3-(4-Meth­oxy­phen­yl)-6,7-dihydro-1H-furo[3,4-c]pyran-4(3H)-one

Zhang, J.; An, Y.; Zhang, Y.; Shi, G.

doi:10.1107/S160053681204723X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3451

doi:10.1107/S160053681204723X

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3-(4-Methoxyphenyl)-6,7-dihydro-1H-furo[3,4-c]pyran-4(3H)-one

Jingyi Zhang,^a ^* Ye An,^a Yikai Zhang ^b and Guobing Shi ^a ^*

^aDepartment of Pharmacy, General Hospital of Shenyang Military Command, Shenyang 110016, People's Republic of China, and ^bDepartment of Medicinal Chemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, People's Republic of China
^*Correspondence e-mail: hu829Zh213@yahoo.com.cn, sgsgb@126.com

(Received 13 November 2012; accepted 16 November 2012; online 24 November 2012)

In the title compound, C₁₄H₁₄O₄, the dihedral angle between the hydrofuran and benzene rings is 88.41 (15)°. The hydropyran ring adopts an envelope conformation, with the O-bound methylene C atom as the flap. In the crystal, weak aromatic π–π stacking is observed [centroid–centroid separation = 3.848 (2) Å].

Related literature

For medicinal background, see: Wang et al. (2011 ).

Experimental

Crystal data

C₁₄H₁₄O₄
M_r = 246.25
Monoclinic, P 2₁ /n
a = 7.240 (3) Å
b = 8.635 (4) Å
c = 19.545 (8) Å
β = 97.352 (6)°
V = 1212.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.976, T_max = 0.981
4872 measured reflections
2127 independent reflections
1494 reflections with I > 2σ(I)
R_int = 0.104

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.227
S = 1.06
2127 reflections
164 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053681204723X/hb6991sup1.cif

Supporting information file. DOI: 10.1107/S160053681204723X/hb6991Isup2.cdx

Supporting information file. DOI: 10.1107/S160053681204723X/hb6991Isup6.cdx

Structure factors: contains datablock I. DOI: 10.1107/S160053681204723X/hb6991Isup4.hkl

checkCIF report

Related literature top

For medicinal background, see: Wang et al. (2011).

Experimental top

NaH (60% in mineral oil, 24 mmol) was added to a solution of but-2-yne-1,4-diol (2.58 g, 30 mmol) in THF (50 ml) under nitrogen, and the solution was stirred for 5 min at 20 C. Diethyl 2-(4-methoxybenzylidene)malonate (5.56 g, 20 mmol) and CuI (0.38 g, 2 mmol) were then added successively. When consumption of the starting materials was observed by TLC, the reaction mixture was added 3% HCl solution until the PH value was 7. Then the mixture was extracted with CH₂Cl₂ (30 ml × 3). The combined organic layers were dried and solids were combined. The solid (0.973 g, 3 mmol) subsequently was reacted with 20% KOH in EtOH/THF (15/15 ml) at room temperature for 6 h. Then the reaction mixture was diluted with CH₂Cl₂ (30 ml) and washed with saturated Na₂CO₃, brine and dried with MgSO4. The mixture was purified with silica gel column chromagraphy. The Trans-form compounds could be obtained. Yield: 10%. M. p.: 407 K.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A view of the unit-cell contents for the title compound.

3-(4-Methoxyphenyl)-6,7-dihydro-1H-furo[3,4-c]pyran-4(3H) -one top

Crystal data top

C₁₄H₁₄O₄	F(000) = 520
M_r = 246.25	D_x = 1.350 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 735 reflections
a = 7.240 (3) Å	θ = 2.6–24.3°
b = 8.635 (4) Å	µ = 0.10 mm⁻¹
c = 19.545 (8) Å	T = 293 K
β = 97.352 (6)°	Prism, colorless
V = 1212.0 (9) Å³	0.25 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2127 independent reflections
Radiation source: fine-focus sealed tube	1494 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.104
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→7
T_min = 0.976, T_max = 0.981	k = −10→10
4872 measured reflections	l = −23→19

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.227	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1396P)²] where P = (F_o² + 2F_c²)/3
2127 reflections	(Δ/σ)_max = 0.001
164 parameters	Δρ_max = 0.55 e Å⁻³
6 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₄O₄	V = 1212.0 (9) Å³
M_r = 246.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.240 (3) Å	µ = 0.10 mm⁻¹
b = 8.635 (4) Å	T = 293 K
c = 19.545 (8) Å	0.25 × 0.25 × 0.20 mm
β = 97.352 (6)°

