3-Acetyl-7-[2-(morpholin-4-yl)eth­oxy]chromen-2-one

Wang, J.; Zhu, Y.; Wang, H.; Yang, M.

doi:10.1107/S2414314618013275

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181327

https://doi.org/10.1107/S2414314618013275

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3-Acetyl-7-[2-(morpholin-4-yl)ethoxy]chromen-2-one

Junjun Wang,^a Yin Zhu,^a Haiyan Wang ^b and Mingdi Yang ^c,^d ^*

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 August 2018; accepted 18 September 2018; online 21 September 2018)

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.

Figure 1
The molecular structure of title compound, showing displacement ellipsoids drawn at the 30% probability level.

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).

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 2
The crystal packing of the title compound. The weak C—H⋯O hydrogen bonds are shown as yellow and turquoise dashed lines, and the weak π–π stacking contacts are drawn as red dashed lines. H atoms not involved in this network have been omitted.

Figure 3
The sheets generated by C18—H18B⋯O1 (purple dashed lines) interactions. H atoms not involved in directional interactions have been omitted.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₉NO₅
M_r	317.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.4620 (14), 16.243 (3), 11.477 (2)
β (°)	93.091 (2)
V (Å³)	1575.2 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	11443, 2916, 2427
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.03
No. of reflections	2916
No. of parameters	209
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.30
Computer programs: SMART and SAINT (Bruker, 2004 ) and SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1860342

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013275/hb4255sup1.cif

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

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: 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).

3-Acetyl-7-[2-(morpholin-4-yl)ethoxy]chromen-2-one top

Crystal data top

C₁₇H₁₉NO₅	F(000) = 672
M_r = 317.33	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	2427 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.5°, θ_min = 2.2°
ω scans	h = −10→10
11443 measured reflections	k = −19→19
2916 independent reflections	l = −13→12

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)] = 0.043	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(F_o²) + (0.0681P)² + 0.2289P] where P = (F_o² + 2F_c²)/3
2916 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.30 e Å⁻³

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.

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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