2-Oxo-2H-chromen-7-yl tert-butyl­acetate

Bazié, H.; Ziki, E.; Brahima, S.; Ratsimbazafy, V.; Roge, P.; Wenger, E.; Djandé, A.; Lecomte, C.

doi:10.1107/S2414314625001890

organic compounds

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ISSN: 2414-3146

Volume 10| Part 3| March 2025| x250189

https://doi.org/10.1107/S2414314625001890

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2-Oxo-2H-chromen-7-yl tert-butylacetate

Hypolite Bazié,^a Eric Ziki,^b ^* Sorgho Brahima,^a ^* Veroarisinima Ratsimbazafy,^c Patrick Roge,^c Emmanuel Wenger,^d Abdoulaye Djandé ^a and Claude Lecomte ^d

^aLaboratory of Molecular Chemistry and Materials (LC2M), University Joseph KI-ZERBO, 03 BP 7021 Ouagadougou 03, Burkina Faso, ^bLaboratory of Matter, Environmental and Solar Energy Sciences, Research Team: Crystallography and Molecular Physics, University Félix Houphouët-Boigny, 08 BP 582, Abidjan 22, Côte d'Ivoire, ^cLaboratory of Solid State Physics and Experimental Physics, University of Antananarivo, BP 566, Antananarivo 101, Madagascar, and ^dCRM2, CNRS-Université de Lorraine, Vandoeuvre-lès-Nancy CEDEX BP 70239, France
^*Correspondence e-mail: eric.ziki@gmail.com, sorghobrahima3@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 19 February 2025; accepted 27 February 2025; online 4 March 2025)

In the title compound, C₁₅H₁₆O₄, the dihedral angle between the 2H-chromen-2-one ring system and the tert-butylacetate moiety is 72.72 (9)°. In the crystal, the molecules are connected through C—H⋯O hydrogen bonds, generating C(6) chains and R₂²(20) loops that are reinforced by weak aromatic π–π stacking interactions. The H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and C⋯C contacts contribute 50.6, 29.1, 8.5 and 6.8%, respectively, to the Hirshfeld surface.

Keywords: crystal structure; Hirshfeld surface; coumarin; hydrogen bond.

CCDC reference: 2427772

Structure description

The title coumarin derivative, C₁₅H₁₆O₄ (I), was synthesized by a research team led by Professor Djandé (LC2M, Ouagadougou, Burkina Faso) as part of the AFRAMED project (Kenfack Tsobnang et al., 2024 ). Coumarin-derived compounds exhibit various biological activities, such as anticancer (Yadav et al., 2024 ; Rawat et al., 2022 ), anticoagulant (Singh et al., 2019), anti-inflammatory (Todeschini et al., 1998 ) and anti-glaucoma (Ziki et al., 2023 ) properties.

As shown in Fig. 1, the 2H-chromen-2-one moiety formed by atoms C1–C9/O1/O2 in (I) is almost planar with an r.m.s deviation of 0.027 Å and the dihedral angle between this ring system and the plane formed by atoms C10–C12/C14 in the tert-butylacetate moiety is 72.72 (9)°. An S(6) ring motif resulting from an intramolecular C13—H13B⋯O4 hydrogen bond is observed (Table 1). The plane passing through atoms C10–C12/C14 of the tert-butylacetate moiety contains the ester function atoms (r.m.s = 0.228 Å), but methyl atoms C13 and C15 atoms are on either side of this plane with deviations of 1.275 (1) and −1.244 (1) Å, respectively.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O4ⁱ	0.95	2.50	3.4144 (13)	161
C11—H11B⋯O2ⁱⁱ	0.99	2.52	3.2523 (13)	131
C13—H13B⋯O4	0.98	2.43	3.0924 (14)	124
Symmetry codes: (i) ; (ii) .

Figure 1
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

In the crystal of (I), molecules are linked by weak hydrogen bonds of the C—H⋯O type. A pair of C11—H11B⋯O2(−x + 2, −y, −z + 1) hydrogen bonds generates a centrosymmetric R₂²(20) loop, as shown in Fig. 3. The C5—H5⋯O4(x − 1, y, z) hydrogen bonds form C(6) chains propagating in the [100] direction (Fig. 2). Aromatic π–π stacking interactions between the pyrone ring (centroid Cg1) and benzene ring (centroid Cg2) of a symmetry-related (1 − x, −y, 1 − z) molecule reinforce the cohesion of molecules [Cg1⋯Cg2 = 3.5485 (8) with a slippage of 1.042 Å],

Figure 2
Part of the crystal of (I) showing the formation of an undulating network along the b axis [C(6) and R₂²(20) motifs]. Dashed lines indicate hydrogen bonds.

