5-Hy­droxy-2-phenyl-7-(prop-2-yn-1-yl­oxy)-4H-chromen-4-one

Yang, F.; Li, Y.; Zhou, S.-J.

doi:10.1107/S2414314617004904

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170490

https://doi.org/10.1107/S2414314617004904

Open

access

5-Hydroxy-2-phenyl-7-(prop-2-yn-1-yloxy)-4H-chromen-4-one

Fan Yang,^a ‡ Yang Li ^a ‡ and Shu-Jing Zhou ^a ^*

^aCollege of Pharmacy, Jiamusi University, Jiamusi 154007, People's Republic of China
^*Correspondence e-mail: sjzhou_jmsu@163.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 23 March 2017; accepted 29 March 2017; online 7 April 2017)

In the title compound, C₁₈H₁₂O₄, the essentially planar chromenone ring system [the maximum deviation = 0.016 (2) Å] is nearly co-planar with the phenyl ring [dihedral angle = 3.85 (8)°]. An intramolecular O—H⋯O hydrogen bond occurs. In the crystal, weak C—H⋯O hydrogen bonds and π–π stacking interactions link the molecules into a three-dimensional supramolecular network.

Keywords: chrysin; crystal structure; alkynylation; chromenone.

CCDC reference: 1540979

Structure description

Chrysin (5,7-dihydroxy-2-phenyl-4H-chromen-4-one) is usually extracted from the passion flower and from honeycomb (Sun et al., 2012 ). It has the characteristics of flavonoids (Wang et al., 2014 ). Chrysin has been confirmed to possess pharmacological effects including anti-diarrhoeal, anti-carcinogenic and anti-inflammatory activities (Yang et al., 2014 ; Ronnekleiv-Kelly et al., 2016 ; Rauf et al., 2015 ). Thus, the modification of chrysin is of interest in flavonoid research.

The title compound is similar to its chrysin precursor, which contains three aromatic ring moieties, except for the replacement of hydrogen by an alkynyl group (Fig. 1). The carbonyl C=O bond length is 1.263 (2) Å, while the other C—O bonds are in the range 1.357 (2) to 1.433 (2) Å. The C17—C18 bond length is 1.165 (3) Å, indicating that the alkynyl group has successfully replaced the hydroxy hydrogen atom of the chrysin precursor. The essentially planar chromenone ring system [maximum deviation = 0.016 (2) Å] is nearly co-planar with the phenyl ring [dihedral angle = 3.85 (8)°]. An intramolecular O1—H1A⋯O2 hydrogen bond occurs (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82	1.85	2.584 (2)	148
C3—H3⋯O2ⁱ	0.93	2.48	3.408 (2)	177
C18—H18⋯O2ⁱⁱ	0.93	2.45	3.330 (3)	157
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound. The dashed line indicates the intramolecular hydrogen bond.

In the crystal, weak C—H⋯O hydrogen bonds (Table 1) and π–π interactions [centroid–centroid distances Cg1⋯Cg3(1 − x, 1 − y, 1 − z) = 3.6071 (12) Å and Cg2⋯Cg3(1 − x, 1 − y, 1 − z) = 3.8933 (12) Å; Cg1, Cg2 and Cg3 are the centroids of the O1/C5–C9, C1–C6 and C10–C15 rings, respectively] link the molecules into a three-dimensional supramolecular network.

A search of the Cambridge Structural Database (Groom et al., 2016 ) revealed the structure of a related compound, 5,7-dihydroxy-3,6-dimethoxy-2-(4-methoxyphenyl)-4H-chromen-4-one monohydrate (Mohammad et al., 2010 ), in which the 4-hydroxyl group of chrysin is replaced by a 3-bromopropyne group.

