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

Bazié, H.; Ziki, E.; Brahima, S.; Djandé, A.; Kakou-Yao, R.

doi:10.1107/S2414314625009496

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 11| November 2025| x250949

https://doi.org/10.1107/S2414314625009496

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

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

^aLaboratory of Molecular Chemistry and Materials (LC2M), University Joseph KI-ZERBO, 03 BP 7021 Ouagadougou 03, Burkina Faso, and ^bLaboratory of Matter, Environmental and Solar Energy Sciences, Research Team: Crystallography and Molecular Physics, University Félix Houphouët-Boigny, 08 BP 582 Abidjan 08, Ivory Coast
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 28 August 2025; accepted 29 October 2025; online 18 November 2025)

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.

Keywords: crystal structure; coumarin; Hirshfeld surface analysis.

CCDC reference: 2498840

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).

Figure 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. 3a. 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. 3c 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
Symmetry code: (i) .

Figure 2
Part of the extended structure of the title compound showing the formation of [100] hydrogen bonded chains. Symmetry code: (a) x + 1, y, z.

Figure 3
(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 $[\overline{1}]$
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
Computer programs: APEX4 and SAINT (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2498840

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625009496/hb4533sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625009496/hb4533Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625009496/hb4533Isup3.cml

checkCIF report

Computing details top

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

Crystal data top

C₁₄H₁₄O₄	Z = 2
M_r = 246.25	F(000) = 260
Triclinic, P1	D_x = 1.354 Mg m⁻³
Hall symbol: -P 1	Melting point: 403 K
a = 6.242 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.191 (8) Å	Cell parameters from 3418 reflections
c = 13.652 (16) Å	θ = 2.9–30.7°
α = 99.05 (6)°	µ = 0.10 mm⁻¹
β = 92.85 (5)°	T = 296 K
γ = 91.99 (3)°	Prism, colourless
V = 603.9 (12) Å³	0.41 × 0.12 × 0.04 mm

Data collection top

Bruker D8 Venture diffractometer	2693 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Mirror monochromator	θ_max = 30.7°, θ_min = 2.9°
φ and ω scans	h = −8→8
43182 measured reflections	k = −10→10
3718 independent reflections	l = −19→19