Data collection top

Bruker SMART CCD diffractometer	2127 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1494 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.981	R_int = 0.104
4872 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	6 restraints
wR(F²) = 0.227	H-atom parameters constrained
S = 1.06	Δρ_max = 0.55 e Å⁻³
2127 reflections	Δρ_min = −0.31 e Å⁻³
164 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O1	0.3995 (3)	0.6361 (2)	0.04179 (10)	0.0677 (6)
O2	0.5812 (3)	0.8161 (3)	0.00885 (11)	0.0771 (7)
O3	0.9242 (3)	0.4487 (2)	0.14388 (12)	0.0777 (7)
O4	0.2905 (3)	0.5087 (3)	0.33985 (12)	0.0800 (7)
C1	0.5550 (4)	0.6850 (3)	0.04378 (13)	0.0541 (7)
C2	0.7206 (3)	0.6116 (3)	0.07879 (13)	0.0542 (7)
C3	0.7270 (3)	0.4668 (3)	0.12146 (15)	0.0569 (7)
H3	0.6841	0.3796	0.0915	0.068*
C4	1.0291 (4)	0.5583 (4)	0.1116 (2)	0.0805 (10)
H4A	1.1033	0.5076	0.0803	0.097*
H4B	1.1116	0.6153	0.1457	0.097*
C5	0.8909 (4)	0.6629 (3)	0.07366 (15)	0.0622 (8)
C6	0.9218 (4)	0.8021 (4)	0.03314 (19)	0.0838 (10)
H6A	1.0260	0.8605	0.0563	0.101*
H6B	0.9517	0.7719	−0.0120	0.101*
C7	0.7547 (6)	0.8987 (5)	0.0253 (3)	0.1143 (15)
H7A	0.7502	0.9555	0.0679	0.137*
H7B	0.7654	0.9740	−0.0108	0.137*
C8	0.6177 (3)	0.4702 (3)	0.18107 (14)	0.0525 (7)
C9	0.4688 (4)	0.3726 (3)	0.18314 (15)	0.0593 (7)
H9	0.4417	0.2997	0.1483	0.071*
C10	0.3579 (4)	0.3798 (3)	0.23563 (16)	0.0646 (8)
H10	0.2584	0.3119	0.2360	0.077*
C11	0.3952 (4)	0.4871 (3)	0.28691 (15)	0.0593 (7)
C12	0.5476 (4)	0.5848 (3)	0.28669 (16)	0.0657 (8)
H12	0.5769	0.6556	0.3223	0.079*
C13	0.6550 (4)	0.5765 (3)	0.23382 (15)	0.0613 (8)
H13	0.7550	0.6439	0.2335	0.074*
C14	0.1150 (5)	0.4338 (5)	0.33449 (19)	0.0881 (11)
H14A	0.0466	0.4550	0.2901	0.132*
H14B	0.0464	0.4716	0.3699	0.132*
H14C	0.1330	0.3241	0.3398	0.132*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0474 (11)	0.0838 (13)	0.0720 (13)	0.0007 (9)	0.0075 (9)	−0.0005 (10)
O2	0.0686 (13)	0.0824 (14)	0.0777 (14)	−0.0039 (10)	−0.0007 (11)	0.0275 (11)
O3	0.0481 (11)	0.0835 (13)	0.1019 (17)	0.0080 (9)	0.0110 (11)	0.0278 (12)
O4	0.0760 (15)	0.0989 (16)	0.0681 (14)	−0.0059 (12)	0.0208 (11)	0.0058 (11)
C1	0.0532 (16)	0.0636 (15)	0.0458 (14)	−0.0009 (12)	0.0077 (11)	−0.0025 (12)
C2	0.0493 (14)	0.0612 (14)	0.0532 (15)	−0.0073 (11)	0.0109 (12)	−0.0019 (12)
C3	0.0467 (14)	0.0597 (14)	0.0643 (16)	−0.0031 (11)	0.0076 (12)	0.0027 (13)
C4	0.0480 (16)	0.091 (2)	0.103 (2)	−0.0051 (14)	0.0124 (16)	0.0236 (19)
C5	0.0490 (15)	0.0732 (17)	0.0647 (17)	−0.0080 (12)	0.0085 (12)	0.0031 (14)
C6	0.067 (2)	0.098 (2)	0.086 (2)	−0.0250 (17)	0.0082 (17)	0.0274 (19)
C7	0.092 (3)	0.104 (3)	0.144 (4)	−0.017 (2)	0.006 (3)	0.053 (3)
C8	0.0444 (14)	0.0499 (12)	0.0615 (16)	−0.0012 (10)	0.0007 (12)	0.0103 (12)
C9	0.0571 (16)	0.0583 (14)	0.0620 (16)	−0.0110 (12)	0.0051 (13)	0.0006 (13)
C10	0.0543 (15)	0.0695 (16)	0.0691 (18)	−0.0151 (13)	0.0048 (13)	0.0096 (15)
C11	0.0540 (16)	0.0656 (15)	0.0590 (17)	0.0025 (12)	0.0095 (13)	0.0131 (13)
C12	0.0650 (17)	0.0652 (16)	0.0653 (17)	−0.0068 (13)	0.0018 (14)	−0.0034 (14)
C13	0.0507 (15)	0.0629 (15)	0.0696 (18)	−0.0127 (12)	0.0058 (13)	0.0028 (14)
C14	0.068 (2)	0.114 (3)	0.087 (2)	−0.0002 (18)	0.0279 (18)	0.022 (2)

