2-(1-Phenyl-1H-benzimidazol-2-yl)phenol

A Thiruvalluvar; S Rosepriya; K Jayamoorthy; J Jayabharathi; Sema Öztürk Yildirim; R J Butcher

doi:10.1107/S1600536812049859

. 2012 Dec 8;69(Pt 1):o62. doi: 10.1107/S1600536812049859

2-(1-Phenyl-1H-benzimidazol-2-yl)phenol

A Thiruvalluvar ^a,^*, S Rosepriya ^a, K Jayamoorthy ^b, J Jayabharathi ^b, Sema Öztürk Yildirim ^c,^d, R J Butcher ^c

PMCID: PMC3588362 PMID: 23476443

Abstract

In the title molecule, C₁₉H₁₄N₂O, the benzimidazole unit is close to being planar [maximum deviation = 0.0253 (11) Å] and forms dihedral angles of 68.98 (6) and 20.38 (7)° with the adjacent phenyl and benzene rings; the dihedral angle between the latter two planes is 64.30 (7)°. An intramolecular O—H⋯N hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked by C—H⋯N and C—H⋯O hydrogen bonds, and consolidated into a three-dimensional architecture by π–π stacking interactions, with a centroid–centroid distance of 3.8428 (12) Å.

Related literature

For the range of pharmacological activities and toxicological properties of benzimidazole derivatives, see: Spasov et al. (1999 ▶). For closely related crystal structures, see: Jayamoorthy et al. (2012 ▶); Rosepriya et al. (2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₁₄N₂O
M _r = 286.32
Triclinic,
a = 8.1941 (6) Å
b = 9.5983 (14) Å
c = 10.3193 (18) Å
α = 64.637 (16)°
β = 80.356 (10)°
γ = 83.610 (9)°
V = 722.3 (2) Å³
Z = 2
Cu Kα radiation
μ = 0.66 mm⁻¹
T = 123 K
0.76 × 0.46 × 0.32 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ▶), using a multi-faceted crystal model (Clark & Reid, 1995 ▶)] T _min = 0.731, T _max = 0.811
4335 measured reflections
2826 independent reflections
2420 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.171
S = 1.04
2826 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(19.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812049859/tk5179sup1.cif

e-69-00o62-sup1.cif^{(19.6KB, cif)}

Click here for additional data file.^{(135.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049859/tk5179Isup2.hkl

e-69-00o62-Isup2.hkl^{(135.9KB, hkl)}

Click here for additional data file.^{(2.6KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536812049859/tk5179Isup3.cdx

Click here for additional data file.^{(5.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812049859/tk5179Isup4.cml

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
O26—H26⋯N3	0.97 (3)	1.70 (3)	2.583 (2)	150 (3)
C14—H14⋯N3ⁱ	0.95	2.60	3.456 (3)	151
C16—H16⋯O26ⁱⁱ	0.95	2.49	3.388 (2)	157

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

KJ thanks the DST (No. SRS1IC-73/2010) for a fellowship. JJ thanks the DST (No. SRSIC-73/2010), the UGC [F. No. 36–21/2008 (SR)] and the DRDO (NRB-213/MAT/10–11) for providing funds for this research. RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Spasov et al. (1999) have reviewed the wide range of pharmacological activities and toxicological properties of benzimidazole derivatives. Since our research group is working in organic light emitting devices, we are interested to use the title compound as ligand for synthesizing Ir^III complexes. Further, we are interested to use the title compound as a ligand to study excited state intramolecular proton transfer (ESIPT) processes. Jayamoorthy et al. (2012) and Rosepriya et al. (2012) have reported closely related crystal structures of benzimidazole derivatives.

In the title molecule, C₁₉H₁₄N₂O (Fig. 1), the benzimidazole unit is almost planar [maximum deviation = 0.0253 (11) Å for C2]. The dihedral angles between the planes of the benzimidazole and the phenyl ring at N1 and the benzene ring at C2 are 68.98 (6) and 20.38 (7)°, respectively. The dihedral angle between the planes of the adjacent phenyl and benzene rings is 64.30 (7)°. The molecular conformation is stabilized by an intramolecular O26—H26···N3 hydrogen bond, which generates an S(6) ring motif (Bernstein et al., 1995). In the crystal (Fig. 2), molecules are linked by C14—H14···N3 and C16—H16···O26 hydrogen bonds (Table 1). Further, π—π stacking interactions between symmetry-related imidazole and benzene rings [Cg1—Cg4ⁱⁱⁱ = Cg4—Cg1ⁱⁱⁱ = 3.8428 (12) Å, symmetry code (iii): 2 - x, - y, - z where Cg1 is the centroid of the imidazole ring (N1/C2/N3/C9/C8) and Cg4 is the centroid of the benzene ring defined by atoms C21—C26, respectively] (Fig. 3) are noted.

Experimental

To N-phenyl-o-phenylenediamine (3.128 g, 17 mmol) in ethanol (10 ml), 2-hydroxybenzaldehyde (1.8 ml, 17 mmol) and ammonium acetate (4 g) were added over about 1 h while maintaining the temperature at 353 K. The reaction mixture was refluxed for the appropriate time and the completion of reaction was monitored by TLC. The reaction mixture extracted with dichloromethane. The solid that separated was purified by column chromatography using petroleum ether (60–80 °C) as the eluent. Yield: 2.43 g (50%). The title compound was dissolved in petroleum ether and chloroform (9:1) mixture and allowed to slow evaporate for two days to obtain crystals suitable for X-ray diffraction studies.