3-Benzoyl-7-meth­oxy-2H-chromen-2-one

Li, W.; Xiao, Y.; Yuan, J.; Yang, L.; Mao, P.

doi:10.1107/S241431461700373X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170373

https://doi.org/10.1107/S241431461700373X

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3-Benzoyl-7-methoxy-2H-chromen-2-one

Weijie Li,^a Yongmei Xiao,^a Jinwei Yuan,^a ^* Liangru Yang ^a and Pu Mao ^a

^aSchool of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: yuanjinweigs@126.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 February 2017; accepted 8 March 2017; online 14 March 2017)

In the title compound, C₁₇H₁₂O₄, the dihedral angle between the coumarin ring system (r.m.s. deviation = 0.018 Å) and the phenyl ring is 55.96 (8)°. In the crystal, weak C—H⋯O interactions connect the molecules into a three-dimensional network and aromatic π–π stacking interactions are also observed [shortest centroid–centroid separation = 3.6692 (9) Å].

Keywords: crystal structure; 3-aroylcoumarin derivative; C—H⋯O interactions; π–π stacking.

CCDC reference: 1521448

Structure description

3-Carbonylcoumarin represents an important structural element in anticoagulant agents (Sandhu et al., 2014 ), and acts as a monoamine oxidase (MAO)-B inhibitor (Mertens et al., 2014 ). As part of our work on the synthesis of 3-aroylcoumarins, we report the crystal structure of the title compound (Fig. 1). This study provides an opportunity to investigate the geometry of 3-aroylcoumarin derivatives with no strong intermolecular interactions.

Figure 1
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

The C7—O1 and C8—O2 bond lengths are 1.218 (2) and 1.205 (2) Å, respectively. They are shorter than the standard C=O bond length (1.231 Å; Gao et al., 2014 ) due to conjugation with the aromatic ring. The coumarin ring is almost planar (r.m.s. deviation = 0.018 Å) and subtends a dihedral angle of 55.96 (8)° with the phenyl ring. The main twist occurs about the C7—C9 bond [C6—C7—C9—C8 = −51.8 (2)°]. The methyl group (atom C17) is approximately coplanar with its attached ring [deviation = 0.111 (2) Å].

In the crystal, weak C—H⋯O interactions (Table 1) connect the molecules into a three-dimensional network and aromatic π–π stacking interactions are also observed [shortest centroid–centroid separation = 3.6692 (9) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.93	2.58	3.503 (2)	171
C5—H5⋯O2ⁱⁱ	0.93	2.49	3.330 (2)	151
C13—H13⋯O1ⁱⁱⁱ	0.93	2.37	3.281 (2)	165
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Synthesis and crystallization

The synthesis of 3-benzoyl-7-methoxy-2H-chromen-2-one is based on our reported literature procedure (Yuan et al., 2015 ). In a 25 ml Schlenk tube, 7-methoxyl coumarin (0.25 mmol, 44 mg), benzaldehyde (1.0 mmol, 106 mg), TBHP (1.0 mmol) and FeCl₂ (0.025 mmol, 31.5 mg) were added and charged with nitrogen (3 cycles). Chlorobenzene (2 ml) was then added, and the reaction mixture was heated on an oil bath at 120°C for 12 h (monitored by TLC). After the reaction mixture had cooled to room temperature and the solvent had been removed with the aid of a rotary evaporator, 2 ml ethylacetate was added to the residue. The solution was filtrated, and the filtrate was distilled under vacuum. The crude product was purified by silica gel column chromatography using ethyl acetate/petroleum ether (1:5) as eluant to obtain the desired product as colourless prismatic crystals, m.p. 134–135°C.

¹H NMR (400 MHz, CDCl₃) δ: 8.06 (s, 1H), 7.87 (d, J_H—H = 7.2 Hz, 2H), 7.65 (td, J_H—H = 8.7 Hz, J_H—H = 1.5 Hz, 1H), 7.60 (dd, J_H—H = 7.9 Hz, J_H—H = 1.5 Hz, 1H), 7.48 (d, J_H—H = 7.9 Hz, 2H), 7.40 (t, J_H—H = 8.3 Hz, 1H), 7.35 (td, J_H—H = 7.8 Hz, J_H—H = 0.8 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ: 191.7 (C=O), 158.4 (C=O), 154.7, 145.4 (CH), 136.2, 133.8 (CH), 133.7 (CH), 129.6 (CH), 129.2 (CH), 128.6 (CH), 125.0 (CH), 118.2, 116.9 (CH). IR (KBr) ν (cm⁻¹): 1714, 1654 (C=O), 1608, 1565, 1448 (Ar–). MS (ESI) m/z: 251.3 [M + H]⁺ (calculated for C₁₆H₁₁O₃⁺ 251.1).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₂O₄
M_r	280.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	4.07206 (11), 11.9589 (3), 27.5626 (7)
β (°)	90.306 (2)
V (Å³)	1342.21 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.946, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4863, 2384, 1994
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.122, 1.07
No. of reflections	2384
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.22
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1521448

