Crystal structure of 2-oxo-2H-chromen-3-yl propano­ate

Ziki, E.; Yoda, J.; Djandé, A.; Saba, A.; Kakou-Yao, R.

doi:10.1107/S2056989016015279

research communications

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ISSN: 2056-9890

Volume 72| Part 11| November 2016| Pages 1562-1564

https://doi.org/10.1107/S2056989016015279

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Crystal structure of 2-oxo-2H-chromen-3-yl propanoate

Eric Ziki,^a ^* Jules Yoda,^b Abdoulaye Djandé,^b Adama Saba ^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 Matériaux, Equipe de Chimie Organique et Phytochimie, Université Ouaga I Pr Joseph KI-ZERBO 03 BP 7021 Ouagadougou 03, Burkina Faso
^*Correspondence e-mail: eric.ziki@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 31 August 2016; accepted 28 September 2016; online 11 October 2016)

In the title compound, C₁₂H₁₀O₄, the dihedral angle between the coumarin ring system [maximum deviation = 0.033 (8) Å] and the propionate side chain is 78.48 (8)°. In the crystal, weak C—H⋯O hydrogen bonds generate inversion dimers and and C—H⋯π and π–π interactions link the dimers into a three-dimensional network. A quantum chemical calculation is in good agreement with the observed structure.

Keywords: crystal structure; π–π interactions; C—H⋯π interactions; chromane; quantum-chemical calculations.

CCDC reference: 1507161

1. Chemical context

Coumarin and its derivatives are widely recognized for their multiple biological activities, including anticancer (Lacy et al., 2004 ; Kostova, 2005 ), anti-inflammatory (Todeschini et al., 1998 ), antiviral (Borges et al., 2005 ), antimalarial (Agarwal et al., 2005 ) and anticoagulant (Maurer et al., 1998 ) properties. As part of our studies in this area, we now describe the synthesis and crystal structure of the title compound, (I).

2. Structural commentary

In compound (I) (Fig. 1), the coumarin ring system is almost planar [maximum deviation = 0.033 (1)Å] and is oriented at an angle of 70.84 (8)° with respect to the plane formed by the propanoate group. An inspection of the bond lengths shows that there is a slight asymmetry of the electronic distribution around the coumarin ring: the C2—C3 [1.329 (2) Å] and C2—C1 [1.460 (2) Å] bond lengths are 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-3-carboxamide derivatives (Gomes et al., 2016 ).

Figure 1
The molecular structure of compound (I)

, with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the molecules are linked by pairs of C8—H8⋯O2(x, −y, 1 − z) weak hydrogen bonds to form R₂²(12) loops, which lie in a chain running along the c axis direction (Fig. 2). Weak aromatic π–π stacking interactions of 3.7956 (8) Å (Janiak, 2000 ) are present between the coumarin pyran ring (centroid Cg1) and benzene ring (centroid Cg2) of symmetry-related (−x, 1 − y, 1 − z) molecules, thus forming a three-dimensional supramolecular network. A weak C—H⋯Cg (π–ring) interaction is also present (Figs. 3 and 4, and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.59	3.4783 (19)	161
C5—H5⋯Cg2ⁱⁱ	0.93	2.78	3.4959 (16)	134
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
View of an inversion dimer linked by a pair of C8—H8⋯O2 (−x, −y, −z + 1) interactions, generating an R₂²(12) loop. This dimers stack by unit translation along the c axis. H atoms not involved in hydrogen bonding have been omitted.

Figure 3
A view of the crystal packing, showing the π–π stacking and C—H⋯π interactions (dashed lines). The green dots are ring centroids. H atoms not involved in the C—H⋯π interactions have been omitted for clarity.

Figure 4
Part of the crystal structure of (I)

, showing C—H⋯π and π–π interactions as dashed lines. H atoms have been omitted for clarity.

4. Theoretical calculations

Quantum-chemical calculations were performed to compare with the experimental analysis. An ab-initio Hartree–Fock (HF) method was used with the standard basis set of 6-31G using the GAUSSIAN03 software package (Frisch et al., 2004 ; Dennington et al., 2007 ) to obtain the optimized molecular structure. The computational results are in good agreement with the experimental crystallographic data (Table 2).

