2-Oxo-2H-chromen-3-yl benzoate

Kambo, K.R.; Sosso, S.; Mansilla-Koblavi, F.; Djandé, A.; Kakou-Yao, R.

doi:10.1107/S2414314617006630

organic compounds

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ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170663

https://doi.org/10.1107/S2414314617006630

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2-Oxo-2H-chromen-3-yl benzoate

Konan René Kambo,^a ^* Siaka Sosso,^b F. Mansilla-Koblavi,^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, and ^bLaboratoire de Chimie Moléculaire et de Matériaux, Equipe de Chimie, Organique et de Phytochimie, Université Ouaga I Pr Joseph KI-ZERBO, 03 BP 7021, Burkina Faso
^*Correspondence e-mail: kamborene@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 28 April 2017; accepted 3 May 2017; online 19 May 2017)

In the title compound, C₁₆H₁₀O₄, the dihedral angle between the coumarin ring system (r.m.s. deviation = 0.015 Å) and the benzoate group is 83.58 (9)°, which compares to a value of 81.8° obtained from a DFT calculation at the B3LYP/6–311 G(d,p) level. In the crystal, C—O⋯π and C—H⋯π interactions and aromatic π–π [Cg⋯Cg = 3.7214 (14) and 3.7059 (14) Å] stacking generate a three-dimensional network.

Keywords: crystal structure; density functional theory; packing features.

CCDC reference: 1547586

Structure description

Coumarin-based ion receptors, fluorescent probes, and biological stains have extensive applications in monitoring enzyme activity as well as accurate pharmacological and pharmacokinetic properties in living cells (Chen et al., 2013 ; Guha et al., 2012 ). As part of our ongoing studies in this area, we now present herein the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

As expected, the coumarin ring system is almost planar, the maximum deviation from the plane of 0.022 (2) Å is for atom C9. The torsion angles C10—C8—O4—C7 [107.8 (2)°], C8—O4—C7—C6 [−170.95 (15)°] and O4—C7—C6—C1 [176.48 (15)°] are typical of the torsional freedom permitted by the rotation of the benzoate group at position 3. The greatest conformational freedom of the molecule resides, therefore, in the benzoate bridge of compound, composed by C8—O4—C7—C6.

In the crystal, there are C—H⋯π and C—O⋯π contacts present (Table 1 and Fig. 2) and also π-π- stacking interactions. The H⋯π and O⋯π separations are comparable with those cited by Imai et al. (2008 ) from a database analysis, which concluded that such interactions were attractive, with interaction energies of ca 2 kcal mol⁻¹, comparable to those typical of weak hydrogen bonds. These interactions result in the formation of zigzag chains propagating along the c-axis direction. The supramolecular aggregation in the crystal is completed by the presence of slipped parallel π–π interactions, forming columns along the c-axis direction. The most significant interactions are Cg2⋯Cg2ⁱ = 3.7216 (14) Å [inter-planar distance = 3.4024 (9) Å, slippage = 1.508 Å, where Cg2 is the centroid of the C1/C2/C4–C6 ring; symmetry code: (i) −x, 1 − y, 1 − z] and Cg2⋯Cg2ⁱⁱ = 3.7058 (14) Å [inter-planar distance = 3.4309 (9) Å, slippage = 1.401 Å, symmetry code: (ii) 1 − x, 1 − y, 1 − z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg3ⁱ	1.00 (2)	2.94 (2)	3.841 (2)	150.5 (2)
C9—O1⋯Cg1ⁱⁱ	1.20 (1)	3.15 (1)	3.464 (2)	95 (1)
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z.

Figure 2
Packing diagram of the title compound, viewed along the b axis.

Synthesis and crystallization

In a 100 ml flask with a water condenser were introduced successively 25 ml of dried diethyl ether, 6.17 mmol of benzoyl chloride and 3.2 ml of dried triethylamine. While stirring strongly, 6.17 mmol of chroman-2,3-dione were added in small portions. The reaction mixture was left under agitation for 2 h at room temperature and then refluxed for 2 h. The mixture was poured in a separating funnel containing 40 ml of chloroform and washed with diluted hydrochloric acid solution until the pH was 2-3. The organic layer was extracted, washed with water to neutrality, dried over MgSO₄ and the solvent removed. The resulting precipitate (crude product) was filtered off with suction, washed with petroleum ether and recrystallized from a solvent mixture of chloroform–hexane (1:3, v/v). Yellow crystals of the title compound were obtained in a yield of 84%; m.p. 423–426 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Two reflections were omitted owing to bad agreement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₀O₄
M_r	266.24
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	298
a, b, c (Å)	6.9243 (6), 7.7262 (8), 11.8168 (6)
α, β, γ (°)	84.550 (6), 81.852 (6), 83.023 (8)
V (Å³)	619.22 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.34 × 0.12 × 0.06