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S241431461700373X/hb4121sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700373X/hb4121Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3-Benzoyl-7-methoxy-2H-chromen-2-one top

Crystal data top

C₁₇H₁₂O₄	F(000) = 584
M_r = 280.27	D_x = 1.387 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 4.07206 (11) Å	Cell parameters from 2065 reflections
b = 11.9589 (3) Å	θ = 3.7–71.9°
c = 27.5626 (7) Å	µ = 0.82 mm⁻¹
β = 90.306 (2)°	T = 291 K
V = 1342.21 (6) Å³	Prism, colourless
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	2384 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.2312 pixels mm^-1	θ_max = 67.1°, θ_min = 3.2°
ω scans	h = −3→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→14
T_min = 0.946, T_max = 1.000	l = −32→32
4863 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.064P)² + 0.1354P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2384 reflections	Δρ_max = 0.14 e Å⁻³
191 parameters	Δρ_min = −0.22 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.

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

	x	y	z	U_iso*/U_eq
O1	−0.0239 (5)	0.58205 (12)	0.35344 (5)	0.0833 (5)
O2	−0.1454 (3)	0.88869 (10)	0.30432 (4)	0.0551 (3)
O3	0.1358 (3)	0.86182 (9)	0.23776 (4)	0.0443 (3)
O4	0.6558 (4)	0.80906 (12)	0.08545 (4)	0.0626 (4)
C1	0.0047 (5)	0.71111 (17)	0.43741 (7)	0.0596 (5)
H1	−0.1134	0.6447	0.4389	0.071*
C2	0.0569 (6)	0.7723 (2)	0.47901 (7)	0.0698 (6)
H2	−0.0263	0.7473	0.5084	0.084*
C3	0.2323 (6)	0.8706 (2)	0.47706 (7)	0.0723 (6)
H3	0.2659	0.9123	0.5051	0.087*
C4	0.3582 (6)	0.90725 (18)	0.43354 (7)	0.0664 (5)
H4	0.4782	0.9734	0.4324	0.080*
C5	0.3070 (4)	0.84630 (15)	0.39172 (6)	0.0516 (4)
H5	0.3932	0.8713	0.3625	0.062*
C6	0.1279 (4)	0.74808 (14)	0.39307 (6)	0.0454 (4)
C7	0.0744 (5)	0.67775 (14)	0.34951 (6)	0.0506 (4)
C8	0.0393 (4)	0.82732 (13)	0.28306 (5)	0.0422 (3)
C9	0.1607 (4)	0.71949 (12)	0.29987 (5)	0.0434 (4)
C10	0.3356 (4)	0.65378 (13)	0.26960 (6)	0.0465 (4)
H10	0.3984	0.5828	0.2799	0.056*
C11	0.4259 (4)	0.69057 (12)	0.22246 (6)	0.0432 (4)
