6-Chloro-9-(2-nitro­phenyl­sulfon­yl)-9H-purine

Ning-Yu Wang; Mei Deng; Yong Xia; Luo-Ting Yu

doi:10.1107/S1600536811003102

. 2011 Feb 23;67(Pt 3):o687. doi: 10.1107/S1600536811003102

6-Chloro-9-(2-nitrophenylsulfonyl)-9H-purine

Ning-Yu Wang ^a, Mei Deng ^a, Yong Xia ^a, Luo-Ting Yu ^a,^*

PMCID: PMC3052074 PMID: 21522432

Abstract

The title compound, C₁₁H₆ClN₅O₄S, crystallized with two independent molecules in the asymmetric unit. The benzene ring makes dihedral angles of 66.46 (8) and 85.77 (9)° with the mean plane of the purine ring in the two molecules. In the crystal, intermolecular π–π stacking interactions [centroid–centroid distance = 3.8968 (12) Å], C—Cl⋯π interactions [Cl⋯centroid = 3.2505 (10) Å, C—Cl⋯centroid = 161.56 (18)°] and non-classical C—H⋯O and C—H⋯N hydrogen bonds link the molecules.

Related literature

For general background to the chemistry, biological activity and applications of purine derivatives, see: Scozzafava et al. (2001 ▶); Bakkestuen et al. (2005 ▶).

Experimental

Crystal data

C₁₁H₆ClN₅O₄S
M _r = 339.72
Triclinic,
a = 10.0055 (3) Å
b = 10.6931 (5) Å
c = 12.5378 (5) Å
α = 93.692 (3)°
β = 97.136 (3)°
γ = 93.995 (3)°
V = 1324.16 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 293 K
0.42 × 0.40 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 ▶) T _min = 0.992, T _max = 1.0
10984 measured reflections
5403 independent reflections
4389 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.092
S = 1.02
5403 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003102/su2246sup1.cif

e-67-0o687-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003102/su2246Isup2.hkl

e-67-0o687-Isup2.hkl^{(264.5KB, 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
C13—H13⋯O6	0.93	2.60	3.222 (3)	125
C24—H24⋯O7ⁱ	0.93	2.41	3.327 (3)	170
C28—H28⋯O2ⁱⁱ	0.93	2.56	3.469 (3)	165
C30—H30⋯N23ⁱⁱⁱ	0.93	2.62	3.489 (3)	155

Open in a new tab

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

Acknowledgments

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

supplementary crystallographic information

Comment

Purine derivatives are of great importance owing to their wide-ranging biological properties (Scozzafava et al., 2001; Bakkestuen et al., 2005). As there are several kinds of tautomers in purine derivatives, it is difficult to determine their structures by NMR, MS or IR sepctroscopy. The title compound is one of the key intermediates in our synthetic investigations of antimicrobial agents. Here we determined the accurate structure of the title compound by X-ray analysis.

As shown in Fig. 1, the title compound crystallized with two independent molecules (A and B) in the asymmetric unit. The conformation of the molecules is different. The benzene ring makes a dihedral angle of 66.46 (8)° with the mean plane of the purine ring in molecule A, while in molecule B this same angle is 85.77 (9)°.

In the crystal, the two molecules and symmetry related molecules, are linked into a three-dimensional network by intermolecular π···π stacking interactions involving ring (C10-C15) and a symmetry related ring (code: 1-x, 2-x, 1-z)], with a centroid-to-centroid distance of 3.8968 (12) Å, and nonclassical C—H···O and C—H···N hydrogen bonds (Table 1 and Fig. 2). There are also C-Cl···π interactions involving chlorine Cl2 and ring (C10-C15 = Cg), with a Cl···centroid distance of 3.2505 (10) Å, angle C17-Cl2···Cgⁱ being 161.56 (18)° [symmetry code: (i) -x, -y+1, -z+1] - see Fig. 1.

Experimental

A mixture of 6-chloropurine (0.463 g, 3 mmol), 2-nitrobenzenesulfonyl chloride (1.33 g, 6 mmol), Triethylamine (0.607 g, 6 mmol), DMAP (0.037 g, 0.3 mmol), THF (10 ml) and DCM (10 ml) was stirred for 12 h at room temperiture. The solvent was removed under vacuum. The residue was extracted with ethyl acetate (50 ml) and water (50 ml). The organic layer was washed three times with 30 ml ammonia solution (5 N) and 30 ml brine, and then dried with anhydrous sodium sulfate. The product was isolated by column chromatography on silica gel. Yield 0.712 g (69.8%). Crystals, suitable for X-ray analysis, were obtained by slow evaporation from a solution of ethyl acetate.