organic compounds
3-Acetyl-7-[2-(morpholin-4-yl)ethoxy]chromen-2-one
aDepartment of Chemistry, Anhui University, Hefei 230601, People's Republic of China, bInstitute of Physical Science and Information Technology, Anhui University, Hefei 230601, People's Republic of China, cCollege of Chemistry and Chemical Engineering, Anhui University, and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Hefei, 230601, People's Republic of China, and dSchool of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, People's Republic of China
*Correspondence e-mail: youthmd98@163.com
In the title compound, C17H19NO5, the morpholine ring adopts a chair conformation with the exocyclic N—C bond in an equatorial orientation. In the crystal, the molecules are linked by C—H⋯O and weak aromatic π–π stacking interactions, thereby generating a layered structure.
Keywords: crystal structure; coumarin; hydrogen bonds.
CCDC reference: 1860342
Structure description
Coumarin derivatives display many biological activities, such as antiviral, anti-HIV, anti-neoplasm and are used as fluorescent dyes (Bai & Dong, 2016). We have reported good luminescent properties and excellent cell biocompatibility (Jiao et al., 2018) in coumarin derivatives. In the title compound, a morpholine ring, a typical lysosome-targeting moiety (Li et al., 2018), is linked to a 7-hydroxy-3-acetylcoumarin unit via a flexible-chain (–O–CH2–).
The molecular structure of the title compound is shown in Fig. 1. The coumarin ring system is essentially planar with a dihedral angle of 0.24 (5)° between the fused rings. The morpholine ring adopts a chair conformation with the exocyclic N—C bond in an equatorial orientation.
In the crystal, a one-dimensional chain-like structure is consolidated by C17—H17A⋯O4 and C17—H17B⋯O1 hydrogen bonds (Table 1) and weak aromatic π–π stacking [centroid–centroid separation = 3.6422 (10) Å] (Fig. 2). The chains are connected through very weak C18—H18B⋯O1 interactions (Fig. 3).
Synthesis and crystallization
To a solution of 3-acetyl-7-hydroxy-chromen-2-one (0.50 g, 2.47 mmol) in acetonitrile (15 ml) were added potassium carbonate (1.02 g, 7.41 mmol) and 4-(2-chloro-ethyl)-morpholine (0.55 g, 2.97 mmol). The mixture was refluxed for 6 h. After completion of the reaction, the solvent was evaporated under reduced pressure. The crude compound was purified on a silica gel column (petroleum ether: ethyl acetate = 1:1 v/v) giving a yellow solid (0.65 g, 83%) and yellow block-shaped crystals were recrystallized from a petroleum ether–ethyl acetate solvent mixture.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1860342
