(2E,5E)-2,5-Difurfurylidenecyclo­penta­none

Ma, S.-Y.; Zheng, Z.-B.

doi:10.1107/S1600536809047278

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3084

doi:10.1107/S1600536809047278

Open

access

(2E,5E)-2,5-Difurfurylidenecyclopentanone

Shi-Ying Ma ^a ^* and Ze-Bao Zheng ^a

^aDepartment of Chemistry and Environmental Science, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: mashy910@163.com

(Received 5 November 2009; accepted 9 November 2009; online 14 November 2009)

In the title molecule, C₁₅H₁₂O₃, the three five-membered rings are nearly coplanar: the dihedral angles between the cyclopentanone ring and the furan rings are 3.5 (2) and 9.7 (2)°, and the two furan rings form a dihedral angle of 7.2 (2)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds help to consolidate the crystal packing.

Related literature

For background to the use of bis(arylmethylidene)cycloalkanones as building blocks for the synthesis of biologically active heterocycles, see Guilford et al. (1999 ). For related structures, see: Du et al. (2007 ); Sun & Cui (2007 ); Wei et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₂O₃
M_r = 240.25
Monoclinic, P 2₁ /c
a = 5.9280 (9) Å
b = 8.5031 (13) Å
c = 23.280 (3) Å
β = 92.139 (3)°
V = 1172.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.12 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.989, T_max = 0.995
5793 measured reflections
2076 independent reflections
1083 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.129
S = 0.99
2076 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯O1ⁱ	0.93	2.49	3.221 (4)	136
C4—H4A⋯O1ⁱⁱ	0.97	2.45	3.393 (3)	165
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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 global, I. DOI: 10.1107/S1600536809047278/cv2656sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047278/cv2656Isup2.hkl

checkCIF report

Comment top

Bis(arylmethylidene)cycloalkanones are widely used as building blocks for the synthesis of biologically active heterocycles (Guilford et al., 1999). In the present paper, we describe the crystal stucture of the title compound.

The title molecule adopts an E-configuration about the central olefinic bonds (Fig.1). The cyclopentanone ring and the furan rings are alomst coplanar. All bond lengths and angles are normal and correspond to those observed in the related substituted cyclopentanone and cyclohexanone analogues reported by Du et al. (2007), Sun & Cui (2007) and Wei et al. (2008). The crystal packing exhibits weak intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For background to the use of bis(arylmethylidene)cycloalkanones as building blocks for the synthesis of biologically active heterocycles, see Guilford et al. (1999). For related structures, see: Du et al. (2007); Sun & Cui (2007); Wei et al. (2008).

Experimental top

Tetrabutylammonium bromide (0.3 mmol) and NaOH (5 mmol) were dissolved in the mixture of water (5 ml) and ethanol (2 ml). The solution was stirred at room temperature for 10 min,followed by added dropwise the mixture of furaldehyde (10 mmol) and cyclopentanone (5 mmol).The mixture was stirred at the temperature of 303 K for 2 h. When the reaction was complete, the residue was filtered. The precipitate was washed by water and recrystallized from ethyl acetate. Analysis calculated for C₁₅H₁₂O₃: C 75.00,H 5.00%; found: C 74.90,H 5.03%. Crystals of (I) suitable for single-crystal X-ray analysis were selected after recrystallization.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (I), with displacement ellipsoids drawn at the 30% probability level.

(2E,5E)-2,5-Difurfurylidenecyclopentanone top

Crystal data top

C₁₅H₁₂O₃	F(000) = 504
M_r = 240.25	D_x = 1.361 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 405 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.9280 (9) Å	Cell parameters from 461 reflections
b = 8.5031 (13) Å	θ = 3.0–18.7°
c = 23.280 (3) Å	µ = 0.10 mm⁻¹
β = 92.139 (3)°	T = 298 K
V = 1172.6 (3) Å³	Block, yellow
Z = 4	0.12 × 0.08 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2076 independent reflections
Radiation source: fine-focus sealed tube	1083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.989, T_max = 0.995	k = −10→9
5793 measured reflections	l = −27→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.049P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
2076 reflections	Δρ_max = 0.17 e Å⁻³
164 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (2)

