9-Benzyl-6-benzyl­sulfanyl-9H-purin-2-amine

Maywan Hariono; Habibah A Wahab; Mei Lan Tan; Mohd Mustaqim Rosli; Ibrahim Abdul Razak

doi:10.1107/S1600536814001986

. 2014 Feb 12;70(Pt 3):o288. doi: 10.1107/S1600536814001986

9-Benzyl-6-benzylsulfanyl-9H-purin-2-amine

Maywan Hariono ^a, Habibah A Wahab ^a,^b,^‡, Mei Lan Tan ^b, Mohd Mustaqim Rosli ^c, Ibrahim Abdul Razak ^c,^*,^§

PMCID: PMC3998501 PMID: 24764997

Abstract

In the title compound, C₁₉H₁₇N₅S, the dihedral angles between the purine ring system (r.m.s. deviation = 0.009 Å) and the S-bound and methylene-bound phenyl rings are 74.67 (8) and 71.28 (7)°, respectively. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R ₂ ²(8) loops. C—H⋯N interactions link the dimers into (100) sheets.

Related literature

For background to the biological activity of thiopurine derivatives, see: Hadda et al. (2009 ▶); Nguyen et al. (2009 ▶). For further synthetic details, see: Banh et al. (2011 ▶); Salvatore et al. (2002 ▶, 2005 ▶).

Experimental

Crystal data

C₁₉H₁₇N₅S
M _r = 347.44
Monoclinic,
a = 16.7346 (7) Å
b = 5.5511 (3) Å
c = 20.4817 (10) Å
β = 121.325 (3)°
V = 1625.31 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.69 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.868, T _max = 0.972
16728 measured reflections
4956 independent reflections
3416 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.137
S = 1.06
4956 reflections
234 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.58 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814001986/hb7176sup1.cif

e-70-0o288-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001986/hb7176Isup2.hkl

e-70-0o288-Isup2.hkl^{(242.8KB, hkl)}

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814001986/hb7176Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=983914

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H1N5⋯N3ⁱ	0.91 (3)	2.14 (3)	3.040 (3)	173 (2)
C7—H7B⋯N3ⁱⁱ	0.99	2.57	3.548 (2)	172
C8—H8A⋯N2ⁱⁱⁱ	0.95	2.39	3.274 (2)	155

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

Acknowledgments

MH and HAW acknowledge the Malaysian Ministry of Science, Technology and Innovations (MOSTI) for funding the synthetic chemistry work under 304/PFARMASI/650600/I121. MH thanks Universiti Sains Malaysia for the award of a postgraduate fellowship

supplementary crystallographic information

1. Introduction

Thiopurine and its analogues possess a broad pharmacological activity for example as a cytotoxic agent (Nguyen et al., 2009) and in the treatment of lupus nephritis (Hadda et al., 2009). As part of our studies in this area, we report the synthesis and structure of the title compound.

2. Experimental

The method to synthesize the title compound was modified from a few papers (Banh et al., 2011; Salvatore et al., 2002; Salvatore et al., 2005). 2-amino-9H-purine-6-thiol (0.598 mmol) was mixed with cesium carbonate (0.598 mmol) in 3.5 ml of dimethylformamide and then stirred vigorously for 15 minutes. Another mixture containing benzyl bromide (1.315 mmol), tetrabutylammonium iodide (0.598 mmol) in 3.5 ml of DMF was added to the first mixture and the stirring was continued at room temperature for six hours. The reaction progress was monitored by TLC using n-hexane:ethyl acetate (0.5:3.5) as a solvent. After the product being formed, the reaction mixture was diluted with 70 mL of water and then extracted using 3 × 70 ml of ethyl acetate. The organic phase was collected, washed with 3× 70 ml of water and then dried over anhydrous magnesium sulfate. This organic phase was then evaporated in vacuo and the crude product was re-crystallized from a hot methanol to afford the title compound as colourless blocks.

2.1. Refinement

N bound H atoms were located from difference Fourier maps and freely refined. The remaining H atoms were positioned geometrically and refined using a riding model with with C–H = 0.95–0.99 Å and U_iso(H) = 1.2U_eq(C).

3. Results and discussion

The purin ring is almost planar with the maximum deviation of 0.014 (2)Å at atom C11. It makes a dihedral angle of 71.28 and 74.67 (8)° with the two benzene rings, C1—C6 and C14—C19, respectively and these two benzene rings make a dihedral angle of 76.04)10)° with each other (Fig. 1).

In the crytsal structure, two dimers involving N5—H1N5···N3ⁱ and C7—H7B···N3ⁱⁱ are observed. These two dimers formed stacked molecules down the b-axis. Intermolecular interactions of C8—H8A···N2ⁱⁱⁱ further expand the molecules into infinite layers parallel to the bc-plane (Fig. 2).