https://doi.org/10.1107/S2414314618013275/hb4255sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013275/hb4255Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618013275/hb4255Isup3.cml
Data collection: SMART (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C17H19NO5 | F(000) = 672 |
Mr = 317.33 | Dx = 1.338 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4620 (14) Å | Cell parameters from 5468 reflections |
b = 16.243 (3) Å | θ = 2.5–27.1° |
c = 11.477 (2) Å | µ = 0.10 mm−1 |
β = 93.091 (2)° | T = 296 K |
V = 1575.2 (5) Å3 | Block, yellow |
Z = 4 | 0.2 × 0.2 × 0.2 mm |
Bruker SMART CCD diffractometer | 2427 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 25.5°, θmin = 2.2° |
ω scans | h = −10→10 |
11443 measured reflections | k = −19→19 |
2916 independent reflections | l = −13→12 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.2289P] where P = (Fo2 + 2Fc2)/3 |
2916 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.15 e Å−3 |
1 restraint | Δρmin = −0.30 e Å−3 |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O3 | 0.78260 (11) | 1.00250 (6) | 1.05321 (8) | 0.0496 (3) | |
C2 | 0.62360 (15) | 1.09671 (8) | 1.16169 (12) | 0.0462 (3) | |
C3 | 0.71768 (15) | 1.03229 (8) | 0.94956 (11) | 0.0420 (3) | |
C4 | 0.60334 (15) | 1.09440 (8) | 0.94933 (12) | 0.0446 (3) | |
O6 | 0.73725 (13) | 0.99507 (6) | 0.63799 (8) | 0.0571 (3) | |
C6 | 0.55908 (16) | 1.12462 (8) | 1.05895 (12) | 0.0476 (3) | |
H6 | 0.4822 | 1.1655 | 1.0601 | 0.057* | |
C7 | 0.74346 (16) | 1.03202 (9) | 1.16160 (12) | 0.0479 (3) | |
C8 | 0.76948 (15) | 0.99760 (8) | 0.84890 (11) | 0.0449 (3) | |
H8 | 0.8468 | 0.9568 | 0.8518 | 0.054* | |
C9 | 0.70248 (16) | 1.02551 (8) | 0.74304 (12) | 0.0466 (3) | |
O1 | 0.81172 (13) | 0.99990 (7) | 1.24383 (9) | 0.0643 (3) | |
N1 | 0.94110 (13) | 0.82784 (7) | 0.49385 (10) | 0.0480 (3) | |
O4 | 0.46331 (15) | 1.18477 (7) | 1.26493 (11) | 0.0730 (4) | |
O2 | 1.02784 (15) | 0.67139 (7) | 0.40415 (11) | 0.0727 (4) | |
C14 | 0.54063 (18) | 1.12231 (9) | 0.84065 (13) | 0.0535 (4) | |
H14 | 0.4653 | 1.1640 | 0.8375 | 0.064* | |
C15 | 0.56956 (17) | 1.13410 (9) | 1.27201 (13) | 0.0541 (4) | |
C16 | 0.58914 (18) | 1.08882 (9) | 0.73952 (13) | 0.0558 (4) | |
H16 | 0.5470 | 1.1080 | 0.6680 | 0.067* | |
C17 | 0.84068 (16) | 0.92492 (9) | 0.63441 (12) | 0.0508 (3) | |
H17A | 0.8035 | 0.8809 | 0.6830 | 0.061* | |
H17B | 0.9473 | 0.9397 | 0.6619 | 0.061* | |
