2.29	3.1419 (12)	152
C10—H10A···O3ⁱⁱⁱ	0.93	2.58	3.3010 (14)	135

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₅FO₃
M_r	192.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.7294 (1), 6.2347 (2), 34.6518 (11)
β (°)	90.740 (1)
V (Å³)	805.65 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.52 × 0.20 × 0.08

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.935, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	20369, 2937, 2622
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.125, 1.03
No. of reflections	2937
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3ⁱ	0.93	2.39	3.2147 (11)	148
C3—H3A···O2ⁱⁱ	0.93	2.29	3.1419 (12)	152
C10—H10A···O3ⁱⁱⁱ	0.93	2.58	3.3010 (14)	135

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+2, −z+1.

Footnotes

‡Additional correspondence author, e-mail: oocw@usm.my.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MA, CWO and HO thank Universiti Sains Malaysia (USM) for providing necessary research facilities and RU research funding under grant No. 1001/PKIMIA/811134. MA also thanks USM for the award of post-doctoral fellowship. HKF and MH thank the Malaysian Government and USM for the Research University grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

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