Crystal structure of 1-(4-fluoro­phen­yl)-4-(4-meth­oxy­phen­yl)-1H-1,2,3-triazole

Balbir Kumar; Madhvi Bhardwaj; Satya Paul; Rajni Kant; Vivek K Gupta

doi:10.1107/S2056989015012153

. 2015 Jul 4;71(Pt 8):o534–o535. doi: 10.1107/S2056989015012153

Crystal structure of 1-(4-fluorophenyl)-4-(4-methoxyphenyl)-1H-1,2,3-triazole

Balbir Kumar ^a, Madhvi Bhardwaj ^b, Satya Paul ^b, Rajni Kant ^a, Vivek K Gupta ^a,^*

PMCID: PMC4571383 PMID: 26396783

Abstract

In the title compound, C₁₅H₁₂FN₃O, the triazole ring forms dihedral angles of 30.57 (8) and 21.81 (9)° with the fluoro-substituted and methoxy-substituted benzene rings, respectively. The dihedral angle between the benzene rings is 51.53 (7)°. In the crystal, π–π interactions between the triazole rings [centroid–centroid seperations = 3.774 (2) and 3.841 (2) Å] form chains along [010].

Keywords: crystal structure; 1,2,3-triazole; π–π interactions

Related literature

For related literature on 1,2,3-triazoles, see: Aher et al. (2009 ▸); Jordao et al. (2009 ▸); Vijaya Raghava Reddy et al. (2010 ▸); Soltis et al. (1996 ▸). For applications of 1,2,3-triazoles, see: Pérez-Balderas et al. (2003 ▸); Wu et al. (2004 ▸); Kumar & Pandey (2008 ▸); Haridas et al. (2008 ▸); Turner et al., (2007 ▸); Angell & Burgess (2007 ▸); For the synthesis of 1,2,3-triazoles, see: Huisgen et al. (1965 ▸); Wang et al. (2010 ▸). For related structures, see: Abdel-Wahab et al. (2012 ▸); Zhang et al. (2004 ▸).

Experimental

Crystal data

C₁₅H₁₂FN₃O
M _r = 269.28
Triclinic,
a = 5.6572 (5) Å
b = 7.3692 (8) Å
c = 15.5711 (15) Å
α = 79.202 (9)°
β = 81.159 (8)°
γ = 89.442 (8)°
V = 629.95 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▸) T _min = 0.806, T _max = 1.000
4369 measured reflections
2461 independent reflections
1575 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.179
S = 1.04
2461 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015012153/lh5772sup1.cif

e-71-0o534-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012153/lh5772Isup2.hkl

e-71-0o534-Isup2.hkl^{(118.4KB, hkl)}

Click here for additional data file.^{(5.2KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015012153/lh5772Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015012153/lh5772fig1.tif

The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.

Click here for additional data file.^{(1.9MB, tif)}

a . DOI: 10.1107/S2056989015012153/lh5772fig2.tif

The packing arrangement of molecules viewed along the a axis.

CCDC reference: 1408544

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

Acknowledgments

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under Project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

S1. Comment

1,2,3-Triazoles are an important class of organic compounds which have become prominent in recent years as superbly versatile five membered nitrogen heterocycles. The 1,2,3-triazole family exhibit a broad spectrum of bioactivities such as antifungal (Aher et al., 2009) antiviral (Jordao et al., 2009), antibacterial (Vijaya Raghava Reddy et al., 2010) and anticancer (Soltis et al., 1996) activities. Furthermore 1,4-disubstituted 1,2,3-triazoles have also been used as a ligation tool for the synthesis of neoglyco-conjugates (Perez-Balderas et al., 2003), multivalent dendrimeric peptides (Wu et al., 2004), ionic receptors (Kumar et al., 2008), triazolophanes (Haridas et al., 2008), cyclic peptides (Turner et al., 2007) and peptidomimetics (Angell et al., 2007). 1,2,3-Triazoles are traditionally obtained using the thermal 1,3-dipolar cycloaddition of organic azides with alkynes (Huisgen et al., 1965) that has been known for nearly five decades. Recently, copper based catalysis was found to dramatically accelerate the reaction under mild conditions while achieving a high regioselectivity towards the 1,4-regioisomer of the triazole product (Wang et al., 2010). This powerful, highly reliable, and selective reaction is the paradigm of a click reaction, which placed it in a class of its own and has enabled many novel applications.

The molecular structure of the title compound is shown in Fig. 1. The triazole ring forms dihedral angles of 30.57 (8)° and 21.81 (9)° with the fluoro-substituted and methoxy-substituted benzen rings, respectively. The dihedral angle between the benzene rings is 51.53 (7)°. All bond lengths and angles are normal and correspond to those observed in the related structures (Zhang et al., 2004; Abdel-Wahab et al., 2012). The C15—F1 bond length [1.357 (4) Å] agrees well with the accepted value of 1.340 Å for the F-C_aromatic length and is in good agreement with a structure of this type (Abdel-Wahab et al., 2012). In the crystal, π–π interactions observed between the triazole rings [centroid–centroid seperations = 3.774 (2) and 3.841 (2) Å] form chains along [010] (Fig. 2).

S2. Experimental

Synthesis of 1-(4-flourophenyl)-4-(4-methoxyphenyl) -1H-1,2,3-triazole: To 4-fluoroaniline (0.22 g, 2 mmol) in a round bottomed flask maintained at 273-278 K, mixture of conc. HCl: H₂O (1.5 ml, 1:1) was added and stirred for 5 min. Then solution of NaNO₂ (0.17 g, 2.5 mmol in 1 ml water) was added dropwise over a period of 5 min. After stirring for another 5 min, sodium azide (0.19 g, 3 mmol) was added and the reaction mixture was further stirred for another 10 min. Finally, 4-methoxyphenylacetylene (0.19 g, 1.5 mmol) and catalyst [Cu(0)-Fe₃O₄@SiO₂/NH₂Cel] (0.05 g) were added to the reaction mixture followed by stirring at room temperature for 6 h. The reaction was then stopped and the catalyst was separated using an external magnet. The reaction mixture was extracted with EtOAc, washed with water and dried over Na₂SO₄. Finally, the product was obtained after removal of the solvent under reduced pressure followed by crystallization with EtOAc: pet ether. The product, 1-(4-flourophenyl)-4-(4-methoxyphenyl) -1H-1,2,3-triazole was obtained as shiny white crystals.