C18 | 0.83778 (18) | 0.89834 (10) | 0.50911 (12) | 0.0559 (4) | |
H18A | 0.7304 | 0.8840 | 0.4830 | 0.067* | |
H18B | 0.8716 | 0.9437 | 0.4615 | 0.067* | |
C19 | 0.8765 (2) | 0.75130 (9) | 0.53613 (15) | 0.0635 (4) | |
H19A | 0.7783 | 0.7386 | 0.4923 | 0.076* | |
H19B | 0.8538 | 0.7571 | 0.6177 | 0.076* | |
C20 | 0.6433 (2) | 1.11053 (14) | 1.38787 (15) | 0.0812 (6) | |
H20A | 0.5949 | 1.1412 | 1.4479 | 0.122* | |
H20B | 0.7545 | 1.1225 | 1.3899 | 0.122* | |
H20C | 0.6281 | 1.0527 | 1.4005 | 0.122* | |
C21 | 0.9933 (2) | 0.68219 (10) | 0.52273 (17) | 0.0733 (5) | |
H21A | 1.0902 | 0.6944 | 0.5685 | 0.088* | |
H21B | 0.9498 | 0.6315 | 0.5523 | 0.088* | |
C22 | 0.9760 (2) | 0.81673 (11) | 0.37205 (15) | 0.0721 (5) | |
H22A | 1.0234 | 0.8665 | 0.3429 | 0.087* | |
H22B | 0.8787 | 0.8063 | 0.3258 | 0.087* | |
C23 | 1.0882 (2) | 0.74535 (11) | 0.36046 (16) | 0.0733 (5) | |
H23A | 1.1090 | 0.7380 | 0.2788 | 0.088* | |
H23B | 1.1879 | 0.7580 | 0.4023 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0526 (5) | 0.0503 (6) | 0.0454 (5) | 0.0114 (4) | −0.0014 (4) | −0.0040 (4) |
C2 | 0.0437 (7) | 0.0437 (7) | 0.0516 (7) | −0.0062 (5) | 0.0063 (5) | −0.0074 (6) |
C3 | 0.0411 (7) | 0.0383 (7) | 0.0464 (7) | 0.0002 (5) | −0.0004 (5) | −0.0005 (5) |
C4 | 0.0433 (7) | 0.0388 (7) | 0.0516 (8) | 0.0021 (5) | 0.0035 (6) | −0.0021 (6) |
O6 | 0.0705 (7) | 0.0564 (6) | 0.0450 (5) | 0.0185 (5) | 0.0066 (5) | −0.0004 (4) |
C6 | 0.0440 (7) | 0.0402 (7) | 0.0591 (7) | 0.0026 (5) | 0.0070 (6) | −0.0055 (6) |
C7 | 0.0466 (7) | 0.0495 (8) | 0.0475 (8) | −0.0036 (6) | 0.0022 (6) | −0.0048 (6) |
C8 | 0.0433 (7) | 0.0404 (7) | 0.0511 (8) | 0.0062 (5) | 0.0025 (6) | −0.0026 (6) |
C9 | 0.0503 (7) | 0.0435 (7) | 0.0464 (7) | 0.0011 (6) | 0.0063 (6) | −0.0006 (6) |
O1 | 0.0696 (7) | 0.0736 (7) | 0.0489 (6) | 0.0128 (6) | −0.0047 (5) | 0.0008 (5) |
N1 | 0.0522 (6) | 0.0453 (6) | 0.0472 (6) | 0.0026 (5) | 0.0087 (5) | −0.0012 (5) |
O4 | 0.0785 (8) | 0.0678 (7) | 0.0741 (8) | 0.0116 (6) | 0.0158 (6) | −0.0191 (6) |
O2 | 0.0882 (8) | 0.0531 (7) | 0.0777 (8) | 0.0008 (6) | 0.0135 (6) | −0.0180 (5) |
C14 | 0.0559 (8) | 0.0464 (7) | 0.0584 (8) | 0.0143 (6) | 0.0045 (6) | 0.0032 (6) |
C15 | 0.0514 (8) | 0.0526 (8) | 0.0593 (9) | −0.0098 (7) | 0.0114 (6) | −0.0127 (7) |
C16 | 0.0636 (9) | 0.0535 (8) | 0.0503 (8) | 0.0139 (7) | 0.0017 (6) | 0.0072 (6) |
C17 | 0.0499 (8) | 0.0516 (8) | 0.0510 (8) | 0.0085 (6) | 0.0041 (6) | −0.0037 (6) |
C18 | 0.0613 (9) | 0.0596 (9) | 0.0471 (8) | 0.0132 (7) | 0.0070 (6) | 0.0000 (7) |