Table 2
Experimental and calculated bond lengths (Å)

Bond	X-ray	HF(6–31G)
O1—C1	1.3628 (17)	1.371
O1—C9	1.3769 (17)	1.378
O2—C1	1.2004 (18)	1.227
O3—C10	1.3713 (18)	1.359
O3—C2	1.3893 (17)	1.381
O4—C10	1.1932 (19)	1.21
C1—C2	1.460 (2)	1.468
C2—C3	1.329 (2)	1.355
C3—C4	1.4403 (19)	1.441
C4—C5	1.401 (2)	1.406
C4—C9	1.3928 (18)	1.407
C5—C6	1.370 (2)	1.387
C6—C7	1.386 (2)	1.395
C7—C8	1.379 (2)	1.383
C8—C9	1.3842 (19)	1.408
C10—C11	1.495 (2)	1.497
C11—C12	1.491 (3)	1.525

5. Synthesis and crystallization

In a 100 ml round-necked flask topped with a water condenser were introduced successively 25 ml of dried diethyl ether, 6.17 × 10 ⁻³ mol (≃ 0.8 ml) of propionic anhydride and 2.35 ml (4.7 molar equivalents) of dried pyridine. While stirring strongly, 6.17 × 10⁻³ mol (1 g) of 3-hydroxycoumarin was added in small portions over 30 min. The reaction mixture was left under agitation at room temperature for 3 h. The mixture was then 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 petroleum ether and recrystallized from a solvent mixture of chloroform–hexane (1/3, v/v). Colourless prisms of the title compound were obtained in a yield of 65%, m. p. = 351–353 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed in calculated positions [C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene)] and refined using a riding-model approximation with U_iso(H) constrained to 1.2 (aromatic and methylene group) or 1.5 (methyl group) times U_eq of the respective parent atom.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀O₄
M_r	218.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.1179 (4), 5.7243 (2), 15.3275 (5)
β (°)	94.881 (3)
V (Å³)	1059.36 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.87
Crystal size (mm)	0.46 × 0.16 × 0.08

Data collection
Diffractometer	Agilent SuperNova Dual (Cu at zero) Source diffractometer with an AtlasS2 detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.778, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6028, 1930, 1655
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.117, 1.06
No. of reflections	1930
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1507161

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989016015279/hb7613sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016015279/hb7613Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016015279/hb7613Isup3.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 propanoate top

Crystal data top

C₁₂H₁₀O₄	F(000) = 456
M_r = 218.20	D_x = 1.368 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 351 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 12.1179 (4) Å	Cell parameters from 3028 reflections
b = 5.7243 (2) Å	θ = 5.8–68.6°
c = 15.3275 (5) Å	µ = 0.87 mm⁻¹
β = 94.881 (3)°	T = 293 K
V = 1059.36 (6) Å³	Prism, colourless
Z = 4	0.46 × 0.16 × 0.08 mm

Data collection top

Agilent SuperNova Dual (Cu at zero) Source diffractometer with an AtlasS2 detector	1930 independent reflections
Radiation source: sealed X-ray tube	1655 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
Detector resolution: 5.3048 pixels mm^-1	θ_max = 68.9°, θ_min = 3.7°
ω scan	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −6→6
T_min = 0.778, T_max = 1.000	l = −15→18
6028 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0631P)² + 0.1085P] where P = (F_o² + 2F_c²)/3
1930 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³
40 constraints