The Hirshfeld surface and two-dimensional fingerprint (FP) plot of (1) (Fig. 3) generated by CrystalExplorer21.5 (Spackman et al., 2021 ) confirmed the above interactions. The fingerprint plots show the different contributions of the atoms in the crystal-to-surface contacts. The most important contributions are H⋯H and H⋯O/O⋯H contacts with 50.6 and 29.1%, respectively (Fig. 3d and 3f). The H⋯C/C⋯H and C⋯C contacts contribute 8.5 and 6.8%, respectively. These values are close to those of 2-oxo-2H-chromen-6-yl 4- tert-butylbenzoate (Kenfack Tsobnang et al., 2024).

Figure 3
(a), (b) Hirshfeld surface of (I) mapped over d_norm, (c) overall two-dimensional fingerprint plot of and those delineated into contributions from different contacts: (d) H⋯H, (d) H⋯C/C⋯H and (e) H⋯O/O⋯H.

Synthesis and crystallization

To a solution of tert-butylacetyl chloride (6.2 mmol, 0.9 ml) in dried diethyl ether (16 ml) was added dried pyridine (4.7 molar equivalents; 2.31 ml) and 7-hydroxycoumarin (6.17 mmol, 1.00 g) in small portions over 30 min. The mixture was left under agitation at room temperature for 3 h and then poured into 40 ml of chloroform. The solution was acidified with dilute hydrochloric acid (5%) until the pH was 2–3. The organic layer was extracted, washed four times with 25 ml of water to neutrality, dried over MgSO₄ and the solvent removed. The resulting crude product was filtered off with suction, washed with petroleum ether and recrystallized from acetone solution as colorless crystals of the title compound. Yield = 79%, m.p. = 368–371 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₆O₄
M_r	260.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	6.1599 (9), 7.2029 (11), 15.202 (2)
α, β, γ (°)	98.765 (5), 99.335 (5), 91.228 (5)
V (Å³)	657.05 (17)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.12 × 0.07

Data collection
Diffractometer	Bruker D8 Venture
No. of measured, independent and observed [I > 2σ(I)] reflections	53961, 4064, 3720
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.137, 1.05
No. of reflections	4064
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.28
Computer programs: APEX4 and SAINT (Bruker, 2019 ), SHELXS2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2427772

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625001890/hb4507sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625001890/hb4507Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625001890/hb4507Isup3.cml

checkCIF report

Computing details top

2-Oxo-2H-chromen-7-yl tert-butylacetate top

Crystal data top

C₁₅H₁₆O₄	Z = 2
M_r = 260.28	F(000) = 276
Triclinic, P1	D_x = 1.316 Mg m⁻³
Hall symbol: -P 1	Melting point: 368 K
a = 6.1599 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2029 (11) Å	Cell parameters from 4066 reflections
c = 15.202 (2) Å	θ = 2.9–30.8°
α = 98.765 (5)°	µ = 0.10 mm⁻¹
β = 99.335 (5)°	T = 100 K
γ = 91.228 (5)°	Prism, yellow
V = 657.05 (17) Å³	0.20 × 0.12 × 0.07 mm

Data collection top

Bruker D8 Venture diffractometer	3720 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Mirror monochromator	θ_max = 30.8°, θ_min = 2.9°
φ and ω scan	h = −8→8
53961 measured reflections	k = −10→10
4064 independent reflections	l = −21→21

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0778P)² + 0.2223P] where P = (F_o² + 2F_c²)/3
4064 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