C12	0.3228 (4)	0.79611 (12)	0.20769 (5)	0.0401 (3)
C13	0.3930 (4)	0.84099 (13)	0.16282 (5)	0.0437 (4)
H13	0.3213	0.9122	0.1542	0.052*
C14	0.5743 (4)	0.77607 (14)	0.13099 (6)	0.0478 (4)
C15	0.6868 (5)	0.66990 (15)	0.14458 (7)	0.0543 (4)
H15	0.8112	0.6278	0.1231	0.065*
C16	0.6141 (4)	0.62805 (13)	0.18936 (6)	0.0516 (4)
H16	0.6898	0.5575	0.1981	0.062*
C17	0.5324 (6)	0.91387 (18)	0.06893 (7)	0.0675 (5)
H17A	0.5942	0.9250	0.0357	0.101*
H17B	0.6225	0.9728	0.0885	0.101*
H17C	0.2974	0.9144	0.0714	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1370 (15)	0.0514 (8)	0.0617 (8)	−0.0372 (9)	0.0034 (9)	0.0076 (6)
O2	0.0616 (7)	0.0509 (7)	0.0531 (6)	0.0095 (6)	0.0150 (5)	0.0038 (5)
O3	0.0553 (7)	0.0364 (5)	0.0413 (5)	0.0069 (5)	0.0065 (4)	0.0026 (4)
O4	0.0776 (9)	0.0641 (8)	0.0462 (6)	0.0104 (7)	0.0148 (6)	−0.0017 (6)
C1	0.0651 (11)	0.0604 (10)	0.0534 (10)	−0.0051 (9)	0.0078 (8)	0.0128 (8)
C2	0.0811 (14)	0.0863 (15)	0.0422 (9)	0.0055 (11)	0.0101 (8)	0.0071 (9)
C3	0.0889 (15)	0.0808 (14)	0.0472 (10)	0.0024 (12)	−0.0054 (9)	−0.0113 (10)
C4	0.0786 (13)	0.0625 (11)	0.0581 (11)	−0.0120 (10)	−0.0084 (9)	−0.0057 (9)
C5	0.0548 (10)	0.0535 (9)	0.0466 (8)	−0.0071 (8)	0.0004 (7)	0.0034 (7)
C6	0.0480 (8)	0.0460 (8)	0.0421 (8)	−0.0007 (7)	0.0018 (6)	0.0060 (6)
C7	0.0598 (10)	0.0399 (8)	0.0521 (9)	−0.0081 (7)	−0.0010 (7)	0.0071 (7)
C8	0.0461 (8)	0.0377 (7)	0.0428 (8)	−0.0039 (6)	0.0022 (6)	−0.0005 (6)
C9	0.0512 (8)	0.0352 (7)	0.0438 (8)	−0.0069 (6)	−0.0033 (6)	0.0008 (6)
C10	0.0552 (9)	0.0334 (7)	0.0508 (8)	−0.0013 (6)	−0.0080 (7)	0.0010 (6)
C11	0.0477 (8)	0.0346 (7)	0.0473 (8)	−0.0004 (6)	−0.0040 (6)	−0.0035 (6)
C12	0.0417 (8)	0.0365 (7)	0.0419 (7)	0.0000 (6)	−0.0011 (6)	−0.0055 (6)
C13	0.0491 (9)	0.0380 (7)	0.0440 (8)	0.0033 (6)	0.0002 (6)	−0.0011 (6)
C14	0.0498 (9)	0.0493 (9)	0.0443 (8)	−0.0002 (7)	0.0023 (6)	−0.0073 (7)
C15	0.0603 (10)	0.0475 (9)	0.0551 (9)	0.0064 (8)	0.0062 (7)	−0.0143 (7)
C16	0.0587 (10)	0.0360 (8)	0.0603 (10)	0.0077 (7)	−0.0024 (7)	−0.0067 (7)
C17	0.0833 (14)	0.0706 (13)	0.0488 (9)	0.0062 (11)	0.0108 (9)	0.0070 (9)

