N-(2-Amino­pyridin-3-yl)-4-methyl-N-(4-methyl­phenyl­sulfon­yl)benzene­sulfonamide

Abu Taher; Vincent J Smith

doi:10.1107/S1600536812010872

. 2012 Mar 21;68(Pt 4):o1136. doi: 10.1107/S1600536812010872

N-(2-Aminopyridin-3-yl)-4-methyl-N-(4-methylphenylsulfonyl)benzenesulfonamide

Abu Taher ^a,^*, Vincent J Smith ^a

PMCID: PMC3344082 PMID: 22606085

Abstract

The title compound, C₁₉H₁₉N₃O₄S₂, was prepared by the reaction of 2,3-diaminopyridine with tosyl chloride in a mixture of dichloromethane–pyridine as solvent. In the crystal, molecules associate via pairs of N—H⋯N hydrogen bonds, forming a centrosymmetric eight-membered {⋯HNCN}₂ synthon. The dihedral angles between the aminopyridine ring and the tosyl benzene rings are 50.01 (6) and 32.01 (4)°.

Related literature

For the synthesis of related compounds, see: Schetty (1969 ▶); Dubey & Kumar (2000 ▶). For background to the application of ring-closing metathesis (RCM) on substrates protected with sulfonamide groups, see: Yadav et al. (2011 ▶); Morgans et al. (2009 ▶); van Otterlo et al. (2004 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₁₉N₃O₄S₂
M _r = 417.49
Triclinic,
a = 8.6343 (15) Å
b = 9.6486 (17) Å
c = 12.701 (2) Å
α = 111.324 (2)°
β = 90.109 (2)°
γ = 98.097 (2)°
V = 974.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 102 K
0.25 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.928, T _max = 0.928
11658 measured reflections
4644 independent reflections
4381 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.086
S = 1.03
4644 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: X-SEED.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010872/tk5064sup1.cif

e-68-o1136-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010872/tk5064Isup2.hkl

e-68-o1136-Isup2.hkl^{(227.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812010872/tk5064Isup3.cml

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
N2—H2A⋯N1ⁱ	0.88	2.13	2.9948 (17)	166

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Symmetry code: (i) Inline graphic .

Acknowledgments

AT thanks the South African National Research Foundation (NRF), Pretoria, for providing an Innovation Fellowship, and Professor Willem A. L. van Otterlo for his valuable input and research oversight. Stellenbosch University’s Science Faculty is also acknowledged for providing laboratory space and additional financial research support.

supplementary crystallographic information

Comment

Aminopyridines and sulfonamides are structural units frequently found in the skeletons of bioactive compounds (Dubey et al., 2000). In this present communication the main aim was to synthesize pyridine-annulated heterocycles by using ring-closing metathesis (RCM) and in which the 2,3-disulfonamide-protected 2,3-diaminopyridine was required as substrate in continuation of previous work in our group combining sulfonamide protecting groups and RCM (Yadav et al., 2011; Morgans et al., 2009). However, in this particular case, when tosyl chloride was utilized in an attempt to 'mono' protect both amino groups on 2,3-diaminopyridine, only the 3,3-ditosyl compound, N-(2-amino-3-pyridinyl)-4-methyl-N-[(4-methylphenyl)sulfonyl]benzenesulfonamide (I), was isolated. In previous work by our group this behaviour was not observed with 2,3-diaminopyridine or 1,2-diaminobenzene as the substrate (van Otterlo et al., 2004). A literature search indicated that this type of selectivity is not common, see for instance Schetty (1969).

Crystallizing in the space group P1, (I) has a single molecule in the asymmetric unit (Fig. 1). In the crystal packing, the molecules associate via a centrosymmetric hydrogen bonded dimer with N—H···N hydrogen bonds interacting to form the hydrogen bonded ring motif R²₂(8) (Bernstein et al., 1995), Fig. 2. The mean planes passing through the tosyl benzene rings (C6–C11 and C13–C18) form dihedral angles with the aminopyridine ring (N1,C1–C5) of 50.01 (6) and 32.01 (4)°, respectively.

Experimental

2,3-Diaminopyridine (0.100 g, 0.917 mmol) was dissolved in a mixture of CH₂Cl₂ and pyridine (10 ml, 15:1). 4-Methylbenzene-1-sulfonyl chloride (0.524 g, 2.75 mol) was added and the solution was heated, with stirring, to 313 K for 24 h. The solution was allowed to cool to room temperature and washed with dilute HCl (15 ml, 1 M) and brine (3 × 15 ml), and then dried over Na₂SO₄. After filtration and removal of the solvent under vacuum, the residue was recrystallized from EtOH to give the product as a colourless crystalline material (0.260 g, 68%).