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
O3	0.53573 (12)	0.19418 (10)	0.29426 (5)	0.02062 (16)
O1	0.88247 (11)	0.15470 (10)	0.59464 (5)	0.01913 (16)
O4	0.84148 (12)	0.38219 (10)	0.30532 (5)	0.02129 (16)
O2	1.04542 (14)	0.10787 (12)	0.72944 (5)	0.02755 (18)
C9	0.51037 (15)	0.26016 (12)	0.56924 (6)	0.01750 (18)
C6	0.53813 (16)	0.22422 (13)	0.38729 (6)	0.01796 (18)
C5	0.34391 (15)	0.28555 (13)	0.41609 (7)	0.01937 (18)
H5	0.222778	0.314675	0.374030	0.023*
C4	0.33122 (15)	0.30309 (13)	0.50706 (7)	0.01946 (19)
H4	0.200134	0.344549	0.527611	0.023*
C8	0.70128 (15)	0.20004 (13)	0.53717 (6)	0.01673 (17)
C7	0.71880 (15)	0.18000 (13)	0.44623 (6)	0.01781 (18)
H7	0.849197	0.137745	0.425327	0.021*
C10	0.70385 (15)	0.27069 (13)	0.26024 (6)	0.01775 (18)
C1	0.88143 (17)	0.15948 (14)	0.68557 (6)	0.02053 (19)
C3	0.50766 (17)	0.27137 (14)	0.66442 (7)	0.02070 (19)
H3	0.380241	0.311803	0.688282	0.025*
C2	0.68492 (18)	0.22481 (14)	0.71993 (7)	0.0225 (2)
H2	0.681287	0.234916	0.782707	0.027*
C11	0.68111 (16)	0.19153 (14)	0.16148 (6)	0.01956 (18)
H11A	0.522872	0.186209	0.134991	0.023*
H11B	0.728920	0.060533	0.156411	0.023*
C12	0.80830 (16)	0.29648 (14)	0.10383 (6)	0.02054 (19)
C13	1.05795 (18)	0.29276 (19)	0.13479 (8)	0.0305 (2)
H13A	1.135176	0.360602	0.096951	0.046*
H13B	1.096000	0.353175	0.197906	0.046*
H13C	1.102008	0.162119	0.129266	0.046*
C15	0.7374 (2)	0.50003 (16)	0.10722 (7)	0.0284 (2)
H15A	0.820076	0.565015	0.070105	0.043*
H15B	0.579442	0.500204	0.083962	0.043*
H15C	0.767411	0.564855	0.169777	0.043*
C14	0.74935 (19)	0.19270 (17)	0.00628 (7)	0.0277 (2)
H14A	0.827400	0.255304	−0.033149	0.041*
H14B	0.792917	0.062204	0.003871	0.041*
H14C	0.590176	0.194470	−0.014024	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0191 (3)	0.0257 (3)	0.0169 (3)	−0.0023 (3)	0.0020 (2)	0.0045 (3)
O1	0.0186 (3)	0.0219 (3)	0.0171 (3)	0.0041 (2)	0.0023 (2)	0.0040 (2)
O4	0.0204 (3)	0.0241 (3)	0.0187 (3)	−0.0014 (3)	0.0019 (2)	0.0032 (3)
O2	0.0274 (4)	0.0334 (4)	0.0216 (4)	0.0057 (3)	−0.0004 (3)	0.0074 (3)
C9	0.0181 (4)	0.0150 (4)	0.0201 (4)	0.0005 (3)	0.0050 (3)	0.0028 (3)
C6	0.0184 (4)	0.0182 (4)	0.0177 (4)	−0.0005 (3)	0.0030 (3)	0.0041 (3)
C5	0.0156 (4)	0.0199 (4)	0.0229 (4)	0.0003 (3)	0.0018 (3)	0.0058 (3)
C4	0.0163 (4)	0.0188 (4)	0.0244 (4)	0.0015 (3)	0.0057 (3)	0.0042 (3)
C8	0.0167 (4)	0.0155 (4)	0.0181 (4)	0.0014 (3)	0.0026 (3)	0.0034 (3)
C7	0.0175 (4)	0.0186 (4)	0.0180 (4)	0.0023 (3)	0.0041 (3)	0.0035 (3)
C10	0.0176 (4)	0.0189 (4)	0.0176 (4)	0.0031 (3)	0.0024 (3)	0.0054 (3)
C1	0.0244 (5)	0.0197 (4)	0.0173 (4)	0.0006 (3)	0.0024 (3)	0.0037 (3)
C3	0.0222 (4)	0.0195 (4)	0.0214 (4)	0.0010 (3)	0.0078 (3)	0.0019 (3)
C2	0.0274 (5)	0.0232 (4)	0.0174 (4)	0.0008 (4)	0.0060 (3)	0.0021 (3)
C11	0.0197 (4)	0.0213 (4)	0.0171 (4)	0.0010 (3)	0.0020 (3)	0.0029 (3)
C12	0.0202 (4)	0.0258 (4)	0.0156 (4)	0.0012 (3)	0.0030 (3)	0.0032 (3)
C13	0.0198 (5)	0.0468 (7)	0.0245 (5)	−0.0003 (4)	0.0048 (4)	0.0032 (4)
C15	0.0382 (6)	0.0250 (5)	0.0223 (5)	0.0003 (4)	0.0024 (4)	0.0075 (4)
C14	0.0294 (5)	0.0354 (6)	0.0172 (4)	0.0008 (4)	0.0040 (4)	0.0011 (4)