Synthesis and crystallization

A mixture of chrysin (5 mmol, 1.23 g) and K₂CO₃ (10 mmol, 1.38 g) in acetone (20 ml) stirred at 353 K until the solids were dissolved completely. Then 3-bromo-1-propyne (7.5 mmol, 0.89 g) was added dropwise to the above solution. The mixture was stirred under reflux for 6 h. Colourless bipyramidal crystals were obtained from an acetone solution after 3 d by slow evaporation of the solvent at room temperature.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₂O₄
M_r	292
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.2074 (10), 13.1851 (15), 14.848 (2)
β (°)	102.505 (14)
V (Å³)	1377.5 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.1 × 0.08 × 0.06

Data collection
Diffractometer	Agilent New Gemini, Dual, Cu at zero, EosS2
Absorption correction	Multi-scan (SCALE3 ABSPACK in CrysAlis PRO; Agilent, 2015 )
T_min, T_max	0.992, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8328, 2715, 1659
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.111, 0.98
No. of reflections	2715
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17
Computer programs: CrysAlis PRO (Agilent, 2015), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and DIAMOND (Brandenburg & Berndt, 1999 ).

Structural data

CCDC reference: 1540979

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617004904/xu4026sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004904/xu4026Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617004904/xu4026Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2015); cell refinement: CrysAlis PRO (Agilent, 2015); data reduction: CrysAlis PRO (Agilent, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

5-Hydroxy-2-phenyl-7-(prop-2-yn-1-yloxy)-4H-chromen-4-one top

Crystal data top

C₁₈H₁₂O₄	F(000) = 608
M_r = 292	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1686 reflections
a = 7.2074 (10) Å	θ = 3.8–26.5°
b = 13.1851 (15) Å	µ = 0.10 mm⁻¹
c = 14.848 (2) Å	T = 295 K
β = 102.505 (14)°	Bipyramid, colorless
V = 1377.5 (3) Å³	0.1 × 0.08 × 0.06 mm
Z = 4

Data collection top

Agilent New Gemini, Dual, Cu at zero, EosS2 diffractometer	2715 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1659 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 16.1280 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scan	h = −8→6
Absorption correction: multi-scan (SCALE3 ABSPACK in CrysAlisPro; Agilent, 2015)	k = −16→15
T_min = 0.992, T_max = 1.000	l = −18→18
8328 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0425P)²] where P = (F_o² + 2F_c²)/3
2715 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Special details top

Experimental. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

H atoms were placed in calculated positions and refined in riding mode, U_iso(H) = 1.5U_eq(O) for the hydroxyl-H atom and 1.2_eq(C) for the others.

