1-(Hydroxy­meth­yl)pyrene

Tobias Gruber; Wilhelm Seichter; Edwin Weber

doi:10.1107/S1600536810002424

. 2010 Jan 23;66(Pt 2):o443. doi: 10.1107/S1600536810002424

1-(Hydroxymethyl)pyrene

Tobias Gruber ^a,^‡, Wilhelm Seichter ^a, Edwin Weber ^a,^*

PMCID: PMC2979693 PMID: 21579858

Abstract

The asymmetric unit of the title compound, C₁₇H₁₂O, contains two molecules, in which the fused aromatic ring systems are almost planar [maximum deviations = 0.0529 (9) and 0.0256 (9) Å]. In the crystal, aromatic π–π stacking interactions (perpendicular distance of centroids of about 3.4 Å) and strong O—H⋯O hydrogen bonds result in a helical arrangement of pyrenyl dimers.

Related literature

For the solid–state structures of pyrenes, see: Robertson & White (1947 ▶); Camerman & Trotter (1965 ▶); Allmann (1970 ▶); Hazell et al. (1972 ▶); Kai et al. (1978 ▶); Frampton et al. (2000 ▶). For the synthesis and structures of pyrene derivatives, see: Steward (1960 ▶); Gruber et al. (2006 ▶, 2008 ▶, 2009 ▶). For the use of pyrenes in fluorescence sensors, see: Bren (2001 ▶).

Experimental

Crystal data

C₁₇H₁₂O
M _r = 232.27
Monoclinic,
a = 19.9182 (6) Å
b = 8.8880 (3) Å
c = 13.0882 (4) Å
β = 91.719 (2)°
V = 2316.00 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 153 K
0.59 × 0.29 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
29632 measured reflections
5051 independent reflections
3801 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.111
S = 1.06
5051 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002424/rk2186sup1.cif

e-66-0o443-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002424/rk2186Isup2.hkl

e-66-0o443-Isup2.hkl^{(242.4KB, hkl)}

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—H1⋯O1Aⁱ	0.84	1.87	2.6972 (12)	167
O1A—H1A⋯O1ⁱⁱ	0.84	1.89	2.7163 (12)	167

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

Acknowledgments

The authors are indebted to F. Eissmann for his swift assistance. Financial support from the German Federal Ministry of Economics and Technolgy (BMWi) under grant No. 16IN0218 ‘ChemoChips’ is gratefully acknowledged.

supplementary crystallographic information

Comment

Owing to their electronic, optical and geometric properties, monofunctionalized pyrenes, attachable to a receptor platform, are of special interest for fluorescent sensor development (Bren, 2001). In this respect, 1–(hydroxymethyl)pyrene was prepared as part of our studies on the solid state structure of fluorogenic calixarenes with possible analytical applications (Gruber et al., 2008; Gruber et al., 2009).

Being composed of a plane aromatic region and a methylene bridged hydroxy group, the hybrid nature of the title compound is striking. The pyrene moiety alone shows no significant deviations of bond lengths and angles compared with those of the unsubstituted analogue (Robertson & White, 1947; Camerman & Trotter, 1965; Allmann, 1970; Hazell et al., 1972; Kai et al., 1978), and is almost planar. The largest deviation from the mean plane through the carbon framework of the pyrene unit is observed for atoms C2 [0.0529 (9)Å] and C1A [0.0256 (9)Å], respectively. Similiar to the unsubstituted parent substance, the pyrene moities of two molecules of 1–(hydroxymethyl)pyrene are forming a slightly displaced face–to–face dimer with an average distance of the aromatic units of about 3.4Å, though the latter are not arranged entirely coplanar [2.43 (3)°]. Additionally, within the dimer a strong hydrogen bond involving the two hydroxy groups can be observed [d(O···O) = 2.6972 (12)Å]. Worth mentoining is the varying conformation of the hydroxymethyl residue in both molecules of the asymmetrtic unit. In molecule 1, a nearly coplanar arrangement with regard to the aromatic plane can be observed [C2–C1–C17–O1 = 3.46 (15)°], whereas in molecule 2 the same torsion angle of 116.54 (12)° is adopted (Fig. 1). These findings are explained by the sterical demands of a strong hydrogen bond between two hydroxy groups [d(O···O) = 2.7163 (12)Å], which links the pyrene dimers mentioned above in a helical manner in the direction of the crystallographic b axis. Considering the packing, two of these helices, each in the opposite direction, are connected by edge–to–face interactions of the pyrenyl groups as shown in Fig. 2.

Experimental

The title compound was synthesized from commercially available pyrene–1–carbaldehyde, which was reduced with sodium borohydride in boiling methanol, following an analogous procedure described for the reduction of anthracene–9–carbaldehyde (Steward, 1960; Gruber et al., 2006). Colourless plates (m.p. 393–394 K) of the solvent–free 1–(hydroxymethyl)pyrene suitable for X–ray diffraction were obtained by recrystallization from n–hexane/dichloromethane (1:2).