C19 | 0.0688 (10) | 0.0562 (9) | 0.0672 (10) | −0.0113 (7) | 0.0190 (8) | −0.0057 (7) |
C20 | 0.0825 (12) | 0.1098 (15) | 0.0519 (9) | 0.0095 (11) | 0.0090 (8) | −0.0199 (10) |
C21 | 0.0969 (13) | 0.0463 (9) | 0.0784 (12) | −0.0018 (8) | 0.0191 (10) | −0.0012 (8) |
C22 | 0.0938 (13) | 0.0686 (10) | 0.0565 (9) | 0.0241 (9) | 0.0272 (8) | 0.0052 (8) |
C23 | 0.0868 (12) | 0.0658 (10) | 0.0699 (10) | 0.0166 (9) | 0.0282 (9) | −0.0022 (8) |
O3—C3 | 1.3714 (15) | C14—C16 | 1.365 (2) |
O3—C7 | 1.3898 (16) | C14—H14 | 0.9300 |
C2—C6 | 1.351 (2) | C15—C20 | 1.488 (2) |
C2—C7 | 1.4603 (19) | C16—H16 | 0.9300 |
C2—C15 | 1.4979 (19) | C17—C18 | 1.5003 (19) |
C3—C8 | 1.3780 (18) | C17—H17A | 0.9700 |
C3—C4 | 1.3978 (18) | C17—H17B | 0.9700 |
C4—C14 | 1.404 (2) | C18—H18A | 0.9700 |
C4—C6 | 1.4195 (19) | C18—H18B | 0.9700 |
O6—C9 | 1.3502 (16) | C19—C21 | 1.509 (2) |
O6—C17 | 1.4388 (16) | C19—H19A | 0.9700 |
C6—H6 | 0.9300 | C19—H19B | 0.9700 |
C7—O1 | 1.1991 (17) | C20—H20A | 0.9600 |
C8—C9 | 1.3888 (19) | C20—H20B | 0.9600 |
C8—H8 | 0.9300 | C20—H20C | 0.9600 |
C9—C16 | 1.4053 (19) | C21—H21A | 0.9700 |
N1—C19 | 1.4519 (19) | C21—H21B | 0.9700 |
N1—C22 | 1.4555 (19) | C22—C23 | 1.509 (2) |
N1—C18 | 1.4571 (17) | C22—H22A | 0.9700 |
O4—C15 | 1.2184 (18) | C22—H22B | 0.9700 |
O2—C23 | 1.408 (2) | C23—H23A | 0.9700 |
O2—C21 | 1.418 (2) | C23—H23B | 0.9700 |
C3—O3—C7 | 123.44 (11) | O6—C17—H17B | 110.5 |
C6—C2—C7 | 119.27 (12) | C18—C17—H17B | 110.5 |
C6—C2—C15 | 118.31 (13) | H17A—C17—H17B | 108.7 |
C7—C2—C15 | 122.42 (13) | N1—C18—C17 | 111.25 (11) |
O3—C3—C8 | 116.89 (11) | N1—C18—H18A | 109.4 |
O3—C3—C4 | 120.08 (11) | C17—C18—H18A | 109.4 |
C8—C3—C4 | 123.03 (12) | N1—C18—H18B | 109.4 |
C3—C4—C14 | 117.59 (12) | C17—C18—H18B | 109.4 |
C3—C4—C6 | 117.62 (12) | H18A—C18—H18B | 108.0 |
C14—C4—C6 | 124.79 (12) | N1—C19—C21 | 110.06 (13) |
C9—O6—C17 | 118.54 (11) | N1—C19—H19A | 109.6 |
C2—C6—C4 | 122.96 (13) | C21—C19—H19A | 109.6 |
C2—C6—H6 | 118.5 | N1—C19—H19B | 109.6 |
C4—C6—H6 | 118.5 | C21—C19—H19B | 109.6 |
O1—C7—O3 | 115.23 (12) | H19A—C19—H19B | 108.2 |
O1—C7—C2 | 128.14 (13) | C15—C20—H20A | 109.5 |
O3—C7—C2 | 116.62 (12) | C15—C20—H20B | 109.5 |
C3—C8—C9 | 117.81 (12) | H20A—C20—H20B | 109.5 |
C3—C8—H8 | 121.1 | C15—C20—H20C | 109.5 |
C9—C8—H8 | 121.1 | H20A—C20—H20C | 109.5 |
O6—C9—C8 | 124.29 (12) | H20B—C20—H20C | 109.5 |
O6—C9—C16 | 115.06 (12) | O2—C21—C19 | 111.09 (15) |
C8—C9—C16 | 120.65 (12) | O2—C21—H21A | 109.4 |
C19—N1—C22 | 108.32 (12) | C19—C21—H21A | 109.4 |
C19—N1—C18 | 113.20 (11) | O2—C21—H21B | 109.4 |