Geometric parameters (Å, º) top

O1—C1	1.198 (3)	C6—H6A	0.9700
O2—C1	1.348 (3)	C6—H6B	0.9700
O2—C7	1.445 (4)	C7—H7A	0.9700
O3—C4	1.411 (4)	C7—H7B	0.9700
O3—C3	1.447 (3)	C8—C9	1.374 (4)
O4—C11	1.371 (4)	C8—C13	1.381 (4)
O4—C14	1.418 (4)	C9—C10	1.383 (4)
C1—C2	1.448 (4)	C9—H9	0.9300
C2—C5	1.326 (4)	C10—C11	1.366 (4)
C2—C3	1.501 (4)	C10—H10	0.9300
C3—C8	1.490 (4)	C11—C12	1.390 (4)
C3—H3	0.9800	C12—C13	1.372 (4)
C4—C5	1.476 (4)	C12—H12	0.9300
C4—H4A	0.9700	C13—H13	0.9300
C4—H4B	0.9700	C14—H14A	0.9600
C5—C6	1.472 (4)	C14—H14B	0.9600
C6—C7	1.461 (5)	C14—H14C	0.9600

C1—O2—C7	118.5 (2)	O2—C7—C6	115.2 (3)
C4—O3—C3	111.1 (2)	O2—C7—H7A	108.5
C11—O4—C14	117.3 (3)	C6—C7—H7A	108.5
O1—C1—O2	118.2 (2)	O2—C7—H7B	108.5
O1—C1—C2	125.4 (3)	C6—C7—H7B	108.5
O2—C1—C2	116.4 (2)	H7A—C7—H7B	107.5
C5—C2—C1	122.7 (3)	C9—C8—C13	117.7 (3)
C5—C2—C3	111.0 (2)	C9—C8—C3	120.6 (2)
C1—C2—C3	126.3 (2)	C13—C8—C3	121.6 (2)
O3—C3—C8	111.6 (2)	C8—C9—C10	121.8 (3)
O3—C3—C2	102.55 (19)	C8—C9—H9	119.1
C8—C3—C2	115.9 (2)	C10—C9—H9	119.1
O3—C3—H3	108.9	C11—C10—C9	119.7 (3)
C8—C3—H3	108.9	C11—C10—H10	120.1
C2—C3—H3	108.9	C9—C10—H10	120.1
O3—C4—C5	105.4 (2)	C10—C11—O4	124.7 (3)
O3—C4—H4A	110.7	C10—C11—C12	119.4 (3)
C5—C4—H4A	110.7	O4—C11—C12	115.9 (3)
O3—C4—H4B	110.7	C13—C12—C11	119.8 (3)
C5—C4—H4B	110.7	C13—C12—H12	120.1
H4A—C4—H4B	108.8	C11—C12—H12	120.1
C2—C5—C6	121.4 (3)	C12—C13—C8	121.5 (3)
C2—C5—C4	109.5 (3)	C12—C13—H13	119.3
C6—C5—C4	129.1 (2)	C8—C13—H13	119.3
C7—C6—C5	110.0 (3)	O4—C14—H14A	109.5
C7—C6—H6A	109.7	O4—C14—H14B	109.5
C5—C6—H6A	109.7	H14A—C14—H14B	109.5
C7—C6—H6B	109.7	O4—C14—H14C	109.5
C5—C6—H6B	109.7	H14A—C14—H14C	109.5
H6A—C6—H6B	108.2	H14B—C14—H14C	109.5

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄O₄
M_r	246.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.240 (3), 8.635 (4), 19.545 (8)
β (°)	97.352 (6)
V (Å³)	1212.0 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.976, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	4872, 2127, 1494
R_int	0.104
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.227, 1.06
No. of reflections	2127
No. of parameters	164
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.31

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, T. T., Liu, J., Zhong, H. Y., Chen, H., Lv, Z. L., Zhang, Y. K., Zhang, M. F., Geng, D. P., Niu, C. J., Li, Y. M. & Li, K. (2011). Bioorg. Med. Chem. Lett. 21, 3381–3383. Web of Science CSD CrossRef CAS PubMed Google Scholar