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

	x	y	z	U_iso*/U_eq
C1	0.6978 (3)	0.75602 (14)	0.64191 (13)	0.0385 (5)
H1	0.8083	0.7546	0.6192	0.046*
C2	0.6296 (3)	0.84539 (14)	0.67119 (12)	0.0373 (5)
C3	0.4655 (3)	0.84843 (14)	0.70599 (12)	0.0392 (5)
H3	0.4242	0.9095	0.7262	0.047*
C4	0.3653 (3)	0.76160 (14)	0.71045 (13)	0.0374 (5)
C5	0.4284 (3)	0.66764 (13)	0.68123 (12)	0.0333 (5)
C6	0.5947 (3)	0.66882 (13)	0.64792 (12)	0.0346 (5)
C7	0.3272 (3)	0.57441 (14)	0.68426 (12)	0.0374 (5)
C8	0.4111 (3)	0.48605 (14)	0.65360 (12)	0.0387 (5)
H8	0.3515	0.4237	0.6549	0.046*
C9	0.5730 (3)	0.49037 (13)	0.62307 (12)	0.0342 (5)
C10	0.6740 (3)	0.40468 (14)	0.59232 (12)	0.0352 (5)
C11	0.5985 (3)	0.30727 (15)	0.58787 (15)	0.0517 (6)
H11	0.4826	0.2964	0.6043	0.062*
C12	0.6929 (3)	0.22674 (17)	0.55946 (16)	0.0610 (7)
H12	0.6401	0.1621	0.5567	0.073*
C13	0.8633 (3)	0.24088 (16)	0.53535 (15)	0.0554 (6)
H13	0.9267	0.1860	0.5165	0.066*
C14	0.9411 (3)	0.33648 (16)	0.53894 (14)	0.0535 (6)
H14	1.0567	0.3464	0.5221	0.064*
C15	0.8473 (3)	0.41805 (15)	0.56767 (13)	0.0448 (5)
H15	0.9011	0.4824	0.5704	0.054*
C16	0.8636 (3)	0.94818 (16)	0.62002 (14)	0.0479 (5)
H16A	0.9563	0.8945	0.6379	0.057*
H16B	0.9278	1.0126	0.6354	0.057*
C17	0.7874 (3)	0.94335 (15)	0.52047 (16)	0.0454 (5)
C18	0.7235 (3)	0.94124 (17)	0.44139 (19)	0.0636 (7)
H18	0.6726	0.9396	0.3783	0.076*
O1	0.20205 (19)	0.76456 (10)	0.74190 (10)	0.0533 (4)
H1A	0.1573	0.7073	0.7408	0.080*
O2	0.17536 (19)	0.57122 (10)	0.71351 (10)	0.0512 (4)
O3	0.66511 (17)	0.58021 (9)	0.61863 (9)	0.0401 (4)
O4	0.71629 (19)	0.93772 (9)	0.67054 (9)	0.0475 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0406 (11)	0.0334 (11)	0.0450 (12)	−0.0040 (9)	0.0172 (10)	−0.0026 (9)
C2	0.0455 (12)	0.0302 (11)	0.0353 (11)	−0.0048 (9)	0.0068 (10)	−0.0017 (8)
C3	0.0479 (12)	0.0327 (11)	0.0399 (11)	0.0037 (10)	0.0158 (10)	−0.0032 (9)
C4	0.0389 (11)	0.0386 (12)	0.0367 (11)	0.0045 (10)	0.0125 (10)	0.0030 (9)
C5	0.0365 (11)	0.0331 (11)	0.0307 (10)	0.0002 (9)	0.0084 (9)	0.0026 (8)
C6	0.0413 (11)	0.0281 (11)	0.0349 (10)	0.0037 (9)	0.0095 (9)	−0.0014 (8)
C7	0.0383 (12)	0.0379 (12)	0.0370 (11)	0.0020 (10)	0.0102 (9)	0.0074 (9)
C8	0.0448 (12)	0.0287 (11)	0.0431 (11)	−0.0023 (9)	0.0105 (10)	0.0010 (9)
C9	0.0405 (11)	0.0288 (11)	0.0328 (10)	0.0003 (9)	0.0069 (9)	0.0037 (8)
C10	0.0403 (11)	0.0313 (11)	0.0324 (10)	0.0044 (9)	0.0046 (9)	0.0020 (8)
C11	0.0508 (13)	0.0354 (13)	0.0715 (15)	0.0001 (11)	0.0191 (12)	−0.0036 (11)
C12	0.0649 (16)	0.0341 (13)	0.0852 (18)	0.0014 (12)	0.0191 (14)	−0.0098 (12)
C13	0.0633 (15)	0.0417 (14)	0.0615 (15)	0.0150 (12)	0.0145 (13)	−0.0073 (11)
C14	0.0526 (14)	0.0535 (15)	0.0584 (14)	0.0083 (12)	0.0211 (12)	−0.0032 (11)
C15	0.0520 (13)	0.0349 (12)	0.0492 (12)	0.0008 (10)	0.0147 (11)	−0.0021 (9)
C16	0.0514 (13)	0.0402 (12)	0.0538 (13)	−0.0102 (10)	0.0151 (11)	0.0003 (10)
C17	0.0468 (13)	0.0370 (12)	0.0563 (15)	0.0000 (10)	0.0198 (12)	0.0039 (10)
C18	0.0658 (16)	0.0688 (18)	0.0575 (16)	−0.0028 (13)	0.0162 (14)	0.0067 (13)
O1	0.0519 (9)	0.0429 (8)	0.0748 (10)	0.0028 (7)	0.0349 (8)	−0.0012 (7)
O2	0.0487 (9)	0.0451 (9)	0.0679 (10)	−0.0033 (7)	0.0308 (8)	0.0017 (7)
O3	0.0431 (8)	0.0298 (8)	0.0517 (8)	−0.0002 (6)	0.0198 (7)	−0.0020 (6)
O4	0.0603 (9)	0.0340 (8)	0.0538 (9)	−0.0106 (7)	0.0242 (7)	−0.0084 (6)