Crystal data top

C₁₅H₁₂O₃	V = 1172.6 (3) Å³
M_r = 240.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9280 (9) Å	µ = 0.10 mm⁻¹
b = 8.5031 (13) Å	T = 298 K
c = 23.280 (3) Å	0.12 × 0.08 × 0.05 mm
β = 92.139 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2076 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1083 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.995	R_int = 0.059
5793 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 0.99	Δρ_max = 0.17 e Å⁻³
2076 reflections	Δρ_min = −0.16 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	1.2374 (3)	0.2225 (2)	0.62045 (7)	0.0606 (6)
O2	1.3568 (3)	0.4626 (2)	0.42876 (8)	0.0648 (6)
O3	0.7570 (3)	−0.1375 (2)	0.73472 (8)	0.0640 (6)
C1	1.0690 (5)	0.1894 (3)	0.58984 (11)	0.0443 (7)
C2	1.0293 (4)	0.2376 (3)	0.52998 (10)	0.0416 (7)
C3	0.8083 (4)	0.1745 (3)	0.50780 (10)	0.0496 (7)
H3A	0.8296	0.1048	0.4755	0.059*
H3B	0.7091	0.2597	0.4954	0.059*
C4	0.7065 (4)	0.0834 (3)	0.55845 (10)	0.0487 (7)
H4A	0.5655	0.1311	0.5692	0.058*
H4B	0.6780	−0.0252	0.5478	0.058*
C5	0.8774 (4)	0.0925 (3)	0.60707 (11)	0.0430 (7)
C6	1.1804 (4)	0.3239 (3)	0.50282 (11)	0.0476 (7)
H6	1.3098	0.3508	0.5244	0.057*
C7	1.1698 (5)	0.3802 (3)	0.44512 (12)	0.0459 (7)
C8	1.0169 (5)	0.3795 (3)	0.40086 (12)	0.0569 (8)
H8	0.8755	0.3320	0.4004	0.068*
C9	1.1100 (6)	0.4640 (3)	0.35521 (12)	0.0652 (9)
H9	1.0427	0.4831	0.3192	0.078*
C10	1.3128 (6)	0.5103 (4)	0.37419 (13)	0.0704 (10)
H10	1.4122	0.5684	0.3526	0.084*
C11	0.8754 (4)	0.0258 (3)	0.65893 (11)	0.0499 (7)
H11	1.0011	0.0448	0.6830	0.060*
C12	0.7047 (5)	−0.0711 (3)	0.68205 (11)	0.0465 (7)
C13	0.4940 (5)	−0.1134 (3)	0.66577 (12)	0.0579 (8)
H13	0.4170	−0.0844	0.6319	0.069*
C14	0.4101 (5)	−0.2101 (4)	0.70957 (13)	0.0657 (9)
H14	0.2682	−0.2566	0.7101	0.079*
C15	0.5736 (5)	−0.2212 (4)	0.74968 (13)	0.0642 (9)
H15	0.5640	−0.2786	0.7835	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0480 (12)	0.0831 (16)	0.0497 (12)	−0.0054 (11)	−0.0089 (9)	0.0018 (10)
O2	0.0632 (13)	0.0725 (15)	0.0587 (14)	−0.0127 (11)	0.0024 (10)	0.0110 (11)
O3	0.0670 (14)	0.0815 (16)	0.0430 (12)	−0.0039 (12)	−0.0042 (10)	0.0100 (10)
C1	0.0404 (16)	0.0489 (18)	0.0437 (17)	0.0062 (14)	0.0016 (13)	−0.0033 (13)
C2	0.0419 (16)	0.0414 (17)	0.0413 (16)	0.0049 (13)	0.0006 (12)	−0.0041 (12)
C3	0.0478 (17)	0.0550 (19)	0.0456 (17)	0.0013 (14)	−0.0021 (13)	−0.0022 (13)
C4	0.0449 (17)	0.0526 (18)	0.0484 (17)	−0.0014 (14)	−0.0006 (13)	−0.0019 (13)
C5	0.0422 (16)	0.0451 (17)	0.0417 (17)	0.0039 (13)	0.0022 (13)	−0.0042 (13)
C6	0.0472 (17)	0.0489 (19)	0.0466 (17)	0.0040 (14)	−0.0018 (13)	−0.0021 (13)
C7	0.0457 (17)	0.0408 (17)	0.0515 (18)	−0.0017 (13)	0.0048 (14)	−0.0021 (13)
C8	0.059 (2)	0.059 (2)	0.0522 (19)	−0.0027 (15)	−0.0028 (16)	−0.0025 (15)
C9	0.090 (3)	0.062 (2)	0.0430 (19)	0.0013 (18)	−0.0044 (17)	0.0024 (16)
C10	0.094 (3)	0.064 (2)	0.054 (2)	−0.0035 (19)	0.0106 (19)	0.0113 (17)
C11	0.0482 (17)	0.058 (2)	0.0435 (17)	0.0025 (14)	−0.0019 (13)	−0.0027 (14)
C12	0.0539 (19)	0.0477 (18)	0.0377 (16)	0.0054 (15)	−0.0009 (13)	0.0013 (13)
C13	0.058 (2)	0.066 (2)	0.0493 (18)	−0.0032 (16)	−0.0052 (15)	0.0082 (15)
C14	0.061 (2)	0.078 (2)	0.058 (2)	−0.0164 (17)	0.0007 (17)	0.0083 (17)
C15	0.072 (2)	0.071 (2)	0.050 (2)	−0.0090 (19)	0.0120 (17)	0.0091 (16)

