2-Oxo-2H-chromen-7-yl 2,2-di­methyl­propionate

Hypolite Bazié; Eric Ziki; Sorgho Brahima; Abdoulaye Djandé; Rita Kakou-Yao

doi:10.1107/S2414314625009496

. 2025 Nov 18;10(Pt 11):x250949. doi: 10.1107/S2414314625009496

2-Oxo-2H-chromen-7-yl 2,2-dimethylpropionate

Hypolite Bazié ^a, Eric Ziki ^b, Sorgho Brahima ^a, Abdoulaye Djandé ^a, Rita Kakou-Yao ^b,^*

Editor: W T A Harrison^c

PMCID: PMC12810263 PMID: 41551128

In the title compound, the dihedral angle between the 2H-chromen-2-one moiety and the C—CO₂ ester grouping is 54.30 (5)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds forming C(6) [100] chains.

Keywords: crystal structure, coumarin, Hirshfeld surface analysis

Abstract

In the title compound, C₁₄H₁₄O₄, the dihedral angle between the 2H-chromen-2-one moiety and the C—CO₂ ester grouping is 54.30 (5)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds forming C(6) [100] chains. The contributions to the Hirshfeld surface for the H⋯H, H⋯O/ O⋯H, H⋯C/C⋯H and C⋯C contacts are 49.5, 29.91, 8.6 and 7.7%, respectively.

Structure description

Herein we describe the synthesis, crystal structure and Hirshfeld surface analysis of the title coumarin derivative, C₁₄H₁₄O₄. As reported by several authors, coumarin-derived compounds exhibit various biological activities, such as anticancer (Yadav et al., 2024 ▸; Rawat et al., 2022 ▸), anti-inflammatory (Todeschini et al., 1998 ▸) and anti-glaucoma (Ziki et al., 2023 ▸) properties.

As expected, the fused ring system formed by atoms C1–C9/O1/O2 is almost planar with an r.m.s deviation of 0.009 Å and the dihedral angle between this ring system and the plane formed by atoms C11/C11/O3/O4 in the ester grouping is 54.30 (5)° (Fig. 1 ▸).

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

In the crystal, molecules are linked by weak C5—H5⋯O4(x + 1, y, z) hydrogen bonds (Table 1 ▸), thereby generating [100] C(6) chains (Fig. 2 ▸). The Hirshfeld surface and two-dimensional fingerprint plot of the title compound generated by CrystalExplorer21.5 (Spackman et al., 2021 ▸) confirmed the above interaction: the C5—H5⋯O4 bond is indicated by the red spots on Fig. 3 ▸a. The fingerprint plots show that the most important contributions to the surface are H⋯H and H⋯O/O⋯H contacts with 49.5 and 29.1%, respectively (Fig. 3 ▸c and 3e). The H⋯C/C⋯H and C⋯C contacts contribute 8.6 and 7.7%, respectively. These values are close to those of 2-oxo-2H-chromen-7-yl tert-butylacetate (Bazié et al., 2025 ▸).

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O4ⁱ	0.93	2.49	3.343 (4)	153

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Symmetry code: (i) Inline graphic .

Part of the extended structure of the title compound showing the formation of [100] hydrogen bonded chains. Symmetry code: (a) x + 1, y, z.

(a) Hirshfeld surface of the title compound mapped over d_norm, (b) the overall two-dimensional fingerprint plots and (c)–(e) delineated into contributions from different contacts: H⋯H, H⋯C/C⋯H and H⋯O/O⋯H.

Synthesis and crystallization

In a 100 ml round-bottom flask equipped with a condenser, pivaloyl chloride (0.76 ml, 6.17 mmol, 1 equiv.) was dissolved in 16 ml of dried diethyl ether and then dried pyridine (2.31 ml, 4.7 equiv.) and 7-hydroxycoumarin (1 g, 6.17 mmol, 1 equiv.) were added by small portions over 30 min, with vigorous stirring. The reaction mixture was left stirring at room temperature for 3 h.

The resulting mixture was next poured in a separating funnel containing 40 ml of chloroform and washed with 5% hydrochloric acid until the pH was 2–3. The organic phase was extracted, washed with water to neutrality, dried with magnesium sulfate and the solvent removed in vacuo until a cloudy solution was obtained. The occurred precipitate while cooling in an ice bath was filtered off with suction, washed with petroleum ether and recrystallized from a chloroform/n-hexane solvent mixture (1:3) giving the title compound as a white powder (0.96 g, yield 63%). Colourless prisms suitable for single-crystal X-ray diffraction analysis were then formed from an acetone solution, after the solvent was left to evaporate slowly at room temperature, m.p. 403–405 K.

Refinement

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

Table 2. Experimental details.

Crystal data
Chemical formula	C₁₄H₁₄O₄
M _r	246.25
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	6.242 (7), 7.191 (8), 13.652 (16)
α, β, γ (°)	99.05 (6), 92.85 (5), 91.99 (3)
V (Å³)	603.9 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.41 × 0.12 × 0.04

Data collection
Diffractometer	Bruker D8 Venture
No. of measured, independent and observed [I > 2σ(I)] reflections	43182, 3718, 2693
R _int	0.056
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.160, 1.09
No. of reflections	3718
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.27

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Computer programs: APEX4 and SAINT (Bruker, 2019 ▸), SHELXT2018/2 (Sheldrick, 2015a ▸), SHELXL2018/3 (Sheldrick, 2015b ▸), PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2414314625009496/hb4533sup1.cif

x-10-x250949-sup1.cif^{(1.2MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314625009496/hb4533Isup2.hkl

x-10-x250949-Isup2.hkl^{(296.5KB, hkl)}

x-10-x250949-Isup3.cml^{(5KB, cml)}

Supporting information file. DOI: 10.1107/S2414314625009496/hb4533Isup3.cml

CCDC reference: 2498840

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the PMD2X X-ray diffraction facility (https://crm2.univ-lorraine.fr/lab/fr/services/pmd2x) of the Université de Lorraine, for 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 thank UNESCO, CNRS and the IUCr for their support of the AFRAMED project.

full crystallographic data