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	0.08845 (8)	0.19504 (17)	0.44462 (6)	0.0505 (3)
O3	0.36752 (8)	0.39585 (19)	0.41680 (7)	0.0567 (3)
C9	0.02550 (11)	0.3708 (2)	0.40435 (8)	0.0426 (3)
C2	0.25245 (11)	0.3964 (2)	0.40998 (9)	0.0466 (3)
C3	0.19407 (11)	0.5719 (2)	0.37284 (8)	0.0455 (3)
H3	0.2298	0.6985	0.3497	0.055*
C4	0.07494 (11)	0.5644 (2)	0.36879 (8)	0.0420 (3)
C8	−0.08834 (12)	0.3450 (3)	0.40123 (9)	0.0521 (3)
H8	−0.1198	0.2150	0.4258	0.063*
C1	0.20130 (12)	0.1982 (2)	0.45088 (9)	0.0492 (3)
O4	0.36176 (9)	0.1032 (2)	0.31915 (8)	0.0683 (3)
O2	0.24985 (10)	0.0406 (2)	0.48893 (8)	0.0695 (3)
C5	0.00553 (12)	0.7361 (2)	0.32863 (9)	0.0497 (3)
H5	0.0362	0.8676	0.3045	0.060*
C6	−0.10727 (13)	0.7114 (3)	0.32463 (10)	0.0566 (4)
H6	−0.1527	0.8257	0.2975	0.068*
C7	−0.15398 (12)	0.5169 (3)	0.36080 (10)	0.0567 (4)
H7	−0.2306	0.5022	0.3578	0.068*
C10	0.41542 (12)	0.2272 (3)	0.36892 (10)	0.0530 (3)
C11	0.53858 (13)	0.2315 (4)	0.38698 (13)	0.0728 (5)
H11A	0.5644	0.3905	0.3808	0.087*
H11B	0.5576	0.1839	0.4471	0.087*
C12	0.59736 (16)	0.0768 (5)	0.32791 (15)	0.0858 (6)
H12A	0.6758	0.0871	0.3428	0.129*
H12B	0.5806	0.1252	0.2683	0.129*
H12C	0.5736	−0.0817	0.3346	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0500 (5)	0.0463 (5)	0.0557 (5)	−0.0037 (4)	0.0068 (4)	0.0091 (4)
O3	0.0398 (5)	0.0614 (6)	0.0686 (6)	−0.0025 (4)	0.0019 (4)	−0.0145 (5)
C9	0.0453 (7)	0.0438 (6)	0.0394 (6)	−0.0015 (5)	0.0069 (5)	−0.0014 (5)
C2	0.0395 (7)	0.0505 (7)	0.0499 (7)	−0.0036 (5)	0.0052 (5)	−0.0083 (5)
C3	0.0468 (7)	0.0425 (7)	0.0485 (7)	−0.0072 (5)	0.0109 (5)	−0.0037 (5)
C4	0.0459 (7)	0.0411 (6)	0.0398 (6)	−0.0018 (5)	0.0083 (5)	−0.0037 (5)
C8	0.0473 (7)	0.0570 (8)	0.0535 (7)	−0.0083 (6)	0.0125 (6)	−0.0022 (6)
C1	0.0506 (7)	0.0490 (7)	0.0479 (7)	0.0031 (6)	0.0034 (5)	0.0009 (6)
O4	0.0510 (6)	0.0805 (8)	0.0730 (7)	−0.0006 (5)	0.0025 (5)	−0.0238 (6)
O2	0.0665 (7)	0.0669 (7)	0.0749 (7)	0.0122 (6)	0.0041 (6)	0.0197 (6)
C5	0.0575 (8)	0.0450 (7)	0.0474 (7)	0.0025 (6)	0.0100 (6)	0.0013 (5)
C6	0.0548 (8)	0.0611 (9)	0.0540 (7)	0.0145 (7)	0.0065 (6)	−0.0010 (6)
C7	0.0411 (7)	0.0715 (9)	0.0584 (8)	0.0027 (6)	0.0097 (6)	−0.0069 (7)
C10	0.0450 (8)	0.0594 (8)	0.0545 (7)	0.0007 (6)	0.0038 (6)	−0.0053 (6)
C11	0.0430 (8)	0.0917 (13)	0.0829 (11)	0.0053 (8)	−0.0003 (7)	−0.0168 (10)
C12	0.0526 (10)	0.1094 (16)	0.0951 (13)	0.0179 (10)	0.0050 (9)	−0.0168 (12)

Geometric parameters (Å, º) top

O1—C1	1.3628 (17)	O4—C10	1.1932 (19)
O1—C9	1.3769 (17)	C5—C6	1.370 (2)
O3—C10	1.3713 (18)	C5—H5	0.9300
O3—C2	1.3893 (17)	C6—C7	1.386 (2)
C9—C8	1.3842 (19)	C6—H6	0.9300
C9—C4	1.3926 (18)	C7—H7	0.9300
C2—C3	1.329 (2)	C10—C11	1.495 (2)
C2—C1	1.460 (2)	C11—C12	1.491 (3)
C3—C4	1.4403 (19)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C5	1.401 (2)	C12—H12A	0.9600
C8—C7	1.379 (2)	C12—H12B	0.9600
C8—H8	0.9300	C12—H12C	0.9600
C1—O2	1.2004 (18)

