1,3-Difurfurylbenzimidazolium chloride monohydrate

Mehmet Akkurt; Nihat Şireci; Selma Deniz; Hasan Küçükbay; Orhan Büyükgüngör

doi:10.1107/S1600536809029626

. 2009 Jul 29;65(Pt 8):o2037–o2038. doi: 10.1107/S1600536809029626

1,3-Difurfurylbenzimidazolium chloride monohydrate

Mehmet Akkurt ^a,^*, Nihat Şireci ^b, Selma Deniz ^c, Hasan Küçükbay ^c, Orhan Büyükgüngör ^d

PMCID: PMC2977341 PMID: 21583703

Abstract

The title compound, C₁₇H₁₅N₂O₂ ⁺·Cl⁻·H₂O, was synthesized from benzimidazole and furfryl chloride in dimethylformamide. The cationic benzimidazolium ring is connected to two furan rings via methylene bridges. The furan rings make dihedral angle of 79.09 (18)° with respect to each other, and make dihedral angles of 73.92 (12) and 72.58 (13)° with respect to the benzimidazole ring. O—H⋯Cl, C—H⋯O and C—H⋯Cl hydrogen bonds and C—H⋯π interactions contribute to the stabilization of the crystal structure. Furthermore, there is a π–π interaction between adjacent five- and six-membered rings of the benzimidazole groups [centroid–centroid distance = 3.5305 (8) Å].

Related literature

For the biological activity of furan derivatives, see: Ji et al. (2009 ▶). For the antimicrobial activity of a large number of organic and organometallic derivatives of benzimidazole against standard bacterial strains, see: Küçükbay & Durmaz (1997 ▶); Küçükbay et al. (2001 ▶, 2004 ▶, 2009 ▶); Çetinkaya et al. (1996 ▶). For the catalytic activity of furans, see: Küçükbay et al. (1996 ▶). For related structures, see: Yıldırım et al. (2007 ▶); Akkurt et al. (2006 ▶, 2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₅N₂O₂ ⁺·Cl⁻·H₂O
M _r = 332.78
Triclinic,
a = 9.0201 (5) Å
b = 9.3135 (5) Å
c = 11.2711 (6) Å
α = 66.778 (4)°
β = 81.869 (4)°
γ = 73.656 (4)°
V = 834.50 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.58 × 0.49 × 0.38 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.871, T _max = 0.913
15618 measured reflections
3780 independent reflections
2972 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.122
S = 1.04
3780 reflections
214 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029626/xu2569sup1.cif

e-65-o2037-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029626/xu2569Isup2.hkl

e-65-o2037-Isup2.hkl^{(181.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—HW1⋯Cl1ⁱ	0.93 (3)	2.27 (3)	3.1563 (17)	159 (3)
O3—HW2⋯Cl1	0.98 (3)	2.22 (3)	3.1848 (17)	168 (3)
C7—H7⋯O3	0.93	2.22	3.133 (2)	168
C8—H8A⋯Cl1ⁱⁱ	0.97	2.75	3.7098 (18)	169
C8—H8B⋯Cl1	0.97	2.67	3.6371 (18)	173
C13—H13A⋯Cl1ⁱ	0.97	2.67	3.6332 (18)	171
C13—H13B⋯Cl1ⁱⁱⁱ	0.97	2.66	3.6290 (19)	177
C11—H11⋯Cg2^iv	0.93	2.85	3.641 (4)	144
C12—H12⋯Cg4^iv	0.93	2.96	3.718 (2)	139

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 and Cg4 are the centroids of the O2/C14–C17 furan and C1–C6 benzene rings, respectively.

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund). NŞ, SD and HK wish to thank the İnönü University Research Fund (directed project BAPB-2008/05) for financial support of this study.

supplementary crystallographic information

Comment

Like benzimidazoles, furan derivatives occur widely as key structural subunits in numerous natural products, which exhibit interesting biological activities and also in substances of relevance for industry (Ji et al., 2009). Previously, a large number of organic and organometallic derivatives of benzimidazole were prepared in our research laboratory for their antimicrobial activities against standard bacterial strains (Küçükbay & Durmaz, 1997; Küçükbay et al., 2001; Küçükbay et al., 2004; Çetinkaya et al., 1996; Küçükbay et al., 2009) and catalytic activities in some carbon-carbon bond formation reactions and catalytic synthesis of furans (Küçükbay et al., 1996). In connection with these studies, we planned to synthesize having furfuryl substituted new benzimidazole compound (I) and elucidate its crystal structure.

In the asymmetric unit of the title compound (Fig. 1), there are one Cl^- anion, a 1,3-di(furfuryl)benzimidazolium cation and one water molecule. The bond lengths are comparable with those found in earlier work on similar compounds (Allen et al., 1987). The O1/C9–C12 and O2/C14–C17 furan rings and N1/N2/C1–C7 benzimidazole ring are almost planar, with maximum deviations of 0.011 (2) for O1 atoms and -0.013 (2) for O2 atom, and -0.008 (1) Å for N1 atom, respectively. The furan rings make dihedral angles of 79.09 (18)° with each other and 73.92 (12) and 72.58 (13)°, respectively, with the benzimidazole ring.

In the crystal structure of (I), there are O—H···Cl, C—H···O and C—H···Cl hydrogen-bonds (Fig. 2) and C—H···π interactions to stabilize the structure (Table 1). Furthermore, there are π–π interactions between the sequential five- and six membered rings {Cg2 (ring N1/N2/C1/C6/C7)···Cg4 (ring C1–C6) [-x, 1 - x, 1 - z] = 3.5305 (8) Å} of the benzimidazole groups.

Experimental

A mixture of benzimidazole (1.18 g, 10 mmol) and furfuryl chloride (2.3 g, 20 mmol) in DMF (4 ml) was heated under reflux for 4 h. The solution was allowed to cool to room temperature and Et₂O (5 ml) was added. The precipitate was then crystallized from EtOH / Et₂O(2:1). Yield: 1.43 g, 71%, m.p. 488–489 K. ¹HNMR (DMSO-d₆): δ 5.93(4H, s), 6.51(2H, d), 6.84(2H, d),8.12(2H, d), 7.71 (4H, m), 10.21(1H, s). ¹³CNMR (DMSO-d₆): δ 43.05, 111.00, 111.39, 113.99, 126.93, 130.79, 142.37, 144.38, 146.77. Analysis calculated for C₁₇H₁₇N₂O₃Cl: C 61.35, H 5.11, N 8.42%. Found: C 60.97, H 5.06, N 8.38%.