Data collection
Diffractometer	Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.499, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7628, 2283, 1724
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.159, 1.04
No. of reflections	2283
No. of parameters	221
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1547586

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006630/hb4144sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006630/hb4144Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006630/hb4144Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

2-Oxo-2H-chromen-3-yl benzoate top

Crystal data top

C₁₆H₁₀O₄	Z = 2
M_r = 266.24	F(000) = 276
Triclinic, P1	D_x = 1.428 Mg m⁻³
a = 6.9243 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7262 (8) Å	Cell parameters from 2675 reflections
c = 11.8168 (6) Å	θ = 5.8–69.2°
α = 84.550 (6)°	µ = 0.10 mm⁻¹
β = 81.852 (6)°	T = 298 K
γ = 83.023 (8)°	Prism, yellow
V = 619.22 (9) Å³	0.34 × 0.12 × 0.06 mm

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	2283 independent reflections
Radiation source: sealed X-ray tube	1724 reflections with I > 2σ(I)
Detector resolution: 5.3048 pixels mm^-1	R_int = 0.039
ω scans	θ_max = 25.6°, θ_min = 1.8°
Absorption correction: multi-scan (Crysalis PRO; Agilent, 2011)	h = −8→8
T_min = 0.499, T_max = 1.000	k = −9→9
7628 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	All H-atom parameters refined
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.0998P)² + 0.0263P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2283 reflections	Δρ_max = 0.22 e Å⁻³
221 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints

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.

Refinement. All H atoms were refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic, and C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C) for the methylene H atoms.