Geometric parameters (Å, º) top

C1—C6	1.382 (2)	C10—C15	1.387 (3)
C1—C2	1.383 (2)	C10—C11	1.391 (3)
C1—H1	0.9300	C11—C12	1.376 (3)
C2—O4	1.369 (2)	C11—H11	0.9300
C2—C3	1.390 (2)	C12—C13	1.365 (3)
C3—C4	1.363 (2)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.376 (3)
C4—O1	1.357 (2)	C13—H13	0.9300
C4—C5	1.419 (2)	C14—C15	1.386 (3)
C5—C6	1.392 (2)	C14—H14	0.9300
C5—C7	1.435 (2)	C15—H15	0.9300
C6—O3	1.381 (2)	C16—O4	1.433 (2)
C7—O2	1.263 (2)	C16—C17	1.463 (3)
C7—C8	1.432 (2)	C16—H16A	0.9700
C8—C9	1.341 (2)	C16—H16B	0.9700
C8—H8	0.9300	C17—C18	1.165 (3)
C9—O3	1.367 (2)	C18—H18	0.9300
C9—C10	1.469 (2)	O1—H1A	0.8200

C6—C1—C2	117.11 (18)	C15—C10—C9	121.30 (17)
C6—C1—H1	121.4	C11—C10—C9	120.63 (18)
C2—C1—H1	121.4	C12—C11—C10	120.8 (2)
O4—C2—C1	124.15 (18)	C12—C11—H11	119.6
O4—C2—C3	113.79 (16)	C10—C11—H11	119.6
C1—C2—C3	122.05 (18)	C13—C12—C11	120.5 (2)
C4—C3—C2	119.73 (18)	C13—C12—H12	119.7
C4—C3—H3	120.1	C11—C12—H12	119.7
C2—C3—H3	120.1	C12—C13—C14	119.8 (2)
O1—C4—C3	120.01 (17)	C12—C13—H13	120.1
O1—C4—C5	119.27 (17)	C14—C13—H13	120.1
C3—C4—C5	120.71 (18)	C13—C14—C15	120.1 (2)
C6—C5—C4	117.12 (17)	C13—C14—H14	120.0
C6—C5—C7	120.20 (17)	C15—C14—H14	120.0
C4—C5—C7	122.67 (17)	C14—C15—C10	120.65 (19)
O3—C6—C1	116.35 (17)	C14—C15—H15	119.7
O3—C6—C5	120.38 (16)	C10—C15—H15	119.7
C1—C6—C5	123.27 (17)	O4—C16—C17	111.47 (16)
O2—C7—C8	122.65 (17)	O4—C16—H16A	109.3
O2—C7—C5	121.57 (17)	C17—C16—H16A	109.3
C8—C7—C5	115.78 (17)	O4—C16—H16B	109.3
C9—C8—C7	122.08 (18)	C17—C16—H16B	109.3
C9—C8—H8	119.0	H16A—C16—H16B	108.0
C7—C8—H8	119.0	C18—C17—C16	178.4 (2)
C8—C9—O3	121.36 (17)	C17—C18—H18	180.0
C8—C9—C10	126.74 (18)	C4—O1—H1A	109.5
O3—C9—C10	111.89 (16)	C9—O3—C6	120.17 (15)
C15—C10—C11	118.07 (18)	C2—O4—C16	118.70 (15)

