Crystal structure of trans-1-{2-[4-(di­methyl­amino)­phen­yl]eth­yl}-4-[2-(pyren-1-yl)eth­yl]cyclo­hexa­ne

Sreevidya Thekku Veedu; Simone Techert

doi:10.1107/S2056989015013729

. 2015 Jul 31;71(Pt 8):o629–o630. doi: 10.1107/S2056989015013729

Crystal structure of trans-1-{2-[4-(dimethylamino)phenyl]ethyl}-4-[2-(pyren-1-yl)ethyl]cyclohexane

Sreevidya Thekku Veedu ^a,^b,^*, Simone Techert ^a,^b,^*

PMCID: PMC4650969 PMID: 26594590

Abstract

The title compound, C₃₄H₃₇N, is a pyrene derivative in which the pyrene ring system is linked to an ethylcyclohexane unit which, in turn, carries a [4-(dimethylamino)phenyl]ethyl substituent in the para position. The central cyclohexane ring has a chair conformation, with the exocyclic C—C bonds in equatorial orientations. The benzene ring is inclined to the mean plane of the pyrene ring system [maximum deviation = 0.038 (4) Å] by 14.84 (15)°. In the crystal, molecules are linked by C—H⋯π interactions, forming chains propagating along [010]. The crystal was refined as a non-merohedral twin [domain ratio = 0.9989 (4):0.0011 (4)].

Keywords: crystal structure, pyrene, donor acceptor, electron transfer, C—H⋯π interactions

Related literature

For charge transfer in donor–acceptor systems, see: Wasielewski (1992 ▸); Willemse et al. (2000 ▸); Thekku Veedu et al. (2014a ▸). For related structures, see: Thekku Veedu et al. (2014b ▸); Wang et al. (2010 ▸). For the synthesis of the title compound, see: Dewar & Mole (1956 ▸); Norman et al. (1958 ▸). graphic file with name e-71-0o629-scheme1.jpg

Experimental

Crystal data

C₃₄H₃₇N
M _r = 459.64
Monoclinic,
a = 7.1927 (4) Å
b = 10.4082 (6) Å
c = 33.399 (2) Å
β = 91.473 (4)°
V = 2499.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEXII DUO diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T _min = 0.976, T _max = 0.990
38082 measured reflections
38082 independent reflections
23477 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.069
wR(F ²) = 0.195
S = 1.07
38082 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015013729/su5171sup1.cif

e-71-0o629-sup1.cif^{(1.7MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013729/su5171Isup2.hkl

e-71-0o629-Isup2.hkl^{(2MB, hkl)}

Click here for additional data file.^{(10.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015013729/su5171Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015013729/su5171fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.1MB, tif)}

a . DOI: 10.1107/S2056989015013729/su5171fig2.tif

The crystal packing of the title compound, viewed along the a axis. The C—H⋯π interactions linking the molecules are shown as dashed lines (see Table 1 for details).

CCDC reference: 1413890

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C20C23/C32/C31 ring.

DHA	DH	HA	D A	DHA
C26H26Cg1ⁱ	0.95	2.60	3.4927(15)	156

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Symmetry code: (i) Inline graphic .

Acknowledgments

ST thanks DFG, SFB 755 and SFB 1073 for financial support. STV thanks G. and L. Busse for technical help, and the synthesis group at Max Planck Institute for Biophysical Chemistry, Göttingen.

supplementary crystallographic information

S1. Comment

Electron-transfer reactions are fundamental processes in chemistry and also in biology. Going back to nature, photo-induced electron transfer (PI—ET) is the key step in photosynthesis where light harvesting complexes are functional centers in plants which converts solar energy into chemical energy. In the past decades, to gain more insight into electron transfer processes extensive studies have been carried out on the optical behaviour of systems consisting of donor acceptor groups linked by different bridges (Thekku Veedu et al., 2014a; Wasielewski, 1992; Willemse et al., 2000). These molecules are also ideal systems for studying solvation dynamics and non-linear optical properties. In the title compound (PyDMAD), the electron donor N,N'-dimethylaniline (DMA) unit is covalently linked to the electron acceptor pyrene by an extended diethylcyclohexane bridge between the donor and acceptor.

The molecular structure of the title pyrene derivative is illustrated in Fig. 1. Pyrene is linked to an ethylcyclohexane ring which in turn carries a 4-dimethylaminophenylethyl substituent in the para-position. The bond lengths and angles are within normal ranges and are comparable to those reported for similar structures (Thekku Veedu et al., 2014b; Wang et al., 2010). The cyclohexane ring (C9—C14) has a chair conformation. The benzene ring (C1—C6) is inclined to the mean plane of the pyrene ring system (maximum devation = 0.038 (4) Å for atom C29), by 14.84 (15) °. The various hetero atoms of the dimethylamino group are displaced from the benzene ring by 0.078 (4) Å for N1, 0.102 (4) Å for C33, but 0.549 (4) Å for atom C34.

In the crystal, molecules are linked via C—H···π interactions forming chains along the b axis direction (Table 1 and Fig. 2).

S2. Synthesis and crystallization

Commercially available 1-aminopyrene after diazotization reaction was coupled with N,N'-dimethylaniline according to the previously reported procedure (Dewar & Mole 1956; Norman et al., 1958). The crude product was then purified on an aluminium oxide column with a mixture of cyclohexane/toluene as eluent and applying HPLC. Plate-like colourless crystals of the title compound were obtained by slow evaporation of a solution in ethyl acetate.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 - 1.00 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms. The crystal was refined as a non-merohedral twin [refined BASF ratio = 0.9989 (4):0.0011 (4)].