C1—O1—C9	122.43 (10)	C4—C5—H5	119.8
C10—O3—C2	115.41 (11)	C5—C6—C7	120.31 (14)
O1—C9—C8	116.74 (12)	C5—C6—H6	119.8
O1—C9—C4	121.11 (12)	C7—C6—H6	119.8
C8—C9—C4	122.15 (13)	C8—C7—C6	120.90 (14)
C3—C2—O3	121.88 (12)	C8—C7—H7	119.6
C3—C2—C1	122.80 (12)	C6—C7—H7	119.6
O3—C2—C1	115.22 (12)	O4—C10—O3	121.89 (13)
C2—C3—C4	119.40 (12)	O4—C10—C11	127.56 (15)
C2—C3—H3	120.3	O3—C10—C11	110.52 (13)
C4—C3—H3	120.3	C12—C11—C10	113.50 (15)
C9—C4—C5	117.88 (12)	C12—C11—H11A	108.9
C9—C4—C3	118.03 (12)	C10—C11—H11A	108.9
C5—C4—C3	124.05 (12)	C12—C11—H11B	108.9
C7—C8—C9	118.32 (13)	C10—C11—H11B	108.9
C7—C8—H8	120.8	H11A—C11—H11B	107.7
C9—C8—H8	120.8	C11—C12—H12A	109.5
O2—C1—O1	118.14 (13)	C11—C12—H12B	109.5
O2—C1—C2	125.74 (14)	H12A—C12—H12B	109.5
O1—C1—C2	116.12 (12)	C11—C12—H12C	109.5
C6—C5—C4	120.43 (13)	H12A—C12—H12C	109.5
C6—C5—H5	119.8	H12B—C12—H12C	109.5

C1—O1—C9—C8	179.07 (12)	C9—O1—C1—C2	−1.73 (18)
C1—O1—C9—C4	−0.99 (18)	C3—C2—C1—O2	−176.26 (14)
C10—O3—C2—C3	−113.91 (15)	O3—C2—C1—O2	0.3 (2)
C10—O3—C2—C1	69.53 (17)	C3—C2—C1—O1	3.69 (19)
O3—C2—C3—C4	−179.09 (11)	O3—C2—C1—O1	−179.78 (10)
C1—C2—C3—C4	−2.8 (2)	C9—C4—C5—C6	−0.27 (19)
O1—C9—C4—C5	179.85 (11)	C3—C4—C5—C6	177.46 (12)
C8—C9—C4—C5	−0.21 (19)	C4—C5—C6—C7	0.4 (2)
O1—C9—C4—C3	1.98 (17)	C9—C8—C7—C6	−0.4 (2)
C8—C9—C4—C3	−178.08 (12)	C5—C6—C7—C8	−0.1 (2)
C2—C3—C4—C9	−0.08 (18)	C2—O3—C10—O4	6.2 (2)
C2—C3—C4—C5	−177.81 (12)	C2—O3—C10—C11	−175.47 (14)
O1—C9—C8—C7	−179.53 (12)	O4—C10—C11—C12	6.5 (3)
C4—C9—C8—C7	0.5 (2)	O3—C10—C11—C12	−171.65 (17)
C9—O1—C1—O2	178.23 (13)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.59	3.4783 (19)	161
C5—H5···Cg2ⁱⁱ	0.93	2.78	3.4959 (16)	134

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

Experimental and calculated bond lengths (Å) top

Bond	X-ray	HF(6-31G)
O1—C1	1.3628 (17)	1.371
O1—C9	1.3769 (17)	1.378
O2—C1	1.2004 (18)	1.227
O3—C10	1.3713 (18)	1.359
O3—C2	1.3893 (17)	1.381
O4—C10	1.1932 (19)	1.21
C1—C2	1.460 (2)	1.468
C2—C3	1.329 (2)	1.355
C3—C4	1.4403 (19)	1.441
C4—C5	1.401 (2)	1.406
C4—C9	1.3928 (18)	1.407
C5—C6	1.370 (2)	1.387
C6—C7	1.386 (2)	1.395
C7—C8	1.379 (2)	1.383
C8—C9	1.3842 (19)	1.408
C10—C11	1.495 (2)	1.497
C11—C12	1.491 (3)	1.525

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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