2-(Naphthalen-1-yl)-1-phenyl-1H-benzimid­azole benzene hemisolvate

N Srinivasan; A Thiruvalluvar; S Rosepriya; S M Prakash; R J Butcher

doi:10.1107/S160053681303331X

. 2013 Dec 14;70(Pt 1):o55–o56. doi: 10.1107/S160053681303331X

2-(Naphthalen-1-yl)-1-phenyl-1H-benzimidazole benzene hemisolvate

N Srinivasan ^a,^b, A Thiruvalluvar ^c,^*, S Rosepriya ^c, S M Prakash ^a,^d, R J Butcher ^e

PMCID: PMC3914093 PMID: 24526997

Abstract

In the title compound, C₂₃H₁₆N₂·0.5C₆H₆, the benzimidazole unit [maximum deviation = 0.0258 (6) Å] and the naphthalene ring system [maximum deviation = 0.0254 (6) Å] are both essentially planar and make a dihedral angle of 61.955 (17)°. The imidazole ring makes dihedral angle of 61.73 (4)° with the phenyl ring. An intramolecular C—H⋯N hydrogen bond generates an S(6) ring motif. In the crystal, seven weak C—H⋯π interactions involving the fused ring system, the benzene solvent molecule, the imidazole phenyl rings are observed, leading to a three-dimensional architecture.

Related literature

For linear and non-linear optical properties and the thermal stability of benzimidazole-based chromophores, see: Cross et al. (1995 ▶). For imidazole as a component of vitamin B₁₂, purine and caffeine, see: Brown (2005 ▶). For commercial and therapeutic applications of substituted benzimidazole derivatives, see: Spasov et al. (1999 ▶). For related crystal structures, see: Jayamoorthy et al. (2012 ▶, 2013 ▶); Rosepriya et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-70-00o55-scheme1.jpg

Experimental

Crystal data

C₂₃H₁₆N₂·0.5C₆H₆
M _r = 359.43
Triclinic,
a = 8.5529 (3) Å
b = 9.4517 (3) Å
c = 11.8936 (3) Å
α = 86.334 (2)°
β = 89.838 (2)°
γ = 75.051 (3)°
V = 926.94 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 123 K
0.72 × 0.59 × 0.42 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ▶), using a multifaceted crystal model (Clark & Reid, 1995 ▶)] T _min = 0.963, T _max = 0.977
57784 measured reflections
12045 independent reflections
9086 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.160
S = 1.05
12045 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL2013 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681303331X/jj2179sup1.cif

e-70-00o55-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681303331X/jj2179Isup2.hkl

e-70-00o55-Isup2.hkl^{(659.4KB, hkl)}

Click here for additional data file.^{(2.9KB, cdx)}

Supporting information file. DOI: 10.1107/S160053681303331X/jj2179Isup3.cdx

Click here for additional data file.^{(8KB, cml)}

Supporting information file. DOI: 10.1107/S160053681303331X/jj2179Isup4.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1, Cg2, Cg3, Cg4 and Cg8 are the centroids of the N1/C2/N3/C9/C8 imidazole ring, the C4–C9 fused benzene ring, the C11–C16 phenyl ring, the C21–C24,C30/C29 fused benzene ring and the C1A,C2A,C3A′,C1A′,C2A′,C3A benzene ring, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C28—H28⋯N3	0.95	2.61	3.2113 (10)	121
C7—H7⋯Cg4ⁱ	0.95	2.75	3.6019 (8)	150
C15—H15⋯Cg8ⁱⁱ	0.95	2.99	3.6981 (9)	132
C15—H15⋯Cg8ⁱⁱⁱ	0.95	2.99	3.6981 (9)	132
C22—H22⋯Cg1^iv	0.95	2.91	3.6478 (8)	136
C24—H24⋯Cg3^v	0.95	2.76	3.4888 (9)	134
C26—H26⋯Cg2ⁱⁱⁱ	0.95	2.87	3.5801 (9)	133
C27—H27⋯Cg1ⁱⁱⁱ	0.95	2.97	3.7258 (8)	137

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

SMP thanks Annamaliar College of Engineering, Mudaiyur, for providing constant support for this research. RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

1. Comment

Benzimidazole based chromophores have received increasing attention due to their distinctive linear, non-linear optical properties and also due to their excellent thermal stability in guest-host systems (Cross et al., 1995). They are a component of vitamin B₁₂ (Brown, 2005) and are related to the DNA base purine and the stimulant caffeine. Substituted benzimidazole derivatives have found commercial applications in veterinarian medicine as anthelmintic agents and in diverse human therapeutic areas as an antiulcer and antihistaminic (Spasov et al., 1999). Therefore, the preparation of benzimidazoles has gained considerable attention in recent years. Jayamoorthy et al., (2012, 2013) and Rosepriya et al., (2011) have reported closely related structures of benzimidazole derivatives. We are interested to use 2-(naphthalen-1-yl)-1-phenyl-1H-benzimidazole as ligand to study its photophysical properties.

The assymmetric unit of the title compound, C₂₃H₁₆N₂·0.5C₆H₆, (Fig. 1), contains a 2-(naphthalen-1-yl)-1-phenyl-1H-benzimidazole molecule and a hemibenzene solvent molecule. The benzimidazole unit is essentially planar [maximum deviation of -0.0258 (6) Å for C8]. The naphthalene unit is also essentially planar [maximum deviation of -0.0254 (6) Å for C23]. The benzimidazole unit makes dihedral angle of 61.955 (17)° with the naphthalene unit. The imidazole ring makes dihedral angle of 61.73 (4)° with the phenyl group attached to N1.

An intramolecular C28—H28···N3 hydrogen bond (Fig. 1) generates an S(6) ring motif (Bernstein et al., 1995). The packing of the title compound, viewed along the a axis is shown in Fig. 2. In the crystal, seven weak C7—H7···π interactions involving the fused benzene ring, C15—H15···π interactions involving the solvent benzene ring, C22—H22···π interaction involving the imidazole ring, C24—H24···π interaction involving the phenyl ring, C26—H26···π interaction involving the fused benzene ring, C27—H27···π interaction involving the imidazole ring, are observed, leading to a three dimensional architecture (Fig. 3, Table 1).

2. Experimental

To the pure N-phenyl-o-phenylenediamine (17 mmol, 3.128 g) in ethanol (10 ml), napthaldehyde (17 mmol, 1.9 ml) and ammonium acetate (3 g) was added about 1 h by maintaining the temperature at 353 K. The reaction mixture was refluxed for 48 hrs and the completion of reaction was monitored by TLC, finally the reaction extracted by dichloromethane. The solid separated was purified by column chromatography using benzene as the eluent. Yield: 2.65 g (50%). The compound was dissolved in benzene and ethyl acetate (9:1) mixture and allowed to slow evaporation for two days, to obtain crystals suitable for X-ray diffraction studies.