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.160	w = 1/[σ²(F_o²) + (0.0861P)² + 0.0957P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3718 reflections	Δρ_max = 0.33 e Å⁻³
164 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (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	0.13581 (14)	0.84613 (12)	0.39385 (7)	0.0237 (2)
O4	0.06432 (15)	0.57567 (13)	0.69115 (7)	0.0269 (2)
O3	0.36060 (14)	0.76954 (13)	0.72407 (7)	0.0254 (2)
O2	0.01958 (17)	0.88911 (16)	0.24380 (8)	0.0345 (3)
C8	0.2943 (2)	0.80064 (17)	0.45874 (9)	0.0217 (3)
C9	0.4981 (2)	0.75335 (17)	0.42670 (9)	0.0223 (3)
C7	0.2418 (2)	0.80648 (17)	0.55681 (9)	0.0223 (3)
H7	0.106957	0.841094	0.577328	0.027*
C6	0.3981 (2)	0.75876 (17)	0.62275 (9)	0.0227 (3)
C4	0.6515 (2)	0.70870 (17)	0.49681 (10)	0.0240 (3)
H4	0.787880	0.677217	0.477166	0.029*
C10	0.1826 (2)	0.67743 (17)	0.75051 (9)	0.0223 (3)
C5	0.6034 (2)	0.71067 (18)	0.59473 (10)	0.0242 (3)
H5	0.705698	0.680589	0.640927	0.029*
C3	0.5370 (2)	0.75548 (18)	0.32394 (10)	0.0252 (3)
H3	0.671750	0.727749	0.300907	0.030*
C1	0.1690 (2)	0.84583 (18)	0.29448 (10)	0.0260 (3)
C11	0.1609 (2)	0.71001 (18)	0.86250 (10)	0.0257 (3)
C2	0.3801 (2)	0.79724 (19)	0.26079 (10)	0.0269 (3)
H2	0.407245	0.794946	0.194259	0.032*
C13	−0.0793 (2)	0.7139 (2)	0.88096 (11)	0.0338 (3)
H13A	−0.097988	0.734343	0.951163	0.051*
H13B	−0.141709	0.814129	0.851933	0.051*
H13C	−0.148727	0.595837	0.851352	0.051*
C12	0.2761 (2)	0.8930 (2)	0.91450 (11)	0.0325 (3)
H12A	0.257507	0.906684	0.984621	0.049*
H12B	0.426308	0.889022	0.902742	0.049*
H12C	0.216609	0.998011	0.888773	0.049*
C14	0.2597 (3)	0.5410 (2)	0.90167 (11)	0.0360 (3)
H14A	0.249513	0.555599	0.972376	0.054*
H14B	0.183333	0.426808	0.870998	0.054*
H14C	0.407801	0.535092	0.886066	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0223 (4)	0.0243 (5)	0.0251 (5)	0.0022 (3)	0.0013 (3)	0.0059 (3)
O4	0.0259 (5)	0.0272 (5)	0.0268 (5)	−0.0036 (4)	0.0002 (4)	0.0035 (4)
O3	0.0244 (5)	0.0275 (5)	0.0240 (4)	−0.0028 (4)	0.0014 (3)	0.0045 (4)
O2	0.0309 (5)	0.0431 (6)	0.0320 (5)	0.0033 (4)	−0.0010 (4)	0.0140 (4)
C8	0.0221 (6)	0.0171 (5)	0.0260 (6)	−0.0005 (4)	0.0002 (5)	0.0038 (4)
C9	0.0226 (6)	0.0169 (5)	0.0268 (6)	−0.0018 (4)	0.0032 (5)	0.0015 (4)
C7	0.0212 (6)	0.0195 (5)	0.0264 (6)	0.0006 (4)	0.0027 (5)	0.0035 (4)
C6	0.0249 (6)	0.0192 (5)	0.0236 (6)	−0.0023 (4)	0.0016 (5)	0.0032 (4)
C4	0.0209 (6)	0.0187 (6)	0.0318 (7)	−0.0006 (4)	0.0030 (5)	0.0025 (5)
C10	0.0211 (6)	0.0200 (5)	0.0263 (6)	0.0016 (4)	0.0008 (5)	0.0048 (4)
C5	0.0224 (6)	0.0205 (6)	0.0294 (6)	−0.0008 (4)	−0.0015 (5)	0.0043 (5)
C3	0.0241 (6)	0.0210 (6)	0.0303 (6)	−0.0008 (5)	0.0056 (5)	0.0025 (5)
C1	0.0285 (7)	0.0231 (6)	0.0268 (6)	−0.0008 (5)	0.0015 (5)	0.0062 (5)
C11	0.0278 (6)	0.0261 (6)	0.0232 (6)	0.0011 (5)	0.0009 (5)	0.0042 (5)
C2	0.0302 (7)	0.0250 (6)	0.0256 (6)	−0.0019 (5)	0.0053 (5)	0.0040 (5)
C13	0.0315 (7)	0.0394 (8)	0.0305 (7)	−0.0006 (6)	0.0085 (6)	0.0035 (6)
C12	0.0377 (8)	0.0313 (7)	0.0269 (7)	−0.0007 (6)	−0.0001 (6)	0.0011 (5)
C14	0.0481 (9)	0.0333 (8)	0.0282 (7)	0.0070 (6)	0.0009 (6)	0.0085 (6)

