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

Wang, S.-J.; Gu, Q.; Su, Q.; Chen, X.-D.; Zhang, Y.-M.

doi:10.1107/S1600536809049514

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3194

doi:10.1107/S1600536809049514

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

Shuai-Jun Wang,^a Qiang Gu,^a Qing Su,^a Xiao-Dong Chen ^b and Yu-Min Zhang ^a ^*

^aCollege of Chemistry, Jilin University, Changchun 130012, People's Republic of China, and ^bExperimental Center of Testing Science, Jilin University, Changchun 130023, People's Republic of China
^*Correspondence e-mail: zhang_ym@jlu.edu.cn

(Received 10 November 2009; accepted 19 November 2009; online 25 November 2009)

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 ); Lambardino et al. (1974 ); Bao et al. (2003 ); Fürstner et al. (2000 ); Sundberg et al. (1996 ).

Experimental

Crystal data

C₁₅H₁₀N₂O₃
M_r = 266.25
Monoclinic, C c
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 ) 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[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 1.04
1514 reflections
185 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.97 (3)	1.94 (3)	2.899 (3)	167 (2)
C10—H10⋯Cgⁱⁱ	0.93	2.81	3.6031 (31)	144
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg is the centroid of the N1/C5/C6/N2/C11 ring.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For background to imidazole derivatives, see: Ho et al. (2003); Lambardino et al. (1974); Bao et al. (2003); Fürstner et al. (2000); Sundberg et al. (1996). Cg is the centroid of the N1/C5/C6/N2/C11 ring.

Experimental top

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.

Computing details top

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

Figures top

	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 of the aromatic rings.
	Fig. 4. The formation of the title compound.