Geometric parameters (Å, º) top

O1—C7	1.218 (2)	C7—C9	1.500 (2)
O2—C8	1.205 (2)	C8—C9	1.456 (2)
O3—C8	1.3744 (18)	C9—C10	1.352 (2)
O3—C12	1.3751 (18)	C10—H10	0.9300
O4—C14	1.359 (2)	C10—C11	1.422 (2)
O4—C17	1.424 (2)	C11—C12	1.390 (2)
C1—H1	0.9300	C11—C16	1.410 (2)
C1—C2	1.376 (3)	C12—C13	1.380 (2)
C1—C6	1.395 (2)	C13—H13	0.9300
C2—H2	0.9300	C13—C14	1.387 (2)
C2—C3	1.376 (3)	C14—C15	1.400 (2)
C3—H3	0.9300	C15—H15	0.9300
C3—C4	1.378 (3)	C15—C16	1.366 (3)
C4—H4	0.9300	C16—H16	0.9300
C4—C5	1.379 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C5—C6	1.383 (2)	C17—H17C	0.9600
C6—C7	1.481 (2)

C8—O3—C12	122.55 (12)	C10—C9—C8	119.85 (14)
C14—O4—C17	117.61 (14)	C9—C10—H10	119.2
C2—C1—H1	119.8	C9—C10—C11	121.57 (14)
C2—C1—C6	120.45 (19)	C11—C10—H10	119.2
C6—C1—H1	119.8	C12—C11—C10	118.00 (14)
C1—C2—H2	120.0	C12—C11—C16	117.15 (14)
C3—C2—C1	119.96 (18)	C16—C11—C10	124.85 (14)
C3—C2—H2	120.0	O3—C12—C11	120.63 (14)
C2—C3—H3	120.0	O3—C12—C13	115.85 (13)
C2—C3—C4	120.08 (19)	C13—C12—C11	123.51 (14)
C4—C3—H3	120.0	C12—C13—H13	121.2
C3—C4—H4	119.9	C12—C13—C14	117.56 (14)
C3—C4—C5	120.3 (2)	C14—C13—H13	121.2
C5—C4—H4	119.9	O4—C14—C13	123.72 (16)
C4—C5—H5	119.9	O4—C14—C15	115.43 (15)
C4—C5—C6	120.25 (17)	C13—C14—C15	120.85 (15)
C6—C5—H5	119.9	C14—C15—H15	119.9
C1—C6—C7	118.57 (16)	C16—C15—C14	120.14 (15)
C5—C6—C1	118.99 (16)	C16—C15—H15	119.9
C5—C6—C7	122.38 (15)	C11—C16—H16	119.6
O1—C7—C6	120.57 (16)	C15—C16—C11	120.78 (15)
O1—C7—C9	118.22 (16)	C15—C16—H16	119.6
C6—C7—C9	121.09 (14)	O4—C17—H17A	109.5
O2—C8—O3	116.18 (14)	O4—C17—H17B	109.5
O2—C8—C9	126.62 (14)	O4—C17—H17C	109.5
O3—C8—C9	117.17 (13)	H17A—C17—H17B	109.5
C8—C9—C7	120.28 (14)	H17A—C17—H17C	109.5
C10—C9—C7	119.75 (14)	H17B—C17—H17C	109.5

O1—C7—C9—C8	132.2 (2)	C7—C9—C10—C11	−179.27 (15)
O1—C7—C9—C10	−43.9 (3)	C8—O3—C12—C11	−0.6 (2)
O2—C8—C9—C7	−4.0 (3)	C8—O3—C12—C13	178.34 (14)
O2—C8—C9—C10	172.08 (17)	C8—C9—C10—C11	4.6 (2)
O3—C8—C9—C7	178.13 (13)	C9—C10—C11—C12	−1.3 (2)
O3—C8—C9—C10	−5.8 (2)	C9—C10—C11—C16	178.42 (16)
O3—C12—C13—C14	−178.47 (13)	C10—C11—C12—O3	−0.8 (2)
O4—C14—C15—C16	−179.02 (16)	C10—C11—C12—C13	−179.67 (14)
C1—C2—C3—C4	−0.6 (4)	C10—C11—C16—C15	179.45 (16)
C1—C6—C7—O1	−12.3 (3)	C11—C12—C13—C14	0.5 (2)
C1—C6—C7—C9	171.84 (16)	C12—O3—C8—O2	−174.28 (14)
C2—C1—C6—C5	0.9 (3)	C12—O3—C8—C9	3.8 (2)
C2—C1—C6—C7	178.16 (19)	C12—C11—C16—C15	−0.8 (2)
C2—C3—C4—C5	0.5 (4)	C12—C13—C14—O4	178.81 (15)
C3—C4—C5—C6	0.2 (3)	C12—C13—C14—C15	−1.3 (2)
C4—C5—C6—C1	−0.9 (3)	C13—C14—C15—C16	1.1 (3)
C4—C5—C6—C7	−178.07 (18)	C14—C15—C16—C11	0.0 (3)
C5—C6—C7—O1	164.90 (19)	C16—C11—C12—O3	179.44 (14)
C5—C6—C7—C9	−11.0 (3)	C16—C11—C12—C13	0.6 (2)
C6—C1—C2—C3	−0.2 (3)	C17—O4—C14—C13	−3.4 (3)
C6—C7—C9—C8	−51.8 (2)	C17—O4—C14—C15	176.72 (16)
C6—C7—C9—C10	132.12 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.58	3.503 (2)	171
C5—H5···O2ⁱⁱ	0.93	2.49	3.330 (2)	151
C13—H13···O1ⁱⁱⁱ	0.93	2.37	3.281 (2)	165

Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) −x, y+1/2, −z+1/2.

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (award Nos. 21302042, 21172055); the Program for Innovative Research Team from Zhengzhou (award No. 131PCXTD605); Department of Henan Province Natural Science and Technology Foundation (award No. 142102210410); Natural Science Foundation in Henan Province Department of Education (award No. 14B150053).

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