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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3194.
Published online 2009 November 25. doi:  10.1107/S1600536809049514
PMCID: PMC2972117

2,4,5-Tri-2-furyl-1H-imidazole

Abstract

In the crystal of the title compound, C15H10N2O3, the molecules are linked together by inter­molecular N—H(...)N hydrogen bonds into chains along the c axis. The crystal structure also shows weak inter­molecular C—H(...)π hydrogen bonds. The three furanyl rings bonded to the imidazole core are not coplanar with the latter; the dihedral angles between the furanyl and imidazole ring planes are 29.3 (2), 19.4 (2), and 4.8 (2)°.

Related literature

For background to imidazole derivatives, see: Ho et al. (2003 [triangle]); Lambardino et al. (1974 [triangle]); Bao et al. (2003 [triangle]); Fürstner et al. (2000 [triangle]); Sundberg et al. (1996 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3194-scheme1.jpg

Experimental

Crystal data

  • C15H10N2O3
  • M r = 266.25
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3194-efi1.jpg
  • a = 9.3940 (19) Å
  • b = 17.146 (3) Å
  • c = 9.1484 (18) Å
  • β = 116.29 (3)°
  • V = 1321.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 295 K
  • 0.26 × 0.24 × 0.12 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.975, T max = 0.989
  • 6430 measured reflections
  • 1514 independent reflections
  • 1089 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.119
  • S = 1.04
  • 1514 reflections
  • 185 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.13 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: RAPID-AUTO (Rigaku Corporation, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049514/om2298sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049514/om2298Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors wish to acknowledge their gratitude to Ling Ye of the State Key Laboratory for Supramolecular Structure and Materials for the single-crystal X-ray determination.

supplementary crystallographic information

Comment

As an important member of the five-membered heterocycles, the imidazole moiety is present in a wide range of naturally occurring molecules (Ho et al., 2003). Compounds with an imidazole ring system have many pharmacological properties and play important roles in biochemical processes. (Lambardino & Wiseman, 1974). The biological importance of the imdazole ring system has made it a common substructure in numerous synthetic compounds such as fungicides, herbicides, plant growth regulators and therapeutic agents. Recent advances in green chemistry and organometallic chemistry have extended the boundary of imidazoles to the synthesis and application of a large class of imidazoles as ionic liquids (Bao et al., 2003) and imidazole-related N-heterocyclic carbenes (Fürstner et al., 2000). Compounds containing the furan ring easily react with singlet oxygen (Sundberg et al., 1996). As most devices are operated under an oxygen-free environment, in recent years furan derivatives have been used in research of photoelectric materials.

In the crystal structure of the title molecule (Fig.1), the three furan rings and the imidazole ring are not coplanar. The dihedral angles between the three furan rings C1/C2/C3/C4/O1, C7/C8/C9/C10/O2, C12/C13/C14/C15/O3 and the imidazole ring N1/C5/C6/N2/C11 are 29.3, 19.4 and 4.8°, respectively. The neighbouring molecules are nearly vertical to each other with the dihedral angle 98.0° and linked together by intermolecular N—H···N hydrogen bonds into 1-D infinite chains along the c axis (Table 1, Fig.2). The crystal structure also shows weak intermolecular C—H···π hydrogen bonds (Fig. 3), Cg = centroid of N1/C5/C6/N2/C11.

Experimental

A mixture of furil (5.26 mmol, 1 g) and ammonium acetate (52.6 mmol, 4.05 g) in acetic acid (20 ml) was refluxed. After completion of the reaction confirmed by TLC, the reaction mixture was cooled to room temperature, poured into 100 ml of water, and then neutralized with a 20% NaOH aqueous solution to pH 9. The mixture was extracted with ethyl acetate, and the solvent was removed by rotary evaporation. The crude product was further purified by column chromatography using a mixture of petroleum ether and ethyl acetate (3:1) as eluents. Then 2,4,5-tri(furan-2-yl)-1H-imidazole was recystallized from methanol. Yellow single crystals were obtained by slow evaporation of the solvent at ambient temperature. For C15H10N2O3, MS: 267.2 (M+H)+1, found:266.2.

Refinement

The C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and allowed to ride on their parent atoms in the riding model approximation with Uiso(H) = 1.2 Ueq(C). The H atom attached to N was found in a difference Fourier map and refined isotropically. Friedel opposites were merged.

Figures

Fig. 1.
The molecule of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Fig. 2.
Packing of the molecules showing the intermolecular N—H···N interactions to form a 1-D chain. Color scheme: blue, nitrogen; red, oxygen; grey, carbon; green, hydrogen.
Fig. 3.
Packing of the molecules showing the C—H···π interactions. Cg is the centroid of the imidazole ring (N1/C5/C6/N2/C11). C10···Cg = 3.6031 (31) Å. The green spots are the centers ...
Fig. 4.
The formation of the title compound.