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

Crystal data top

C₁₅H₁₀N₂O₃	Z = 4
M_r = 266.25	F(000) = 552
Monoclinic, Cc	D_x = 1.339 Mg m⁻³
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3940 (19) Å	θ = 3.4–27.5°
b = 17.146 (3) Å	µ = 0.10 mm⁻¹
c = 9.1484 (18) Å	T = 295 K
β = 116.29 (3)°	Block, yellow
V = 1321.1 (5) Å³	0.26 × 0.24 × 0.12 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1514 independent reflections
Radiation source: fine-focus sealed tube	1089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.975, T_max = 0.989	k = −22→22
6430 measured reflections	l = −11→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0752P)²] where P = (F_o² + 2F_c²)/3
1514 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.13 e Å⁻³
2 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₅H₁₀N₂O₃	V = 1321.1 (5) Å³
M_r = 266.25	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 9.3940 (19) Å	µ = 0.10 mm⁻¹
b = 17.146 (3) Å	T = 295 K
c = 9.1484 (18) Å	0.26 × 0.24 × 0.12 mm
β = 116.29 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1514 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1089 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.989	R_int = 0.031
6430 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.13 e Å⁻³
1514 reflections	Δρ_min = −0.14 e Å⁻³
185 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.2149 (4)	0.03841 (17)	0.1765 (4)	0.0969 (10)
O2	0.2353 (3)	0.22150 (13)	−0.1681 (3)	0.0785 (7)
O3	0.7630 (4)	−0.05039 (19)	−0.0235 (3)	0.0887 (8)
N1	0.4736 (3)	0.01826 (14)	0.1105 (3)	0.0514 (6)
H1A	0.484 (5)	−0.016 (2)	0.199 (5)	0.071 (10)*
N2	0.5145 (3)	0.06255 (15)	−0.0952 (3)	0.0523 (6)
C1	0.1128 (7)	0.0677 (3)	0.2310 (8)	0.1106 (17)
H1	0.0680	0.0389	0.2862	0.133*
C2	0.0868 (6)	0.1396 (3)	0.1967 (6)	0.0962 (14)
H2	0.0198	0.1716	0.2203	0.115*
C3	0.1802 (6)	0.1624 (3)	0.1147 (5)	0.0918 (13)
H3	0.1872	0.2118	0.0767	0.110*
C4	0.2547 (4)	0.09777 (18)	0.1044 (4)	0.0558 (7)
C5	0.3664 (3)	0.07872 (16)	0.0416 (3)	0.0488 (6)
C6	0.3936 (3)	0.10452 (16)	−0.0868 (3)	0.0499 (7)
C7	0.3183 (3)	0.16580 (17)	−0.2043 (4)	0.0564 (7)
C8	0.3121 (5)	0.1808 (2)	−0.3509 (4)	0.0832 (11)
H8	0.3586	0.1518	−0.4043	0.100*
C9	0.2190 (5)	0.2505 (3)	−0.4089 (6)	0.0884 (13)
H9	0.1935	0.2754	−0.5077	0.106*
C10	0.1770 (5)	0.2724 (2)	−0.2969 (6)	0.0882 (14)
H10	0.1162	0.3162	−0.3035	0.106*
C11	0.5600 (3)	0.01121 (16)	0.0265 (3)	0.0492 (6)
C12	0.6862 (4)	−0.04443 (19)	0.0694 (4)	0.0588 (8)
C13	0.7492 (5)	−0.0938 (2)	0.1934 (5)	0.0807 (12)
H13	0.7166	−0.1013	0.2747	0.097*
C14	0.8742 (5)	−0.1329 (3)	0.1795 (7)	0.0974 (14)
H14	0.9409	−0.1704	0.2501	0.117*
C15	0.8781 (6)	−0.1061 (3)	0.0482 (7)	0.1003 (15)
H15	0.9489	−0.1224	0.0086	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.102 (2)	0.0895 (19)	0.136 (3)	0.0189 (17)	0.085 (2)	0.0234 (17)
O2	0.0788 (15)	0.0619 (14)	0.0816 (15)	0.0195 (13)	0.0236 (12)	0.0141 (12)
O3	0.0850 (18)	0.111 (2)	0.0780 (15)	0.0260 (16)	0.0436 (14)	0.0038 (15)
N1	0.0502 (13)	0.0540 (13)	0.0454 (12)	0.0098 (11)	0.0170 (10)	0.0059 (10)
N2	0.0473 (12)	0.0571 (14)	0.0476 (12)	−0.0017 (12)	0.0165 (10)	−0.0001 (10)
C1	0.104 (4)	0.124 (4)	0.142 (4)	0.027 (3)	0.089 (4)	0.017 (3)
C2	0.084 (3)	0.118 (4)	0.098 (3)	0.045 (3)	0.051 (2)	0.009 (3)
C3	0.108 (3)	0.077 (2)	0.095 (3)	0.029 (2)	0.049 (2)	0.002 (2)
C4	0.0501 (16)	0.0563 (17)	0.0575 (16)	0.0085 (14)	0.0208 (13)	0.0027 (13)
C5	0.0430 (13)	0.0484 (14)	0.0467 (14)	0.0027 (12)	0.0123 (10)	−0.0007 (11)
C6	0.0469 (14)	0.0453 (15)	0.0464 (14)	−0.0003 (12)	0.0107 (11)	−0.0005 (11)
C7	0.0481 (16)	0.0486 (15)	0.0588 (16)	−0.0060 (13)	0.0111 (12)	0.0037 (12)
C8	0.093 (3)	0.079 (2)	0.072 (2)	0.010 (2)	0.032 (2)	0.0216 (19)
C9	0.084 (3)	0.078 (2)	0.079 (2)	0.001 (2)	0.014 (2)	0.035 (2)
C10	0.073 (2)	0.067 (2)	0.096 (3)	0.0108 (19)	0.011 (2)	0.030 (2)
C11	0.0473 (14)	0.0504 (15)	0.0454 (13)	0.0050 (13)	0.0164 (11)	−0.0010 (12)
C12	0.0528 (17)	0.0630 (18)	0.0578 (16)	0.0080 (14)	0.0222 (14)	−0.0051 (14)
C13	0.086 (3)	0.078 (2)	0.087 (2)	0.037 (2)	0.047 (2)	0.026 (2)
C14	0.080 (3)	0.087 (3)	0.111 (3)	0.039 (2)	0.029 (2)	0.016 (3)
C15	0.072 (2)	0.111 (3)	0.117 (4)	0.031 (3)	0.042 (3)	−0.018 (3)

