1-[2-(4-Chloro­benz­yloxy)-2-phenyl­ethyl]-1H-benzotriazole

Özden Özel Güven; Meral Bayraktar; Simon J Coles; Tuncer Hökelek

doi:10.1107/S1600536810015692

. 2010 May 8;66(Pt 6):o1246–o1247. doi: 10.1107/S1600536810015692

1-[2-(4-Chlorobenzyloxy)-2-phenylethyl]-1H-benzotriazole

Özden Özel Güven ^a, Meral Bayraktar ^a, Simon J Coles ^b, Tuncer Hökelek ^c,^*

PMCID: PMC2979387 PMID: 21579353

Abstract

The asymmetric unit of the title compound, C₂₁H₁₈ClN₃O, contains two crystallographically independent molecules which differ slightly in the orientations of chlorobenzyloxy units. In one of the molecules, the phenyl and chlorophenyl rings are oriented at dihedral angles of 38.09 (6) and 42.15 (6)°, respectively, with respect to the benzotriazole ring [43.23 (6) and 29.80 (6)° in the other molecule]. The dihedral angle between the phenyl and chlorophenyl rings is 77.63 (6)° in one of the molecules and 72.97 (6)° in the other. The crystal structure is stabilized by weak C—H⋯π interactions.

Related literature

For general background to the biological activity of benzotriazole derivatives, see: Hirokawa et al. (1998 ▶); Yu et al. (2003 ▶); Kopanska et al. (2004 ▶). For related structures, see: Caira et al. (2004 ▶); Freer et al. (1986 ▶); Katritzky et al. (2001 ▶); Özel Güven et al. (2007a ▶,b ▶, 2008a ▶,b ▶,c ▶, 2010 ▶); Peeters et al. (1979a ▶,b ▶, 1996 ▶); Swamy et al. (2006 ▶).

Experimental

Crystal data

C₂₁H₁₈ClN₃O
M _r = 363.83
Monoclinic,
a = 7.2163 (2) Å
b = 36.8545 (9) Å
c = 13.3019 (3) Å
β = 91.529 (1)°
V = 3536.42 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 120 K
0.40 × 0.40 × 0.14 mm

Data collection

Nonius Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.910, T _max = 0.966
26731 measured reflections
7993 independent reflections
5918 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.189
S = 1.07
7993 reflections
470 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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 I, global. DOI: 10.1107/S1600536810015692/ci5085sup1.cif

e-66-o1246-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015692/ci5085Isup2.hkl

e-66-o1246-Isup2.hkl^{(383.2KB, hkl)}

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

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

Cg1, Cg2 and Cg3 are centroids of the C9–C14, C9′–C14′ and C16–C21 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯Cg2ⁱ	0.95	2.62	3.515 (2)	157
C11′—H11′⋯Cg1ⁱⁱ	0.95	2.79	3.635 (2)	149
C14—H14⋯Cg2ⁱⁱⁱ	0.95	2.64	3.584 (2)	172
C14′—H14′⋯Cg1^iv	0.95	2.81	3.755 (2)	172
C18′—H18′⋯Cg3^v	0.95	2.83	3.502 (2)	129

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

Acknowledgments

The authors acknowledge the Zonguldak Karaelmas University Research Fund for support.

supplementary crystallographic information

Comment

In recent years, there has been increasing interest in the syntheses of heterocyclic compounds that have biological and commercial importance. Clotrimazole, miconazole, econazole, ketonazole, itraconazole and fluconazole are well-known imidazoles. 1H-1,2,4-Triazole ring containing azole derivatives have been developed for clinical uses as antifungal agents. Recently, structures containing benzimidazole ring in place of miconazole and econazole have been reported, and these molecules have been shown more antibacterial activity than antifungal activity (Özel Güven et al., 2007a,b). The crystal structures of miconazole (Peeters et al., 1979a), ketonazole (Peeters et al., 1979b), econazole (Freer et al., 1986), itraconazole (Peeters et al., 1996) and fluconazole (Caira et al., 2004) have been reported. Recently, we reported crystal structures of related compounds (Özel Güven et al., 2008a,b,c). Benzotriazole derivatives also exhibit a good degree of analgesic, antiinflammatory, diuretic, antiviral and antihypertensive activities (Hirokawa et al., 1998; Yu et al., 2003; Kopanska et al., 2004). Crystal structures of benzotriazole ring possessing compounds have been reported (Katritzky et al., 2001; Swamy et al., 2006; Özel Güven et al., 2010). Now, we report herein the crystal structure of the title benzotriazole derivative.

The asymmetric unit of the title compound (Fig. 1) contains two crystallographically independent molecules which differ slightly in the orientations of the chlorobenzyloxy units. The bond lengths and angles are generally within normal ranges. In each molecule, the planar benzotriazole rings [A (N1-N3/C1-C6) and A' (N1'-N3'/C1'-C6')] are oriented with respect to the phenyl [B (C9-C14) and B' (C9'-C14')] and benzene [C (C16-C21)] and C' (C16'-C21')] rings at dihedral angles of A/B = 37.98 (9), A/C = 42.27 (9) ° and A'/B' = 43.20 (9), A'/C' = 29.82 (9)°. The dihedral angles between phenyl and benzene rings are B/C = 77.63 (6) and B'/C' = 72.97 (6) °. Atoms C7 and C7' are -0.012 (2) and -0.112 (2) Å away from the planes of the benzotriazole rings, respectively.

In the crystal structure, molecules are stacked along the a-axis (Fig. 2). Weak C—H···π interactions (Table 1) involving the C9-C14, C9'-C14' and C16-C21 rings stabilize the structure.

Experimental

The title compound was synthesized by the reaction of 2-(1H-benzotriazol-1-yl)-1-phenylethanol (Özel Güven et al., 2010) with aryl halide using NaH. 2-(1H-Benzotriazol-1-yl)-1-phenylethanol (200 mg, 0.84 mmol) was dissolved in DMF (4 ml). NaH (33 mg, 0.84 mmol) was added to the solution portionwise. After stirring the mixture a few minutes, 4-chlorobenzyl bromide (171.8 mg, 0.84 mmol) was added dropwise. Then, the reaction mixture was stirred additional 3 h at room temperature. The reaction was stopped by adding methanol (5 ml). After evaporation of the solvent, dichloromethane was added to the reaction mixture and extracted with water. Then, the organic phase was separated, dried, filtered and evaporated. The precipitate formed was purified by column chromatography using chloroform and crystallized from iso-propanol to obtain colorless crystals suitable for X-ray analysis (yield; 137 mg, 46%).