2-Oxo-2H-chromen-3-yl 4-fluoro­benzoate

Ziki, E.; Sosso, S.; Cissé, L.; Bany, G.E.; Djandé, A.; Kakou-Yao, R.

doi:10.1107/S2414314617005508

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170550

https://doi.org/10.1107/S2414314617005508

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2-Oxo-2H-chromen-3-yl 4-fluorobenzoate

Eric Ziki,^a ^* Siaka Sosso,^b Lamine Cissé,^c Guy Euloge Bany,^a Abdoulaye Djandé ^b and Rita Kakou-Yao ^a

^aLaboratoire de Cristallographie et Physique Moléculaire, UFR SSMT, Université Félix Houphouët Boigny de Cocody 22 BP 582 Abidjan 22, Côte d'Ivoire, ^bLaboratoire de Chimie Moléculaire et Matériaux, Equipe de Chimie Organique et Phytochimie, Université Ouaga I Pr Joseph KI-ZERBO 03 BP 7021 Ouagadougou 03, Burkina Faso, and ^cLaboratoire de Photochimie et d'Analyse, Faculté des Sciences et Techniques, Université Cheick Anta DIOP, Dakar, Senegal
^*Correspondence e-mail: eric.ziki@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 February 2017; accepted 11 April 2017; online 18 April 2017)

In the title compound, C₁₆H₉FO₄, the dihedral angle between the planar coumarin ring system [maximum deviation = 0.027 (1) Å] and the benzene ring is 70.18 (6)°. In the crystal, π–π interactions [shortest centroid–centroid separation = 3.5338 (8) Å] link the molecules into a three-dimensional framework.

Keywords: crystal structure; chroman; hydrogen bond; π–π interactions.

CCDC reference: 1543492

Structure description

Coumarin and its derivatives are widely recognized for their multiple biological activities, including anticancer (Lacy & O'Kennedy, 2004 ) and anti-inflammatory (Todeschini et al., 1998 ) effects. As part of our studies in this area, we now describe the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

The coumarin ring system is, as expected, almost planar [maximum deviation = 0.027 (1) Å for atom C1] and is oriented at an angle of 70.18 (6)° with respect to the benzene ring. The C3—C2 [1.3332 (18) Å] and C2—C1 [1.4553 (19) Å] bond lengths are slightly shorter and longer, respectively, than those expected for a C_ar—C_ar bond. This suggests that the electron density is preferentially located in the C2—C3 bond at the pyrone ring, as seen in other coumarin derivatives (Gomes et al., 2016 ; Ziki et al., 2017 ).

In the crystal, weak aromatic π–π stacking interactions are present [Cg1⋯Cg2ⁱ = 3.5337 (8) Å and Cg2⋯Cg2ⁱ = 3.6529 (8) Å, where Cg1 and Cg2 are the centroids of the coumarin pyran and benzene rings, respectively; symmetry code: (i) 2 − x, 1 − y, 1 − z]. Together, these lead to a three-dimensional supramolecular network.

Synthesis and crystallization

To a solution of 4-fluorobenzoyl chloride (6.17 mmol, ≃1 g) in dry tetrahydrofuran (31 ml), was introduced dried triethylamine (3 molar equivalents, ≃2.6 ml). While stirring strongly, 6.17 mmol (1 g) of chroman-2,3-dione was added in small portions over 30 min. The reaction mixture was then refluxed for 4 h and poured into a separating funnel containing 40 ml of chloroform. The solution was acidified with dilute hydrochloric acid until the pH was 2–3. The organic layer was extracted, washed with water until neutral, dried over MgSO₄ and the solvent removed. The resulting precipitate (crude product) was washed with petroleum ether and dissolved in a minimum amount of chloroform by heating under agitation. To this hot mixture, hexane was added until the formation of a new precipitate started; this dissolved in the resulting mixture upon heating. Upon cooling, colourless crystals of the title compound precipitated in a yield of 80%, m.p. 452–454 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₆H₉FO₄
M_r	284.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.8116 (2), 7.2402 (2), 13.4826 (3)
α, β, γ (°)	96.943 (2), 90.862 (2), 106.139 (2)
V (Å³)	633.21 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	1.00
Crystal size (mm)	0.36 × 0.26 × 0.16