Crystal data

C15H10N2O3Z = 4
Mr = 266.25F(000) = 552
Monoclinic, CcDx = 1.339 Mg m3
Hall symbol: C -2ycMo Kα radiation, λ = 0.71073 Å
a = 9.3940 (19) Åθ = 3.4–27.5°
b = 17.146 (3) ŵ = 0.10 mm1
c = 9.1484 (18) ÅT = 295 K
β = 116.29 (3)°Block, yellow
V = 1321.1 (5) Å30.26 × 0.24 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer1514 independent reflections
Radiation source: fine-focus sealed tube1089 reflections with I > 2σ(I)
graphiteRint = 0.031
ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −12→12
Tmin = 0.975, Tmax = 0.989k = −22→22
6430 measured reflectionsl = −11→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0752P)2] where P = (Fo2 + 2Fc2)/3
1514 reflections(Δ/σ)max < 0.001
185 parametersΔρmax = 0.13 e Å3
2 restraintsΔρmin = −0.14 e Å3

Special details

Experimental. (See detailed section in the paper)
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)

xyzUiso*/Ueq
O10.2149 (4)0.03841 (17)0.1765 (4)0.0969 (10)
O20.2353 (3)0.22150 (13)−0.1681 (3)0.0785 (7)
O30.7630 (4)−0.05039 (19)−0.0235 (3)0.0887 (8)
N10.4736 (3)0.01826 (14)0.1105 (3)0.0514 (6)
H1A0.484 (5)−0.016 (2)0.199 (5)0.071 (10)*
N20.5145 (3)0.06255 (15)−0.0952 (3)0.0523 (6)
C10.1128 (7)0.0677 (3)0.2310 (8)0.1106 (17)
H10.06800.03890.28620.133*
C20.0868 (6)0.1396 (3)0.1967 (6)0.0962 (14)
H20.01980.17160.22030.115*
C30.1802 (6)0.1624 (3)0.1147 (5)0.0918 (13)
H30.18720.21180.07670.110*
C40.2547 (4)0.09777 (18)0.1044 (4)0.0558 (7)
C50.3664 (3)0.07872 (16)0.0416 (3)0.0488 (6)
C60.3936 (3)0.10452 (16)−0.0868 (3)0.0499 (7)
C70.3183 (3)0.16580 (17)−0.2043 (4)0.0564 (7)
C80.3121 (5)0.1808 (2)−0.3509 (4)0.0832 (11)
H80.35860.1518−0.40430.100*
C90.2190 (5)0.2505 (3)−0.4089 (6)0.0884 (13)
H90.19350.2754−0.50770.106*
C100.1770 (5)0.2724 (2)−0.2969 (6)0.0882 (14)
H100.11620.3162−0.30350.106*
C110.5600 (3)0.01121 (16)0.0265 (3)0.0492 (6)
C120.6862 (4)−0.04443 (19)0.0694 (4)0.0588 (8)
C130.7492 (5)−0.0938 (2)0.1934 (5)0.0807 (12)
H130.7166−0.10130.27470.097*
C140.8742 (5)−0.1329 (3)0.1795 (7)0.0974 (14)
H140.9409−0.17040.25010.117*
C150.8781 (6)−0.1061 (3)0.0482 (7)0.1003 (15)
H150.9489−0.12240.00860.120*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.102 (2)0.0895 (19)0.136 (3)0.0189 (17)0.085 (2)0.0234 (17)
O20.0788 (15)0.0619 (14)0.0816 (15)0.0195 (13)0.0236 (12)0.0141 (12)
O30.0850 (18)0.111 (2)0.0780 (15)0.0260 (16)0.0436 (14)0.0038 (15)
N10.0502 (13)0.0540 (13)0.0454 (12)0.0098 (11)0.0170 (10)0.0059 (10)
N20.0473 (12)0.0571 (14)0.0476 (12)−0.0017 (12)0.0165 (10)−0.0001 (10)
C10.104 (4)0.124 (4)0.142 (4)0.027 (3)0.089 (4)0.017 (3)
C20.084 (3)0.118 (4)0.098 (3)0.045 (3)0.051 (2)0.009 (3)
C30.108 (3)0.077 (2)0.095 (3)0.029 (2)0.049 (2)0.002 (2)
C40.0501 (16)0.0563 (17)0.0575 (16)0.0085 (14)0.0208 (13)0.0027 (13)
C50.0430 (13)0.0484 (14)0.0467 (14)0.0027 (12)0.0123 (10)−0.0007 (11)
C60.0469 (14)0.0453 (15)0.0464 (14)−0.0003 (12)0.0107 (11)−0.0005 (11)
C70.0481 (16)0.0486 (15)0.0588 (16)−0.0060 (13)0.0111 (12)0.0037 (12)
C80.093 (3)0.079 (2)0.072 (2)0.010 (2)0.032 (2)0.0216 (19)
C90.084 (3)0.078 (2)0.079 (2)0.001 (2)0.014 (2)0.035 (2)
C100.073 (2)0.067 (2)0.096 (3)0.0108 (19)0.011 (2)0.030 (2)
C110.0473 (14)0.0504 (15)0.0454 (13)0.0050 (13)0.0164 (11)−0.0010 (12)
C120.0528 (17)0.0630 (18)0.0578 (16)0.0080 (14)0.0222 (14)−0.0051 (14)
C130.086 (3)0.078 (2)0.087 (2)0.037 (2)0.047 (2)0.026 (2)
C140.080 (3)0.087 (3)0.111 (3)0.039 (2)0.029 (2)0.016 (3)
C150.072 (2)0.111 (3)0.117 (4)0.031 (3)0.042 (3)−0.018 (3)

