6-(2-Methoxy­benzyl­amino)purine

Zdeněk Trávníček; Miroslava Matiková-Maľarová; Jiří Mikulík

doi:10.1107/S1600536808009203

. 2008 Apr 10;64(Pt 5):o823. doi: 10.1107/S1600536808009203

6-(2-Methoxybenzylamino)purine

Zdeněk Trávníček ^a,^*, Miroslava Matiková-Maľarová ^a, Jiří Mikulík ^a

PMCID: PMC2961176 PMID: 21202313

Abstract

The title compound, C₁₃H₁₃N₅O, consists of discrete molecules connected by N—H⋯N hydrogen bonds to form infinite chains, with N⋯N separations of 3.0379 (15) and 2.8853 (15) Å. The benzene and purine ring systems make a dihedral angle of 77.58 (3)°. The crystal structure is further stabilized by intramolecular N⋯O interactions [2.9541 (12) Å] and intermolecular C—H⋯C and C⋯C contacts [3.304 (2), 3.368 (2), 3.667 (2), 3.618 (2) and 3.512 (2) Å] which arrange the molecules into graphite-like layers. The interlayer separations are 3.248 and 3.256 Å.

Related literature

For related structures of 6-benzylaminopurine derivatives, see: Maloň et al. (2001 ▶); Trávníček et al. (2006 ▶); Trávníček & Rosenker (2006 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₃H₁₃N₅O
M _r = 255.28
Triclinic,
a = 7.3518 (2) Å
b = 8.0877 (2) Å
c = 9.9771 (3) Å
α = 78.439 (3)°
β = 85.099 (2)°
γ = 83.803 (2)°
V = 576.56 (3) Å³
Z = 2
Mo Kα radiation radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
0.20 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur2 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.947, T _max = 0.990
4904 measured reflections
2026 independent reflections
1709 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.082
S = 1.09
2026 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97 and DIAMOND.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808009203/bh2166sup1.cif

e-64-0o823-sup1.cif^{(15.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009203/bh2166Isup2.hkl

e-64-0o823-Isup2.hkl^{(99.6KB, 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
N6—H6A⋯N7ⁱ	0.88	2.19	3.0379 (15)	162
N9—H9C⋯N3ⁱⁱ	0.88	2.02	2.8853 (15)	167
C16—H16C⋯C14ⁱⁱⁱ	0.98	2.87	3.6666 (18)	139
C16—H16B⋯C15^iv	0.98	2.85	3.6182 (18)	136
C12—H12A⋯C6ⁱⁱⁱ	0.95	2.77	3.5119 (17)	136

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

Acknowledgments

The financial support of this work by the Ministry of Education, Youth and Sports of the Czech Republic (MSM6198959218) and the Grant Agency of the Czech Republic (GAČR 203/08/P436) is gratefully acknowledged.

supplementary crystallographic information

Comment

The structure of the title molecule, (I), extends our crystallographic knowledge regarding aromatic cytokinins and cyclin dependent kinase inhibitors derived from 6-benzylaminopurine.

The molecular structure of (I) is shown in Fig. 1. The molecule contains three different aromatic rings: benzene (A), pyrimidine (B) and imidazole (C). Each ring is essentially planar with the maximum deviations from the least-squares planes being 0.0169 (12) Å for C11 (ring A), 0.0147 (12) Å for C6 (ring B), and 0.0054 (13) Å for C8 (ring C). The dihedral angle between benzene ring (A) and purine skeleton (rings B and C) is 77.58 (3)°, whilst the pyrimidine (B) and imidazole (C) rings are almost coplanar, making a dihedral angle of 3.84 (4)° (Brandenburg, 2006). The interatomic parameters of (I) are comparable to those found for compounds bearing an electroneutral N9—H 6-benzylaminopurine moiety, e.g. 6-(2-chlorobenzylamino)purine dihydrate (Maloň et al., 2001), 6-(2-bromobenzylamino)purine (Trávníček & Rosenker, 2006) and 6-(2-chloro-4-fluorobenzylamino)purine (Trávníček et al., 2006). To date, 59 structures of compounds involving the 6-benzylaminopurine skeleton have been deposited in the CSD (Cambridge Structural Database, Version 5.29; Allen, 2002).

The secondary structure of (I) is stabilized by intermolecular hydrogen bonds of the N—H···N type (Table 1, Fig. 2), which connect the molecules into infinite one-dimensional chains. Moreover, intramolecular N···O interactions [N6···O1 = 2.9541 (12) Å, Fig. 2], and non-bonding intermolecular interactions of the type C···C [C2···C5ⁱⁱⁱ = 3.304 (2) Å, C2···C6ⁱⁱⁱ = 3.368 (2) Å] and C—H···C [C16···C14^iv = 3.667 (2), C16···C15^v = 3.618 (2), and C12···C6^iv = 3.512 (2) Å; symmetry codes: (iii) 1 - x, 2 - y, 1-z; (iv) 1 - x, 1 - y, 2-z; (v) -x, 1 - y, 2 - z] also contribute to the stabilization of the crystal structure (Fig. 3). The later non-bonding interactions arrange the molecules into graphite-like layers (Fig. 4). The separations between two layers formed by purine moieties are not equal, with the shortest distances being 3.248 and 3.256 Å. For comparison, the corresponding layer-to-layer separation has been found to be 3.352 Å (Space group P6₃/mmc, ICSD No. 52230), and 3.395 Å (Space group P6₃mc, ICSD No. 31170) in the crystal structure of graphite, as deposited in the ICSD (The Inorganic Crystal Structure Database, Version 1.4.2, 2007–2 and calculated using DIAMOND (Brandenburg, 2006).

Experimental

The title compound, was synthesized by a recently described method (Trávníček & Rosenker, 2006). The obtained microcrystalline product was recrystallized from hot N,N-dimethylformamide. Well shaped colourless single crystals, suitable for X-ray structural analysis, were formed after slow evaporation of the solvent over a period of few days. The crystals were filtered off, washed with EtOH and Et₂O and dried in air.