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

	x	y	z	U_iso*/U_eq
H10	0.994 (4)	0.658 (3)	0.393 (2)	0.068 (6)*
H4	0.825 (4)	0.121 (4)	0.016 (3)	0.093 (8)*
H3	0.789 (3)	0.243 (3)	−0.168 (2)	0.076 (7)*
H1	0.711 (3)	0.728 (3)	−0.0468 (19)	0.063 (6)*
H5	0.790 (3)	0.285 (3)	0.171 (2)	0.068 (6)*
H2	0.731 (3)	0.548 (3)	−0.202 (2)	0.071 (7)*
H13	0.401 (4)	0.916 (3)	0.688 (2)	0.073 (6)*
H16	1.079 (4)	0.800 (3)	0.565 (2)	0.073 (7)*
H15	0.977 (4)	0.946 (3)	0.732 (2)	0.083 (7)*
H14	0.634 (3)	1.000 (3)	0.791 (2)	0.070 (6)*
O2	0.46650 (18)	0.75322 (17)	0.51161 (11)	0.0538 (4)
O4	0.7627 (2)	0.54314 (18)	0.27349 (11)	0.0618 (4)
O1	0.3793 (2)	0.6280 (2)	0.36899 (13)	0.0666 (4)
C8	0.7208 (3)	0.6366 (2)	0.37014 (15)	0.0543 (5)
C11	0.8071 (3)	0.7664 (2)	0.52978 (16)	0.0518 (5)
O3	0.6978 (2)	0.79125 (18)	0.16416 (12)	0.0661 (4)
C6	0.7503 (2)	0.5198 (2)	0.07680 (15)	0.0496 (4)
C9	0.5118 (3)	0.6699 (2)	0.41218 (16)	0.0532 (5)
C12	0.6084 (3)	0.8027 (2)	0.56933 (15)	0.0495 (4)
C13	0.5431 (3)	0.8890 (2)	0.66733 (16)	0.0570 (5)
C10	0.8604 (3)	0.6801 (3)	0.42525 (17)	0.0561 (5)
C7	0.7320 (3)	0.6361 (2)	0.17134 (15)	0.0522 (4)
C1	0.7338 (3)	0.5970 (3)	−0.03279 (17)	0.0553 (5)
C5	0.7800 (3)	0.3397 (3)	0.0954 (2)	0.0618 (5)
C3	0.7787 (3)	0.3156 (3)	−0.1056 (2)	0.0686 (6)
C16	0.9429 (3)	0.8200 (3)	0.5925 (2)	0.0639 (5)
C2	0.7489 (3)	0.4928 (3)	−0.12395 (18)	0.0636 (5)
C15	0.8781 (4)	0.9067 (3)	0.6904 (2)	0.0676 (6)
C4	0.7933 (3)	0.2371 (3)	0.0027 (2)	0.0718 (6)
C14	0.6802 (4)	0.9404 (3)	0.72688 (18)	0.0650 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0468 (7)	0.0646 (8)	0.0492 (7)	−0.0038 (5)	−0.0054 (5)	−0.0045 (6)
O4	0.0752 (9)	0.0610 (8)	0.0452 (7)	0.0067 (6)	−0.0063 (6)	−0.0045 (6)
O1	0.0644 (9)	0.0749 (9)	0.0638 (9)	−0.0119 (7)	−0.0162 (7)	−0.0064 (7)
C8	0.0605 (11)	0.0560 (10)	0.0428 (9)	0.0012 (8)	−0.0036 (8)	0.0004 (7)
C11	0.0512 (10)	0.0528 (9)	0.0500 (10)	−0.0037 (7)	−0.0073 (8)	0.0024 (7)
O3	0.0836 (10)	0.0595 (8)	0.0517 (8)	0.0027 (7)	−0.0062 (7)	−0.0043 (6)
C6	0.0390 (8)	0.0595 (10)	0.0498 (10)	−0.0045 (7)	−0.0047 (7)	−0.0052 (8)
C9	0.0579 (11)	0.0524 (9)	0.0478 (10)	−0.0040 (8)	−0.0078 (8)	0.0025 (8)
C12	0.0527 (10)	0.0478 (9)	0.0467 (9)	−0.0050 (7)	−0.0075 (8)	0.0040 (7)
C13	0.0605 (12)	0.0576 (10)	0.0505 (10)	−0.0026 (8)	−0.0033 (9)	−0.0026 (8)
C10	0.0484 (10)	0.0640 (11)	0.0513 (10)	0.0006 (8)	0.0000 (8)	0.0003 (8)
C7	0.0478 (9)	0.0599 (11)	0.0459 (9)	−0.0007 (7)	−0.0022 (7)	−0.0015 (8)
C1	0.0512 (10)	0.0630 (11)	0.0520 (10)	−0.0079 (8)	−0.0064 (8)	−0.0046 (8)
C5	0.0575 (11)	0.0640 (11)	0.0630 (12)	−0.0052 (8)	−0.0077 (9)	−0.0019 (9)
C3	0.0591 (12)	0.0822 (14)	0.0702 (14)	−0.0132 (10)	−0.0087 (10)	−0.0273 (12)
C16	0.0545 (11)	0.0672 (12)	0.0698 (13)	−0.0037 (9)	−0.0120 (10)	−0.0018 (10)
C2	0.0588 (11)	0.0835 (14)	0.0515 (11)	−0.0140 (10)	−0.0076 (9)	−0.0113 (10)
C15	0.0754 (14)	0.0645 (12)	0.0673 (13)	−0.0085 (10)	−0.0254 (11)	−0.0033 (10)
C4	0.0674 (13)	0.0594 (12)	0.0905 (17)	−0.0071 (9)	−0.0110 (11)	−0.0156 (11)
C14	0.0832 (15)	0.0563 (11)	0.0547 (11)	−0.0026 (9)	−0.0102 (10)	−0.0061 (9)

Geometric parameters (Å, º) top

O2—C9	1.372 (2)	C13—H13	0.98 (3)
O2—C12	1.381 (2)	C10—H10	0.95 (2)
O4—C7	1.374 (2)	C1—C2	1.390 (3)
O4—C8	1.386 (2)	C1—H1	1.01 (2)
O1—C9	1.202 (2)	C5—C4	1.398 (3)
C8—C10	1.331 (3)	C5—H5	0.96 (2)
C8—C9	1.462 (3)	C3—C2	1.361 (3)
C11—C12	1.392 (3)	C3—C4	1.375 (4)
C11—C16	1.398 (3)	C3—H3	0.96 (2)
C11—C10	1.440 (3)	C16—C15	1.384 (3)
O3—C7	1.191 (2)	C16—H16	0.95 (3)
C6—C5	1.383 (3)	C2—H2	0.99 (2)
C6—C1	1.387 (3)	C15—C14	1.378 (3)
C6—C7	1.481 (3)	C15—H15	0.99 (3)
C12—C13	1.384 (3)	C4—H4	0.90 (3)
C13—C14	1.374 (3)	C14—H14	0.92 (2)

