2-(Mesitylmethylsulfanyl)pyridine N-oxide monohydrate

B Ravindran Durai Nayagam; Samuel Robinson Jebas; H Johnson Jeyakumar; Dieter Schollmeyer

doi:10.1107/S1600536808029255

. 2008 Sep 17;64(Pt 10):o1952. doi: 10.1107/S1600536808029255

2-(Mesitylmethylsulfanyl)pyridine N-oxide monohydrate

B Ravindran Durai Nayagam ^a,^*, Samuel Robinson Jebas ^b, H Johnson Jeyakumar ^c, Dieter Schollmeyer ^d

PMCID: PMC2959397 PMID: 21201156

Abstract

In the title compound, C₁₅H₁₇NOS·H₂O, the benzene and pyridine rings form a dihedral angle of 71.18 (2)°. The intramolecular S⋯O distance [2.737 (3) Å] is shorter than expected and, in terms of hybridization principles, the N—C—S angle [114.1 (2)°] is smaller than expected. The crystal structure is stabilized by intermolecular O—H⋯O and weak C—H⋯O hydrogen bonds. In addition, weak π–π stacking interactions with a centroid–centroid distance of 3.778 (3) Å are also observed.

Related literature

For related structures, see: Jebas et al. (2005 ▶); Hartung et al. (1996 ▶); Ravindran Durai Nayagam et al. (2008 ▶). For biological activities of N-oxide derivatives, see: Bovin et al. (1992 ▶); Katsuyuki et al. (1991 ▶); Leonard et al. (1955 ▶); Lobana & Bhatia (1989 ▶); Symons & West (1985 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₅H₁₇NOS·H₂O
M _r = 277.37
Monoclinic,
a = 12.358 (7) Å
b = 15.404 (6) Å
c = 7.748 (5) Å
β = 106.40 (2)°
V = 1415.0 (13) Å³
Z = 4
Cu Kα radiation
μ = 2.01 mm⁻¹
T = 193 (2) K
0.50 × 0.20 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T _min = 0.67, T _max = 0.99 (expected range = 0.612–0.904)
2896 measured reflections
2684 independent reflections
2048 reflections with I > 2σ(I)
R _int = 0.067
3 standard reflections frequency: 60 min intensity decay: 3%

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.190
S = 1.06
2684 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808029255/lh2692sup1.cif

e-64-o1952-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029255/lh2692Isup2.hkl

e-64-o1952-Isup2.hkl^{(129.1KB, 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
O1W—H1W⋯O18	0.84	2.05	2.875 (4)	165
O1W—H2W⋯O18ⁱ	0.84	2.17	2.869 (4)	141
C16—H16⋯O1W	0.95	2.58	3.226 (6)	125

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

RDN thanks the University Grants Commission, India, for a Teacher Fellowship.

supplementary crystallographic information

Comment

N-oxides and their derivatives show a broad spectrum of biological activity such as antifungal, antimicrobial and antibacterial activities (Lobana & Bhatia, 1989; Symons et al., 1985). These compounds are also found to be involved in DNA strand scission under physiological conditions (Katsuyuki et al., 1991; Bovin et al., 1992). Pyridine N-oxides bearing a sulfur group in the 2 position display significant antimicrobial activity (Leonard et al., 1955). In view of the importance of N-oxides, we have previously reported the crystal structures of N–oxide derivatives (Jebas et al., 2005; Ravindran Durai Nayagam, et al., 2008). As an extension of our work, we report here the crystal structure of the title compound.

The asymmetric unit of (I), consists of one molecule 2-(1-oxo-2-pyridylsulfanylmethyl) mesitylene and a water molecule. The bond lengths and angles agree well with the N-oxide derivatives reported earlier (Jebas et al., 2005; Ravindran Durai Nayagam et al., 2008). The N—O bond length is in good agreement with the mean value of 1.304 (15) Å reported in the literature for pyridine N-oxides (Allen et al., 1987).

The pyridine ring and the benzene rings are essentially individually planar with the maximum deviation from planarity being 0.011 (2) Å for atom C2 and -0.010 (2) Å for atom C12 respectively. The dihedral angle formed by the benzene ring (C1–C6) and the pyridine ring (C12–C16/N17) is 71.18 (2)°. The atom O18 attached to atom N17 of the pyridine ring is essentially co-planar; the relevant torsion angle being O18—N17—C16—C15 = 178.9 (3)°.

The crystal structure is stabilized by intermolecular O—H···O and C—H···O hydrogen bonds. In addition, π–π interactions with Cg1···Cg1ⁱ = 3.778 (3) Å (Cg1 is the centroid defined by ring atoms C12–C16/N17) [symmetry code:(i) 1-x,-y,1-z] are observed. As in the structure of 2-(1-phenyl-4-penten-l-yl-thio)pyridine N-oxide (Hartung et al., 1996) a short intramolecular S···O [2.737 (3) Å] distance is observed.

Experimental

A mixture of mono(bromomethyl)mesitylene (0.213 g, 1 mmol) and 1-hydroxypyridine-2-thione sodium salt (0.149,1 mmol) in water (30 ml) and methanol (30 ml) was heated at 333 K with stirring for 30 min. The compound formed was filtered off, and dried. The compound was dissolved in acetone and water (1: 1v/v) and allowed to undergo slow evaporation. Colourless crystals were obtained after a week