Geometric parameters (Å, º) top

O3—C10	1.3710 (11)	C3—C2	1.3490 (14)
O3—C6	1.3953 (11)	C3—H3	0.9500
O1—C1	1.3785 (11)	C2—H2	0.9500
O1—C8	1.3791 (11)	C11—C12	1.5339 (14)
O4—C10	1.2033 (12)	C11—H11A	0.9900
O2—C1	1.2151 (12)	C11—H11B	0.9900
C9—C8	1.3970 (13)	C12—C15	1.5344 (15)
C9—C4	1.4044 (13)	C12—C13	1.5355 (15)
C9—C3	1.4396 (13)	C12—C14	1.5380 (14)
C6—C7	1.3862 (13)	C13—H13A	0.9800
C6—C5	1.3971 (13)	C13—H13B	0.9800
C5—C4	1.3845 (13)	C13—H13C	0.9800
C5—H5	0.9500	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C8—C7	1.3900 (13)	C15—H15C	0.9800
C7—H7	0.9500	C14—H14A	0.9800
C10—C11	1.5054 (13)	C14—H14B	0.9800
C1—C2	1.4540 (14)	C14—H14C	0.9800

C10—O3—C6	119.43 (7)	C1—C2—H2	119.3
C1—O1—C8	121.85 (8)	C10—C11—C12	117.18 (8)
C8—C9—C4	118.47 (9)	C10—C11—H11A	108.0
C8—C9—C3	117.80 (9)	C12—C11—H11A	108.0
C4—C9—C3	123.72 (9)	C10—C11—H11B	108.0
C7—C6—O3	120.83 (8)	C12—C11—H11B	108.0
C7—C6—C5	122.58 (9)	H11A—C11—H11B	107.2
O3—C6—C5	116.39 (8)	C11—C12—C15	110.51 (8)
C4—C5—C6	118.78 (9)	C11—C12—C13	111.12 (8)
C4—C5—H5	120.6	C15—C12—C13	110.36 (9)
C6—C5—H5	120.6	C11—C12—C14	106.66 (8)
C5—C4—C9	120.60 (9)	C15—C12—C14	109.16 (8)
C5—C4—H4	119.7	C13—C12—C14	108.94 (8)
C9—C4—H4	119.7	C12—C13—H13A	109.5
O1—C8—C7	116.34 (8)	C12—C13—H13B	109.5
O1—C8—C9	121.32 (8)	H13A—C13—H13B	109.5
C7—C8—C9	122.33 (9)	C12—C13—H13C	109.5
C6—C7—C8	117.24 (8)	H13A—C13—H13C	109.5
C6—C7—H7	121.4	H13B—C13—H13C	109.5
C8—C7—H7	121.4	C12—C15—H15A	109.5
O4—C10—O3	123.07 (9)	C12—C15—H15B	109.5
O4—C10—C11	128.49 (9)	H15A—C15—H15B	109.5
O3—C10—C11	108.45 (8)	C12—C15—H15C	109.5
O2—C1—O1	116.63 (9)	H15A—C15—H15C	109.5
O2—C1—C2	126.14 (9)	H15B—C15—H15C	109.5
O1—C1—C2	117.23 (9)	C12—C14—H14A	109.5
C2—C3—C9	120.42 (9)	C12—C14—H14B	109.5
C2—C3—H3	119.8	H14A—C14—H14B	109.5
C9—C3—H3	119.8	C12—C14—H14C	109.5
C3—C2—C1	121.30 (9)	H14A—C14—H14C	109.5
C3—C2—H2	119.3	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4ⁱ	0.95	2.50	3.4144 (13)	161
C11—H11B···O2ⁱⁱ	0.99	2.52	3.2523 (13)	131
C13—H13B···O4	0.98	2.43	3.0924 (14)	124

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

Acknowledgements

The authors thank the PMD2X X-ray diffraction facility (https://crm2.univ-lorraine.fr/lab/fr/services/pmd2x) of the Université de Lorraine for the X-ray diffraction measurements and the AFRAMED project. CCDC is also thanked for providing access to the Cambridge Structural Database through the FAIRE program. The authors are very grateful to UNESCO, CNRS and the IUCr for their support of the AFRAMED project.

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