C9—O2—C12	122.54 (14)	O4—C7—C6	111.59 (15)
C7—O4—C8	115.88 (14)	C6—C1—C2	119.8 (2)
C10—C8—O4	122.46 (17)	C6—C1—H1	120.5 (12)
C10—C8—C9	122.72 (17)	C2—C1—H1	119.7 (13)
O4—C8—C9	114.61 (17)	C6—C5—C4	119.3 (2)
C12—C11—C16	117.93 (18)	C6—C5—H5	120.7 (13)
C12—C11—C10	118.13 (17)	C4—C5—H5	120.0 (13)
C16—C11—C10	123.92 (18)	C2—C3—C4	120.8 (2)
C5—C6—C1	120.07 (18)	C2—C3—H3	120.4 (14)
C5—C6—C7	122.07 (18)	C4—C3—H3	118.8 (14)
C1—C6—C7	117.85 (17)	C15—C16—C11	120.0 (2)
O1—C9—O2	118.14 (17)	C15—C16—H16	121.2 (14)
O1—C9—C8	125.95 (18)	C11—C16—H16	118.8 (14)
O2—C9—C8	115.89 (17)	C3—C2—C1	120.1 (2)
O2—C12—C13	116.78 (16)	C3—C2—H2	120.4 (13)
O2—C12—C11	120.95 (16)	C1—C2—H2	119.5 (13)
C13—C12—C11	122.27 (18)	C14—C15—C16	120.4 (2)
C14—C13—C12	118.38 (19)	C14—C15—H15	121.3 (15)
C14—C13—H13	123.6 (14)	C16—C15—H15	118.3 (15)
C12—C13—H13	117.9 (14)	C3—C4—C5	119.9 (2)
C8—C10—C11	119.75 (17)	C3—C4—H4	122.2 (19)
C8—C10—H10	119.1 (14)	C5—C4—H4	117.5 (19)
C11—C10—H10	121.1 (14)	C13—C14—C15	120.99 (19)
O3—C7—O4	121.79 (17)	C13—C14—H14	117.2 (15)
O3—C7—C6	126.62 (18)	C15—C14—H14	121.8 (15)

C7—O4—C8—C10	−107.8 (2)	C8—O4—C7—O3	9.9 (3)
C7—O4—C8—C9	77.3 (2)	C8—O4—C7—C6	−170.95 (15)
C12—O2—C9—O1	178.33 (15)	C5—C6—C7—O3	−176.40 (19)
C12—O2—C9—C8	−0.2 (3)	C1—C6—C7—O3	2.6 (3)
C10—C8—C9—O1	−176.93 (19)	C5—C6—C7—O4	4.5 (2)
O4—C8—C9—O1	−2.0 (3)	C1—C6—C7—O4	−176.48 (15)
C10—C8—C9—O2	1.4 (3)	C5—C6—C1—C2	−0.6 (3)
O4—C8—C9—O2	176.31 (15)	C7—C6—C1—C2	−179.64 (16)
C9—O2—C12—C13	178.71 (15)	C1—C6—C5—C4	0.1 (3)
C9—O2—C12—C11	−1.4 (3)	C7—C6—C5—C4	179.10 (18)
C16—C11—C12—O2	−179.87 (16)	C12—C11—C16—C15	−0.2 (3)
C10—C11—C12—O2	1.7 (3)	C10—C11—C16—C15	178.12 (19)
C16—C11—C12—C13	0.0 (3)	C4—C3—C2—C1	0.3 (3)
C10—C11—C12—C13	−178.40 (17)	C6—C1—C2—C3	0.4 (3)
O2—C12—C13—C14	−179.91 (16)	C11—C16—C15—C14	0.2 (3)
C11—C12—C13—C14	0.2 (3)	C2—C3—C4—C5	−0.8 (3)
O4—C8—C10—C11	−175.59 (16)	C6—C5—C4—C3	0.6 (3)
C9—C8—C10—C11	−1.1 (3)	C12—C13—C14—C15	−0.2 (3)
C12—C11—C10—C8	−0.5 (3)	C16—C15—C14—C13	0.0 (3)
C16—C11—C10—C8	−178.80 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg3ⁱ	1.00 (2)	2.94 (2)	3.841 (2)	150.5 (2)
C9—O1···Cg1ⁱⁱ	1.20 (1)	3.15 (1)	3.464 (2)	95 (1)

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

Acknowledgements

The authors thank the spectropole service of sciences (Aix-Marseille, France) for the use of the diffractometer and the NMR and MS spectrometers.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
Chen, G., Li, H., Lan, R. & Li, J. (2013). Huaxue Tongbao, 76, 1002–1010. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Guha, S., Dutta, M. & Das, D. (2012). J. Indian Chem. Soc. 89, 1603–1632. CAS Google Scholar
Imai, Y. N., Inoue, Y., Nakanishi, I. & Kitaura, K. (2008). Protein Sci. 17, 1129–1137. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Oxo-2H-chromen-3-yl benzoate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds