organic compounds
3-Benzoyl-7-methoxy-2H-chromen-2-one
aSchool of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, People's Republic of China
*Correspondence e-mail: yuanjinweigs@126.com
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].
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 of the title compound (Fig. 1). This study provides an opportunity to investigate the geometry of 3-aroylcoumarin derivatives with no strong intermolecular interactions.
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].
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 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, JH—H = 7.2 Hz, 2H), 7.65 (td, JH—H = 8.7 Hz, JH—H = 1.5 Hz, 1H), 7.60 (dd, JH—H = 7.9 Hz, JH—H = 1.5 Hz, 1H), 7.48 (d, JH—H = 7.9 Hz, 2H), 7.40 (t, JH—H = 8.3 Hz, 1H), 7.35 (td, JH—H = 7.8 Hz, JH—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 .
details are summarized in Table 2Structural data
CCDC reference: 1521448
https://doi.org/10.1107/S241431461700373X/hb4121sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700373X/hb4121Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2013); cell
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).C17H12O4 | F(000) = 584 |
Mr = 280.27 | Dx = 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 |
Agilent Xcalibur Eos Gemini diffractometer | 2384 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 1994 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 16.2312 pixels mm-1 | θmax = 67.1°, θmin = 3.2° |
ω scans | h = −3→4 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −11→14 |
Tmin = 0.946, Tmax = 1.000 | l = −32→32 |
4863 measured reflections |
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(Fo2) + (0.064P)2 + 0.1354P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2384 reflections | Δρmax = 0.14 e Å−3 |
191 parameters | Δρmin = −0.22 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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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