Geometric parameters (Å, º) top

O1—C1	1.237 (3)	C6—C7	1.425 (3)
O2—C10	1.350 (3)	C6—H6	0.9300
O2—C7	1.377 (3)	C7—C8	1.347 (3)
O3—C15	1.356 (3)	C8—C9	1.412 (4)
O3—C12	1.375 (3)	C8—H8	0.9300
C1—C2	1.463 (3)	C9—C10	1.326 (4)
C1—C5	1.471 (3)	C9—H9	0.9300
C2—C6	1.335 (3)	C10—H10	0.9300
C2—C3	1.490 (3)	C11—C12	1.426 (4)
C3—C4	1.552 (3)	C11—H11	0.9300
C3—H3A	0.9700	C12—C13	1.341 (3)
C3—H3B	0.9700	C13—C14	1.415 (4)
C4—C5	1.493 (3)	C13—H13	0.9300
C4—H4A	0.9700	C14—C15	1.324 (3)
C4—H4B	0.9700	C14—H14	0.9300
C5—C11	1.335 (3)	C15—H15	0.9300

C10—O2—C7	106.5 (2)	C8—C7—C6	136.4 (3)
C15—O3—C12	106.8 (2)	O2—C7—C6	115.1 (2)
O1—C1—C2	125.6 (3)	C7—C8—C9	107.6 (3)
O1—C1—C5	125.8 (2)	C7—C8—H8	126.2
C2—C1—C5	108.6 (2)	C9—C8—H8	126.2
C6—C2—C1	121.2 (2)	C10—C9—C8	106.0 (3)
C6—C2—C3	129.1 (2)	C10—C9—H9	127.0
C1—C2—C3	109.7 (2)	C8—C9—H9	127.0
C2—C3—C4	106.2 (2)	C9—C10—O2	111.4 (3)
C2—C3—H3A	110.5	C9—C10—H10	124.3
C4—C3—H3A	110.5	O2—C10—H10	124.3
C2—C3—H3B	110.5	C5—C11—C12	128.1 (2)
C4—C3—H3B	110.5	C5—C11—H11	115.9
H3A—C3—H3B	108.7	C12—C11—H11	115.9
C5—C4—C3	106.2 (2)	C13—C12—O3	108.6 (2)
C5—C4—H4A	110.5	C13—C12—C11	135.6 (3)
C3—C4—H4A	110.5	O3—C12—C11	115.7 (2)
C5—C4—H4B	110.5	C12—C13—C14	107.5 (3)
C3—C4—H4B	110.5	C12—C13—H13	126.2
H4A—C4—H4B	108.7	C14—C13—H13	126.2
C11—C5—C1	121.2 (2)	C15—C14—C13	106.4 (3)
C11—C5—C4	129.4 (2)	C15—C14—H14	126.8
C1—C5—C4	109.3 (2)	C13—C14—H14	126.8
C2—C6—C7	128.6 (2)	C14—C15—O3	110.8 (3)
C2—C6—H6	115.7	C14—C15—H15	124.6
C7—C6—H6	115.7	O3—C15—H15	124.6
C8—C7—O2	108.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O1ⁱ	0.93	2.49	3.221 (4)	136
C4—H4A···O1ⁱⁱ	0.97	2.45	3.393 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₃
M_r	240.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	5.9280 (9), 8.5031 (13), 23.280 (3)
β (°)	92.139 (3)
V (Å³)	1172.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.12 × 0.08 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.989, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	5793, 2076, 1083
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.129, 0.99
No. of reflections	2076
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O1ⁱ	0.93	2.49	3.221 (4)	135.8
C4—H4A···O1ⁱⁱ	0.97	2.45	3.393 (3)	165.2

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

Acknowledgements

This project was supported by the Postgraduate Foundation of Taishan University (grant No. Y07–2-14).

References

Du, Z.-Y., Zhang, K. & Ng, S. W. (2007). Acta Cryst. E63, o2595–o2596. Web of Science CSD CrossRef IUCr Journals Google Scholar
Guilford, W. J., Shaw, K. J., Dallas, J. L., Koovakkat, S., Lee, W., Liang, A., Light, D. R., McCarrick, M. A., Whitlow, M., Ye, B. & Morrissey, M. M. (1999). J. Med. Chem. 42, 5415–5425. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Sun, Y.-F. & Cui, Y.-P. (2007). Acta Cryst. E63, o1932–o1933. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wei, J., Liang, G., Gai, Y. & Lu, J. (2008). Acta Cryst. E64, o1755. Web of Science CSD CrossRef IUCr Journals Google Scholar