4-[Tris(1H-pyrazol-1-yl)meth­yl]phenol

Xiao-Yan Chen; Xiaoping Yang; Bradley J Holliday

doi:10.1107/S1600536811043042

. 2011 Oct 29;67(Pt 11):o3045. doi: 10.1107/S1600536811043042

4-[Tris(1H-pyrazol-1-yl)methyl]phenol

Xiao-Yan Chen ^a, Xiaoping Yang ^a, Bradley J Holliday ^a,^*

PMCID: PMC3247439 PMID: 22220057

Abstract

The title compound, C₁₆H₁₄N₆O, was prepared by the condensation of 4-(trifluoromethyl)phenol and sodium pyrazol-1-ide in a yield of 58%. The dihedral angles formed by the planes of the pyrazole rings are 50.7 (2), 71.2 (3) and 95.8 (2)°. The molecules are associated into dimers by pairs of intermolecular O—H⋯N hydrogen bonds involving the hydroxy groups and pyrazole N atoms. In addition, π–π stacking between the phenol rings of these inversion-related dimers is observed, with a ring centroid-to-centroid distance of 3.9247 (10) Å.

Related literature

For the preparation and coordination chemistry of tris(pyrazolyl)borates and tris(pyrazolyl)methanes, see: Trofimenko (1966 ▶, 1970 ▶, 1999 ▶); Pettinari & Pettinari (2005 ▶); Reger et al. (2000 ▶). For the chemistry of tris(pyrazolyl)methane derivatives, see: Humphrey et al. (1999 ▶). For similar structures, see: Liddle & Gardinier (2007 ▶).

Experimental

Crystal data

C₁₆H₁₄N₆O
M _r = 306.33
Triclinic,
a = 8.5065 (17) Å
b = 8.6829 (17) Å
c = 10.815 (2) Å
α = 96.97 (3)°
β = 91.51 (2)°
γ = 109.40 (3)°
V = 746.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 K
0.30 × 0.28 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: Gaussian (XPREP in SHELXTL; Sheldrick, 2008 ▶) T _min = 0.973, T _max = 0.983
4225 measured reflections
2609 independent reflections
1975 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.099
S = 1.07
2609 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: XL in SHELXTL/PC (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and POV-RAY (Persistence of Vision Team, 2004 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811043042/pk2340sup1.cif

e-67-o3045-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043042/pk2340Isup2.hkl

e-67-o3045-Isup2.hkl^{(128.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811043042/pk2340Isup3.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
O1—H1A⋯N4ⁱ	0.82	2.02	2.836 (2)	173

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors gratefully acknowledge the Robert A. Welch Foundation (grant No. F-1631), the National Science Foundation (grant Nos. CHE-0741973 and CHE-0847763), the Advanced Research Program of the Texas Higher Education Coordinating Board (grant No. 01916-090-2010) and the University of Texas at Austin for financial support of this research.

supplementary crystallographic information

Comment

Since seminal reports on tris(pyrazolyl)borates and tris(pyrazolyl)methanes (Trofimenko, 1966, 1970), variations on these ligands have been widely studied. Currently, there are great research efforts to study ligands of this type that are functionalized at the back boron or methine positions. The synthesis and coordination chemistry of aryltris(pyrazolyl)borates have also been well investigated, which has allowed significant advances in iron(II) spin-crossover chemistry. However, the chemistry of analogous tris(pyrazolyl)methane derivatives is almost unknown. Herein, we demonstrate the preparation of a new tris(pyrazolyl)methane derivative, 4-[tris(1H-pyrazol-1-yl)methyl]phenol, using a one-pot synthesis method with 4-(trifluoromethyl)phenol and freshly prepared sodium pyrazol-1-ide to give the desired product in good yield.

The solid state structure of 4-[tris(1H-pyrazol-1-yl)methyl]phenol can be seen in Fig. 1. There are two molecules in the unit cell. The molecules are associated into dimers by pairs of intermolecular O—H···N hydrogen bonds involving the hydroxyl groups and pyrazole N atoms. In addition, π–π stacking between the phenol rings of these inversion-related (-x + 2, -y + 2, -z) dimers is observed with a ring centroid-to-centroid distance of 3.9247 (10) Å.

Experimental

The title compound was prepared by refluxing 4-(trifluoromethyl)phenol (0.162 g, 1.0 mmol) and freshly prepared sodium pyrazol-1-ide (0.361 g, 4.0 mmol) in tetrahydrofuran (20 ml) for 12 h under a nitrogen atomsphere. The desired product was purified by column chromatography on silica gel using CH₂Cl₂ as the eluent with a yield of 58%. Single crystals suitable for X-ray diffraction were obtained via slow evaporation from a methanol solution.