Geometric parameters (Å, º) top

O1—C8	1.3772 (19)	C3—C2	1.346 (2)
O1—C1	1.382 (2)	C3—H3	0.9300
O4—C10	1.2058 (19)	C1—C2	1.453 (2)
O3—C10	1.3668 (19)	C11—C12	1.530 (2)
O3—C6	1.405 (2)	C11—C13	1.534 (3)
O2—C1	1.212 (2)	C11—C14	1.539 (2)
C8—C7	1.389 (2)	C2—H2	0.9300
C8—C9	1.402 (2)	C13—H13A	0.9600
C9—C4	1.401 (2)	C13—H13B	0.9600
C9—C3	1.438 (2)	C13—H13C	0.9600
C7—C6	1.383 (2)	C12—H12A	0.9600
C7—H7	0.9300	C12—H12B	0.9600
C6—C5	1.395 (2)	C12—H12C	0.9600
C4—C5	1.383 (2)	C14—H14A	0.9600
C4—H4	0.9300	C14—H14B	0.9600
C10—C11	1.523 (3)	C14—H14C	0.9600
C5—H5	0.9300

C8—O1—C1	121.89 (12)	O1—C1—C2	117.24 (12)
C10—O3—C6	118.83 (11)	C10—C11—C12	112.83 (13)
O1—C8—C7	116.55 (13)	C10—C11—C13	107.60 (12)
O1—C8—C9	121.17 (13)	C12—C11—C13	110.08 (13)
C7—C8—C9	122.28 (12)	C10—C11—C14	106.56 (12)
C4—C9—C8	118.06 (14)	C12—C11—C14	109.61 (14)
C4—C9—C3	124.18 (13)	C13—C11—C14	110.08 (13)
C8—C9—C3	117.76 (12)	C3—C2—C1	121.31 (14)
C6—C7—C8	117.34 (13)	C3—C2—H2	119.3
C6—C7—H7	121.3	C1—C2—H2	119.3
C8—C7—H7	121.3	C11—C13—H13A	109.5
C7—C6—C5	122.65 (14)	C11—C13—H13B	109.5
C7—C6—O3	120.70 (13)	H13A—C13—H13B	109.5
C5—C6—O3	116.50 (12)	C11—C13—H13C	109.5
C5—C4—C9	121.07 (14)	H13A—C13—H13C	109.5
C5—C4—H4	119.5	H13B—C13—H13C	109.5
C9—C4—H4	119.5	C11—C12—H12A	109.5
O4—C10—O3	122.82 (13)	C11—C12—H12B	109.5
O4—C10—C11	124.93 (13)	H12A—C12—H12B	109.5
O3—C10—C11	112.17 (12)	C11—C12—H12C	109.5
C4—C5—C6	118.57 (12)	H12A—C12—H12C	109.5
C4—C5—H5	120.7	H12B—C12—H12C	109.5
C6—C5—H5	120.7	C11—C14—H14A	109.5
C2—C3—C9	120.62 (14)	C11—C14—H14B	109.5
C2—C3—H3	119.7	H14A—C14—H14B	109.5
C9—C3—H3	119.7	C11—C14—H14C	109.5
O2—C1—O1	116.69 (14)	H14A—C14—H14C	109.5
O2—C1—C2	126.05 (15)	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	0.93	2.49	3.343 (4)	153

Symmetry code: (i) x+1, y, z.

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 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.

References

Bazié, H., Ziki, E., Brahima, S., Ratsimbazafy, V., Roge, P., Wenger, E., Djandé, A. & Lecomte, C. (2025). IUCrData 10, x250189. Google Scholar
Bruker (2019). APEX4 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rawat, A. A. & Reddy, V. B. (2022). Eur J. Med. Chem. Rep. 5, 100038. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Todeschini, A. R., de Miranda, A. L. P., da Silva, K. C. M., Parrini, S. C. & Barreiro, E. J. (1998). Eur. J. Med. Chem. 33, 189–199. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yadav, A. K., Maharjan Shrestha, R. & Yadav, P. N. (2024). Eur. J. Med. Chem. 267, 116179. CrossRef PubMed Google Scholar
Ziki, E., Akonan, L., Kouman, K. C., Dali, D., Megnassan, E., Kakou-Yao, R., Tenon, A. J., Frecer, V. & Miertus, S. J. (2023). J. Pharm. Res. Int. 35, 10–33. CrossRef Google Scholar

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