C22—N1—C18 | 111.54 (11) | C19—C21—H21B | 109.4 |
C23—O2—C21 | 109.50 (12) | H21A—C21—H21B | 108.0 |
C16—C14—C4 | 120.67 (13) | N1—C22—C23 | 109.95 (14) |
C16—C14—H14 | 119.7 | N1—C22—H22A | 109.7 |
C4—C14—H14 | 119.7 | C23—C22—H22A | 109.7 |
O4—C15—C20 | 120.38 (14) | N1—C22—H22B | 109.7 |
O4—C15—C2 | 118.38 (14) | C23—C22—H22B | 109.7 |
C20—C15—C2 | 121.24 (14) | H22A—C22—H22B | 108.2 |
C14—C16—C9 | 120.22 (13) | O2—C23—C22 | 112.45 (14) |
C14—C16—H16 | 119.9 | O2—C23—H23A | 109.1 |
C9—C16—H16 | 119.9 | C22—C23—H23A | 109.1 |
O6—C17—C18 | 106.06 (11) | O2—C23—H23B | 109.1 |
O6—C17—H17A | 110.5 | C22—C23—H23B | 109.1 |
C18—C17—H17A | 110.5 | H23A—C23—H23B | 107.8 |
C7—O3—C3—C8 | 179.24 (11) | C3—C4—C14—C16 | 0.8 (2) |
C7—O3—C3—C4 | −1.41 (19) | C6—C4—C14—C16 | −179.21 (13) |
O3—C3—C4—C14 | −179.79 (12) | C6—C2—C15—O4 | 4.1 (2) |
C8—C3—C4—C14 | −0.5 (2) | C7—C2—C15—O4 | −176.30 (13) |
O3—C3—C4—C6 | 0.20 (19) | C6—C2—C15—C20 | −175.74 (14) |
C8—C3—C4—C6 | 179.51 (12) | C7—C2—C15—C20 | 3.8 (2) |
C7—C2—C6—C4 | −0.6 (2) | C4—C14—C16—C9 | 0.2 (2) |
C15—C2—C6—C4 | 179.04 (11) | O6—C9—C16—C14 | 177.72 (14) |
C3—C4—C6—C2 | 0.8 (2) | C8—C9—C16—C14 | −1.6 (2) |
C14—C4—C6—C2 | −179.25 (13) | C9—O6—C17—C18 | 171.99 (12) |
C3—O3—C7—O1 | −179.41 (12) | C19—N1—C18—C17 | 74.45 (16) |
C3—O3—C7—C2 | 1.58 (18) | C22—N1—C18—C17 | −163.10 (14) |
C6—C2—C7—O1 | −179.44 (14) | O6—C17—C18—N1 | 179.07 (11) |
C15—C2—C7—O1 | 1.0 (2) | C22—N1—C19—C21 | 58.51 (18) |
C6—C2—C7—O3 | −0.59 (18) | C18—N1—C19—C21 | −177.26 (13) |
C15—C2—C7—O3 | 179.84 (11) | C23—O2—C21—C19 | 57.98 (19) |
O3—C3—C8—C9 | 178.49 (11) | N1—C19—C21—O2 | −59.95 (19) |
C4—C3—C8—C9 | −0.8 (2) | C19—N1—C22—C23 | −57.02 (18) |
C17—O6—C9—C8 | 5.1 (2) | C18—N1—C22—C23 | 177.77 (14) |
C17—O6—C9—C16 | −174.15 (12) | C21—O2—C23—C22 | −57.3 (2) |
C3—C8—C9—O6 | −177.39 (12) | N1—C22—C23—O2 | 57.8 (2) |
C3—C8—C9—C16 | 1.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O4i | 0.97 | 2.60 | 3.383 (2) | 138 |
C17—H17B···O1ii | 0.97 | 2.46 | 3.4136 (19) | 167 |
C18—H18B···O1iii | 0.97 | 2.68 | 3.459 (2) | 137 |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+2, −z+2; (iii) x, y, z−1. |
Funding information
This work was supported by the Students Innovative and Entrepreneurial Program of Anhui University (201810357273), the Natural Science Foundation of Anhui Province (1508085MB34) the Educational Commission of Anhui Province (KJ2016JD14) and the Anhui Province Postdoctoral Science Foundation (2017B159).
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