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, AtlasS2
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.788, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12676, 2358, 2112
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.09
No. of reflections	2358
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.19
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1543492

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005508/hb7657sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005508/hb7657Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005508/hb7657Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

2-Oxo-2H-chromen-3-yl 4-fluorobenzoate top

Crystal data top

C₁₆H₉FO₄	Z = 2
M_r = 284.23	F(000) = 292
Triclinic, P1	D_x = 1.491 Mg m⁻³
Hall symbol: -P 1	Melting point: 452 K
a = 6.8116 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 7.2402 (2) Å	Cell parameters from 7530 reflections
c = 13.4826 (3) Å	θ = 6.6–69.4°
α = 96.943 (2)°	µ = 1.00 mm⁻¹
β = 90.862 (2)°	T = 293 K
γ = 106.139 (2)°	Prism, colourless
V = 633.21 (3) Å³	0.36 × 0.26 × 0.16 mm

Data collection top

Agilent SuperNova, Dual, Cu at zero, AtlasS2 diffractometer	2358 independent reflections
Radiation source: fine-focus sealed tube	2112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 5.3048 pixels mm^-1	θ_max = 69.5°, θ_min = 6.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −8→8
T_min = 0.788, T_max = 1.000	l = −16→16
12676 measured reflections

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0435P)² + 0.1315P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2358 reflections	Δρ_max = 0.15 e Å⁻³
191 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (8)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.28843 (13)	0.32990 (14)	0.54636 (7)	0.0486 (3)
O3	0.13270 (16)	0.55441 (14)	0.77556 (7)	0.0526 (3)
C3	−0.06635 (19)	0.37512 (18)	0.63231 (9)	0.0431 (3)
H3	−0.1840	0.3938	0.6607	0.052*
C2	0.1136 (2)	0.44106 (18)	0.68358 (10)	0.0439 (3)
C4	−0.07706 (19)	0.27525 (17)	0.53310 (10)	0.0414 (3)
C8	0.1081 (2)	0.1647 (2)	0.39686 (10)	0.0526 (4)
H8	0.2313	0.1564	0.3706	0.063*
O2	0.47036 (15)	0.47719 (17)	0.68475 (8)	0.0660 (3)
C9	0.1037 (2)	0.25624 (18)	0.49220 (9)	0.0424 (3)
O4	0.19944 (16)	0.32095 (15)	0.85538 (8)	0.0599 (3)
C5	−0.2591 (2)	0.1964 (2)	0.47421 (11)	0.0509 (3)
H5	−0.3823	0.2080	0.4991	0.061*
C1	0.3038 (2)	0.4204 (2)	0.64253 (10)	0.0470 (3)
C11	0.22979 (19)	0.6336 (2)	0.94604 (10)	0.0471 (3)
C10	0.1894 (2)	0.4839 (2)	0.85772 (10)	0.0473 (3)
F	0.34415 (19)	1.0344 (2)	1.19588 (8)	0.1091 (5)
C6	−0.2564 (3)	0.1018 (2)	0.37969 (12)	0.0602 (4)