Geometric parameters (Å, °)

O1—C41.352 (4)C4—C51.440 (4)
O1—C11.358 (5)C5—C61.381 (4)
O2—C71.363 (4)C6—C71.444 (4)
O2—C101.370 (4)C7—C81.341 (5)
O3—C121.340 (4)C8—C91.437 (6)
O3—C151.373 (6)C8—H80.9300
N1—C111.349 (4)C9—C101.306 (7)
N1—C51.387 (4)C9—H90.9300
N1—H1A0.96 (4)C10—H100.9300
N2—C111.332 (4)C11—C121.434 (4)
N2—C61.375 (4)C12—C131.326 (5)
C1—C21.269 (7)C13—C141.406 (6)
C1—H10.9300C13—H130.9300
C2—C31.438 (7)C14—C151.302 (7)
C2—H20.9300C14—H140.9300
C3—C41.336 (5)C15—H150.9300
C3—H30.9300
C4—O1—C1107.1 (3)C8—C7—C6132.3 (3)
C7—O2—C10106.9 (3)O2—C7—C6118.2 (3)
C12—O3—C15106.3 (4)C7—C8—C9106.2 (4)
C11—N1—C5107.9 (2)C7—C8—H8126.9
C11—N1—H1A124 (2)C9—C8—H8126.9
C5—N1—H1A128 (2)C10—C9—C8107.2 (3)
C11—N2—C6105.5 (2)C10—C9—H9126.4
C2—C1—O1111.0 (4)C8—C9—H9126.4
C2—C1—H1124.5C9—C10—O2110.3 (4)
O1—C1—H1124.5C9—C10—H10124.8
C1—C2—C3107.4 (4)O2—C10—H10124.8
C1—C2—H2126.3N2—C11—N1111.4 (2)
C3—C2—H2126.3N2—C11—C12126.1 (3)
C4—C3—C2105.7 (4)N1—C11—C12122.5 (2)
C4—C3—H3127.1C13—C12—O3109.4 (3)
C2—C3—H3127.1C13—C12—C11131.3 (3)
C3—C4—O1108.9 (3)O3—C12—C11119.3 (3)
C3—C4—C5135.5 (3)C12—C13—C14107.5 (4)
O1—C4—C5115.6 (3)C12—C13—H13126.2
C6—C5—N1104.8 (3)C14—C13—H13126.2
C6—C5—C4135.2 (3)C15—C14—C13106.3 (4)
N1—C5—C4119.9 (3)C15—C14—H14126.8
N2—C6—C5110.4 (2)C13—C14—H14126.8
N2—C6—C7118.9 (3)C14—C15—O3110.4 (4)
C5—C6—C7130.7 (3)C14—C15—H15124.8
C8—C7—O2109.4 (3)O3—C15—H15124.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.97 (3)1.94 (3)2.899 (3)167 (2)
C10—H10···Cgii0.932.81 (1)3.6031 (31)144 (1)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2298).

References

  • Bao, W., Wang, Z. & Li, Y. (2003). J. Org. Chem. 68, 591–593. [PubMed]
  • Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fürstner, A., Thiel, O. R., Ackermann, L., Schanz, H.-J. & Nolan, S. P. (2000). J. Org. Chem. 65, 2204–2207. [PubMed]
  • Ho, J. Z., Mohareb, R. M., Ahn, J. H., Sim, T. B. & Rapoport, H. (2003). J. Org. Chem. 68, 109–114. [PubMed]
  • Lambardino, J. G. & Wiseman, E. H. (1974). J. Med. Chem. 17, 1182–1188. [PubMed]
  • Rigaku Corporation (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sundberg, R. J., In: Katrizky, A. R., Rees, C. W. & Scriven, E. F. (1996). Editors, Comprehensive Heterocyclic Chemistry II, Vol. 2, pp. 119–206. Oxford: Pergamon.

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