C6—C1—C2—O4	179.29 (17)	C7—C8—C9—O3	−0.8 (3)
C6—C1—C2—C3	0.5 (3)	C7—C8—C9—C10	178.32 (16)
O4—C2—C3—C4	179.98 (17)	C8—C9—C10—C15	−175.85 (18)
C1—C2—C3—C4	−1.1 (3)	O3—C9—C10—C15	3.4 (2)
C2—C3—C4—O1	−178.12 (16)	C8—C9—C10—C11	3.6 (3)
C2—C3—C4—C5	1.0 (3)	O3—C9—C10—C11	−177.13 (17)
O1—C4—C5—C6	178.83 (16)	C15—C10—C11—C12	−0.2 (3)
C3—C4—C5—C6	−0.3 (3)	C9—C10—C11—C12	−179.75 (18)
O1—C4—C5—C7	−0.6 (3)	C10—C11—C12—C13	0.2 (3)
C3—C4—C5—C7	−179.72 (18)	C11—C12—C13—C14	−0.4 (3)
C2—C1—C6—O3	−179.84 (15)	C12—C13—C14—C15	0.5 (3)
C2—C1—C6—C5	0.2 (3)	C13—C14—C15—C10	−0.5 (3)
C4—C5—C6—O3	179.72 (15)	C11—C10—C15—C14	0.4 (3)
C7—C5—C6—O3	−0.8 (3)	C9—C10—C15—C14	179.90 (17)
C4—C5—C6—C1	−0.3 (3)	C8—C9—O3—C6	1.6 (3)
C7—C5—C6—C1	179.11 (17)	C10—C9—O3—C6	−177.70 (14)
C6—C5—C7—O2	−179.50 (17)	C1—C6—O3—C9	179.34 (16)
C4—C5—C7—O2	−0.1 (3)	C5—C6—O3—C9	−0.7 (2)
C6—C5—C7—C8	1.5 (3)	C1—C2—O4—C16	13.3 (3)
C4—C5—C7—C8	−179.10 (16)	C3—C2—O4—C16	−167.81 (15)
O2—C7—C8—C9	−179.68 (17)	C17—C16—O4—C2	70.0 (2)
C5—C7—C8—C9	−0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	1.85	2.584 (2)	148
C3—H3···O2ⁱ	0.93	2.48	3.408 (2)	177
C18—H18···O2ⁱⁱ	0.93	2.45	3.330 (3)	157

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

Footnotes

‡These authors contributed equally to this work.

Acknowledgements

The data collection was performed at the College of Phamacy, Jiamusi University.

Funding information

Funding for this research was provided by: Graduate Innovation Foundation of Jiamusi University (award No. YZ2016_005).

References

Agilent (2015). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Brandenburg, K. & Berndt, M. (1999). Crystal Impact GbR, Bonn, Germany. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mohammad, A., Anis, I., McKee, V., Frese, J. W. A. & Shah, M. R. (2010). Acta Cryst. E66, o2716–o2717. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rauf, A., Khan, R., Raza, M., Khan, H., Pervez, S., De Feo, V., Maione, F. & Mascolo, N. (2015). Fitoterapia, 103, 129–135. Web of Science CrossRef CAS PubMed Google Scholar
Ronnekleiv-Kelly, S. M., Nukaya, M., Díaz-Díaz, C. J., Megna, B. W., Carney, P. R., Geiger, P. G. & Kennedy, G. D. (2016). Cancer Lett. 370, 91–99. Web of Science CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, L.-P., Chen, A.-L., Hung, H.-C., Chien, Y.-H., Huang, J.-S., Huang, C.-Y., Chen, Y.-W. & Chen, C.-N. (2012). J. Agric. Food Chem. 60, 11748–11758. Web of Science CrossRef CAS PubMed Google Scholar
Wang, J., Zhang, T., Du, J., Cui, S., Yang, F. & Jin, Q. (2014). PLoS One, 9, e89668. Web of Science CrossRef PubMed Google Scholar
Yang, B., Huang, J., Xiang, T., Yin, X., Luo, X., Huang, J., Luo, F., Li, H., Li, H. & Ren, G. (2014). J. Appl. Toxicol. 34, 105–112. Web of Science CrossRef PubMed Google Scholar