H6	−0.3781	0.0482	0.3413	0.072*
C16	0.2040 (2)	0.8158 (2)	0.94244 (11)	0.0550 (4)
H16	0.1610	0.8470	0.8825	0.066*
C15	0.2415 (2)	0.9517 (3)	1.02675 (13)	0.0663 (4)
H15	0.2234	1.0739	1.0247	0.080*
C7	−0.0734 (3)	0.0859 (2)	0.34129 (11)	0.0602 (4)
H7	−0.0733	0.0213	0.2773	0.072*
C12	0.2947 (2)	0.5883 (3)	1.03582 (11)	0.0577 (4)
H12	0.3111	0.4658	1.0390	0.069*
C13	0.3350 (2)	0.7236 (3)	1.12031 (11)	0.0692 (5)
H13	0.3807	0.6949	1.1804	0.083*
C14	0.3060 (2)	0.9012 (3)	1.11331 (12)	0.0703 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0441 (5)	0.0577 (6)	0.0475 (5)	0.0211 (4)	0.0023 (4)	0.0047 (4)
O3	0.0689 (6)	0.0553 (6)	0.0386 (5)	0.0281 (5)	−0.0071 (4)	0.0014 (4)
C3	0.0447 (7)	0.0472 (7)	0.0427 (7)	0.0198 (6)	0.0045 (5)	0.0100 (6)
C2	0.0523 (7)	0.0439 (7)	0.0386 (7)	0.0190 (6)	−0.0022 (5)	0.0053 (5)
C4	0.0465 (7)	0.0389 (6)	0.0412 (7)	0.0148 (5)	−0.0020 (5)	0.0092 (5)
C8	0.0717 (9)	0.0509 (8)	0.0431 (7)	0.0297 (7)	0.0051 (7)	0.0073 (6)
O2	0.0463 (6)	0.0844 (8)	0.0644 (7)	0.0155 (5)	−0.0097 (5)	0.0067 (6)
C9	0.0493 (7)	0.0395 (6)	0.0420 (7)	0.0174 (5)	−0.0010 (5)	0.0084 (5)
O4	0.0687 (7)	0.0593 (6)	0.0574 (6)	0.0261 (5)	−0.0023 (5)	0.0121 (5)
C5	0.0484 (7)	0.0501 (8)	0.0546 (8)	0.0136 (6)	−0.0070 (6)	0.0104 (6)
C1	0.0470 (7)	0.0487 (7)	0.0471 (7)	0.0155 (6)	−0.0033 (6)	0.0085 (6)
C11	0.0377 (6)	0.0651 (9)	0.0397 (7)	0.0162 (6)	0.0005 (5)	0.0075 (6)
C10	0.0421 (7)	0.0588 (8)	0.0438 (7)	0.0175 (6)	0.0001 (5)	0.0101 (6)
F	0.1002 (9)	0.1531 (12)	0.0620 (7)	0.0413 (8)	−0.0124 (6)	−0.0444 (7)
C6	0.0707 (10)	0.0504 (8)	0.0558 (9)	0.0126 (7)	−0.0200 (7)	0.0063 (7)
C16	0.0528 (8)	0.0656 (9)	0.0471 (8)	0.0201 (7)	−0.0054 (6)	0.0017 (7)
C15	0.0600 (9)	0.0731 (10)	0.0630 (10)	0.0225 (8)	−0.0029 (7)	−0.0103 (8)
C7	0.0944 (12)	0.0479 (8)	0.0418 (8)	0.0275 (8)	−0.0080 (8)	0.0027 (6)
C12	0.0478 (8)	0.0856 (11)	0.0455 (8)	0.0253 (7)	0.0033 (6)	0.0156 (7)
C13	0.0516 (9)	0.1223 (16)	0.0361 (8)	0.0295 (9)	0.0000 (6)	0.0087 (8)
C14	0.0496 (8)	0.1086 (14)	0.0460 (9)	0.0234 (9)	−0.0019 (7)	−0.0175 (9)

Geometric parameters (Å, º) top

O1—C1	1.3688 (16)	C5—H5	0.9300
O1—C9	1.3804 (15)	C11—C16	1.385 (2)
O3—C10	1.3676 (16)	C11—C12	1.389 (2)
O3—C2	1.3849 (15)	C11—C10	1.4765 (19)
C3—C2	1.3332 (18)	F—C14	1.3525 (18)
C3—C4	1.4322 (17)	C6—C7	1.386 (2)
C3—H3	0.9300	C6—H6	0.9300
C2—C1	1.4553 (19)	C16—C15	1.381 (2)
C4—C9	1.3914 (18)	C16—H16	0.9300
C4—C5	1.4005 (18)	C15—C14	1.366 (3)
C8—C7	1.376 (2)	C15—H15	0.9300
C8—C9	1.3779 (18)	C7—H7	0.9300
C8—H8	0.9300	C12—C13	1.380 (2)
O2—C1	1.2018 (16)	C12—H12	0.9300
O4—C10	1.1974 (17)	C13—C14	1.368 (3)
C5—C6	1.375 (2)	C13—H13	0.9300