Geometric parameters (Å, º) top

O1—C4	1.352 (4)	C4—C5	1.440 (4)
O1—C1	1.358 (5)	C5—C6	1.381 (4)
O2—C7	1.363 (4)	C6—C7	1.444 (4)
O2—C10	1.370 (4)	C7—C8	1.341 (5)
O3—C12	1.340 (4)	C8—C9	1.437 (6)
O3—C15	1.373 (6)	C8—H8	0.9300
N1—C11	1.349 (4)	C9—C10	1.306 (7)
N1—C5	1.387 (4)	C9—H9	0.9300
N1—H1A	0.96 (4)	C10—H10	0.9300
N2—C11	1.332 (4)	C11—C12	1.434 (4)
N2—C6	1.375 (4)	C12—C13	1.326 (5)
C1—C2	1.269 (7)	C13—C14	1.406 (6)
C1—H1	0.9300	C13—H13	0.9300
C2—C3	1.438 (7)	C14—C15	1.302 (7)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.336 (5)	C15—H15	0.9300
C3—H3	0.9300

C4—O1—C1	107.1 (3)	C8—C7—C6	132.3 (3)
C7—O2—C10	106.9 (3)	O2—C7—C6	118.2 (3)
C12—O3—C15	106.3 (4)	C7—C8—C9	106.2 (4)
C11—N1—C5	107.9 (2)	C7—C8—H8	126.9
C11—N1—H1A	124 (2)	C9—C8—H8	126.9
C5—N1—H1A	128 (2)	C10—C9—C8	107.2 (3)
C11—N2—C6	105.5 (2)	C10—C9—H9	126.4
C2—C1—O1	111.0 (4)	C8—C9—H9	126.4
C2—C1—H1	124.5	C9—C10—O2	110.3 (4)
O1—C1—H1	124.5	C9—C10—H10	124.8
C1—C2—C3	107.4 (4)	O2—C10—H10	124.8
C1—C2—H2	126.3	N2—C11—N1	111.4 (2)
C3—C2—H2	126.3	N2—C11—C12	126.1 (3)
C4—C3—C2	105.7 (4)	N1—C11—C12	122.5 (2)
C4—C3—H3	127.1	C13—C12—O3	109.4 (3)
C2—C3—H3	127.1	C13—C12—C11	131.3 (3)
C3—C4—O1	108.9 (3)	O3—C12—C11	119.3 (3)
C3—C4—C5	135.5 (3)	C12—C13—C14	107.5 (4)
O1—C4—C5	115.6 (3)	C12—C13—H13	126.2
C6—C5—N1	104.8 (3)	C14—C13—H13	126.2
C6—C5—C4	135.2 (3)	C15—C14—C13	106.3 (4)
N1—C5—C4	119.9 (3)	C15—C14—H14	126.8
N2—C6—C5	110.4 (2)	C13—C14—H14	126.8
N2—C6—C7	118.9 (3)	C14—C15—O3	110.4 (4)
C5—C6—C7	130.7 (3)	C14—C15—H15	124.8
C8—C7—O2	109.4 (3)	O3—C15—H15	124.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.97 (3)	1.94 (3)	2.899 (3)	167 (2)
C10—H10···Cgⁱⁱ	0.93	2.81 (1)	3.603 (3)	144 (1)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀N₂O₃
M_r	266.25
Crystal system, space group	Monoclinic, Cc
Temperature (K)	295
a, b, c (Å)	9.3940 (19), 17.146 (3), 9.1484 (18)
β (°)	116.29 (3)
V (Å³)	1321.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.24 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.975, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	6430, 1514, 1089
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.04
No. of reflections	1514
No. of parameters	185
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.14

Computer programs: RAPID-AUTO (Rigaku Corporation, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.97 (3)	1.94 (3)	2.899 (3)	167 (2)
C10—H10···Cgⁱⁱ	0.93	2.8106 (6)	3.6031 (31)	143.807 (19)

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

Acknowledgements

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.

References

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