Crystal structure of 1-meth­oxy­pyrene

Eric G Morales-Espinoza; Ernesto Rivera; Reyna Reyes-Martínez; Simón Hernández-Ortega; David Morales-Morales

doi:10.1107/S2056989015003783

. 2015 Feb 28;71(Pt 3):o210–o211. doi: 10.1107/S2056989015003783

Crystal structure of 1-methoxypyrene

Eric G Morales-Espinoza ^a, Ernesto Rivera ^a,^*, Reyna Reyes-Martínez ^b, Simón Hernández-Ortega ^b, David Morales-Morales ^b

PMCID: PMC4350705 PMID: 25844253

Abstract

The title compound, C₁₇H₁₂O, crystallized with three independent molecules (A, B and C) in the asymmetric unit. In the crystal, the three independent molecules are linked by π–π interactions [centroid–centroid distances = 3.551 (3)–3.977 (2) Å], which lead to the formation of trimers. Between the trimers there are a number of C—H⋯π interactions generating a laminar arrangement parallel to (010). The methoxymethyl group in molecule A is disordered over two sets of sites, with an occupancy ratio of 0.56 (9):0.44 (9).

Keywords: crystal structure, pyrene, organic photovoltaics, π–π interactions, C—H⋯π interactions

Related literature

For information concerning π-conjugate systems, see: Dössel et al. (2012 ▸); Kim et al. (2008 ▸). For the synthesis of the title compound, see: Almeida et al. (2009 ▸). For details of the structures of pyrene and pyrene derivatives, see: Camerman & Trotter (1965 ▸); Gruber et al. (2006 ▸, 2010 ▸).

Experimental

Crystal data

C₁₇H₁₂O
M _r = 232.27
Orthorhombic,
a = 16.4163 (15) Å
b = 15.8838 (15) Å
c = 13.5669 (13) Å
V = 3537.6 (6) Å³
Z = 12
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.38 × 0.35 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer
15159 measured reflections
5670 independent reflections
3664 reflections with I > 2σ(I)
R _int = 0.103

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.170
S = 1.01
5670 reflections
500 parameters
22 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: SHELXL2013 and DIAMOND.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015003783/su5089sup1.cif

e-71-0o210-sup1.cif^{(481.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003783/su5089Isup2.hkl

e-71-0o210-Isup2.hkl^{(310.8KB, hkl)}

Click here for additional data file.^{(4.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015003783/su5089Isup3.cml

Click here for additional data file.^{(2MB, tif)}

A . DOI: 10.1107/S2056989015003783/su5089fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 35% probability level. The minor component of the disordered methyl group of molecule A is not shown.

Click here for additional data file.^{(1.6MB, tif)}

b . DOI: 10.1107/S2056989015003783/su5089fig2.tif

A view along the b axis of the crystal packing of the title compound, showing the laminar arrangement as a result of the π–π and C—H⋯π interactions (dashed lines; see Table 1 for details).

CCDC reference: 1050924

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

Table 1. Hydrogen-bond geometry (, ).

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C38C41/C50/C49, C7C11/C16, C11C16, and C28C33 rings, respectively.

DHA	DH	HA	D A	DHA
C17H17C Cg1ⁱ	0.96	2.93	3.78(3)	148
C34H34C Cg2ⁱ	0.96	2.99	3.770(7)	140
C19H19Cg3ⁱ	0.93	2.99	3.733(6)	138
C44H44Cg4	0.93	2.64	3.529(6)	160

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Symmetry code: (i) Inline graphic .

Acknowledgments

The financial support of this research by CONACYT (grant No. CB2010-154732) and PAPIIT (grant Nos. IN201711-3 and IN213214-3) is gratefully acknowledged. We are also grateful to CONACYT (project 128788) and PAPIIT (project IN100513).

supplementary crystallographic information

S1. Introduction

π-conjugated aromatic compounds are promising materials for use in opto-electronic devices, particularly for organic photovoltaics (OPVs). These compounds exhibit both energy and charge transfer, and their absorption and emission wavelengths can be tuned (Dössel et al., 2012). Pyrene derivatives have been extensively studied due to their excellent optical and electronic properties for example, excimer/monomer emission. Moreover, pyrene shows a long fluorescence lifetime which reaches 400 ns in cyclohexane solution (Kim et al., 2008). Due to its susceptibility to aromatic substitution at the 1-, 3-, 6- and 8-positions, pyrene is often functionalized at these positions in order to improve its properties. In this context the title compound, 1-methoxypyrene, appears in the literature as an important intermediate in the synthesis of more elaborate compounds. Thus, in this context we report herein on the synthesis and crystal structure of the title compound.

S2. Experimental

S2.1. Synthesis and crystallization

1-methoxypyrene was synthesized from 1-pyrenol which is synthesized from 1-pyrenecarboxaldehyde that is commercially available (Aldrich). Pyrenol (0.3 g, 1.37 mmol) was added to a solution of KOH (0.23 g, 4.12 mmol) dissolved in DMSO (7 mL). To this solution, methyl iodide (0.25 g, 1.78 mmol) was added and the resulting reaction mixture was stirred for 1 h at room temperature to produce the desired product (Almeida et al., 2009). Yellow crystals of the title compound were obtained by recrystallization from CHCl₃. ¹H NMR (300 MHz, CDCl₃): d = 8.47 (d, ArH, 1H), 8.09 (m, ArH, 4H), 7.94 (m, ArH, 4H), 7.55 (d, ArH, 1H), 4.17 (s, CH₃, 3H) ppm.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were included in calculated positions and treated as riding: C—H = 0.93 - 0.96 Å with U_iso(H) = 1.5U_eq(C) for the methyl H atoms and = 1.2U_eq(C) for other H atoms. The methoxy methyl group (C17) in molecule A is disordered over two sites with an occupancy ratio of 0.56 (9):0.44 (9).

S3. Results and discussion

The asymmetric unit of the title compound consist of three independent molecules (A, B and C), as shown in Fig. 1. The pyrene moiety shows bond lengths and angles similar to those observed for free pyrene (Camerman & Trotter, 1965) and other pyrene derivatives (Gruber et al., 2006, 2010).

In the crystal, the three molecules are linked by π-π interactions to give a trimeric motif. The distances between centroids of the aromatic rings have values in the range of 3.551 (3) to 3.977 (2) Å. The most significant are those between molecules A and C [Cg1···Cg9ⁱ = 3.755 (3) Å, where Cg1 and Cg9 are the centroids of rings C1—C4/C15/C14 and C35—C38/C49/C48, respectively; symmetry code: (i) x+1/2, -y+1, z] and molecules B and C [Cg6···Cg12ⁱⁱ = 3.551 (3) Å, where Cg6 and Cg12 are the centroids of rings C21—C24/C33/C32 and C45—C50, respectively; symmetry code: (ii) -x+1/2, y, z-1/2]. Between the trimmers there are C—H···π interactions generating a laminar arrangement parallel to the ac plane (Table 1 and Fig. 2).