C1—O1—C9	122.55 (10)	C12—C11—C10	118.42 (14)
C10—O3—C2	118.12 (10)	O4—C10—O3	122.73 (13)
C2—C3—C4	119.50 (12)	O4—C10—C11	126.62 (13)
C2—C3—H3	120.2	O3—C10—C11	110.64 (12)
C4—C3—H3	120.2	C5—C6—C7	120.37 (14)
C3—C2—O3	120.88 (12)	C5—C6—H6	119.8
C3—C2—C1	122.92 (12)	C7—C6—H6	119.8
O3—C2—C1	115.77 (11)	C15—C16—C11	120.84 (15)
C9—C4—C5	117.83 (12)	C15—C16—H16	119.6
C9—C4—C3	118.33 (11)	C11—C16—H16	119.6
C5—C4—C3	123.83 (12)	C14—C15—C16	117.96 (17)
C7—C8—C9	118.66 (14)	C14—C15—H15	121.0
C7—C8—H8	120.7	C16—C15—H15	121.0
C9—C8—H8	120.7	C8—C7—C6	120.63 (14)
C8—C9—O1	116.95 (12)	C8—C7—H7	119.7
C8—C9—C4	122.25 (12)	C6—C7—H7	119.7
O1—C9—C4	120.80 (11)	C13—C12—C11	120.52 (16)
C6—C5—C4	120.23 (14)	C13—C12—H12	119.7
C6—C5—H5	119.9	C11—C12—H12	119.7
C4—C5—H5	119.9	C14—C13—C12	118.18 (15)
O2—C1—O1	118.12 (13)	C14—C13—H13	120.9
O2—C1—C2	126.03 (13)	C12—C13—H13	120.9
O1—C1—C2	115.84 (11)	F—C14—C15	118.14 (19)
C16—C11—C12	119.20 (14)	F—C14—C13	118.57 (16)
C16—C11—C10	122.38 (12)	C15—C14—C13	123.29 (15)

C4—C3—C2—O3	173.63 (11)	O3—C2—C1—O1	−171.86 (10)
C4—C3—C2—C1	1.4 (2)	C2—O3—C10—O4	−9.0 (2)
C10—O3—C2—C3	117.23 (14)	C2—O3—C10—C11	172.17 (11)
C10—O3—C2—C1	−70.06 (16)	C16—C11—C10—O4	−176.64 (14)
C2—C3—C4—C9	−2.15 (18)	C12—C11—C10—O4	3.0 (2)
C2—C3—C4—C5	178.32 (12)	C16—C11—C10—O3	2.11 (18)
C7—C8—C9—O1	178.67 (11)	C12—C11—C10—O3	−178.30 (12)
C7—C8—C9—C4	−1.5 (2)	C4—C5—C6—C7	−0.9 (2)
C1—O1—C9—C8	−178.64 (11)	C12—C11—C16—C15	−0.2 (2)
C1—O1—C9—C4	1.50 (18)	C10—C11—C16—C15	179.41 (13)
C5—C4—C9—C8	0.44 (19)	C11—C16—C15—C14	0.5 (2)
C3—C4—C9—C8	−179.12 (12)	C9—C8—C7—C6	1.3 (2)
C5—C4—C9—O1	−179.71 (11)	C5—C6—C7—C8	−0.2 (2)
C3—C4—C9—O1	0.73 (18)	C16—C11—C12—C13	−0.6 (2)
C9—C4—C5—C6	0.8 (2)	C10—C11—C12—C13	179.79 (13)
C3—C4—C5—C6	−179.72 (12)	C11—C12—C13—C14	1.1 (2)
C9—O1—C1—O2	178.72 (12)	C16—C15—C14—F	179.56 (14)
C9—O1—C1—C2	−2.18 (18)	C16—C15—C14—C13	0.0 (3)
C3—C2—C1—O2	179.71 (14)	C12—C13—C14—F	179.68 (14)
O3—C2—C1—O2	7.2 (2)	C12—C13—C14—C15	−0.8 (3)
C3—C2—C1—O1	0.69 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O3	0.93	2.37	2.7031 (17)	101

Acknowledgements

The authors thank the Spectropole Service of the Faculty of Sciences (Aix-Marseille, France) for the use of the diffractometer and the NMR and MS spectrometers.

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