organic compounds
2-(Benzylsulfanyl)pyridine N-oxide
aDepartment of Chemistry, Popes College, Sawyerpuram 628 251, Tamil Nadu, India, bDepartment of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India, cDepartment of Physics, Popes College, Sawyerpuram 628 251, Tamil Nadu, India, and dInstitut für Organische Chemie, Universität Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
*Correspondence e-mail: b_ravidurai@yahoo.com
In the title compound, C12H11NOS, the dihedral angle between the oxopyridinium and phenyl rings is 58.40 (1)°. The is stabilized by C—H⋯O hydrogen bonds, π–π stacking interactions involving the pyridinium rings [centroid–centroid distance = 3.6891 (9) Å] and C—H⋯π interactions.
Related literature
For bond-length data, see: Allen et al.(1987). 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 related literature, see: Jebas et al. (2005); Ravindran et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell CAD-4 Software; data reduction: CORINC (Draeger & 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) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808011446/ci2583sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011446/ci2583Isup2.hkl
A mixture of benzyl chloride, (0.126 g, 1 mmol) and 1-hydroxypyridine-2-thione sodium salt (0.149 g, 1 mmol) in water and methanol (30 ml each) was heated at 333 K with stirring for 30 min. The compound formed was filtered off, and dried (0.20 g, 92%). The compound was recrystallized from chloroform-methanol (1:1 v/v).
H atoms were positioned geometrically [C-H = 0.93 (aromatic) or 0.97 Å (methylene)] and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (Draeger & 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) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C12H11NOS | F(000) = 456 |
Mr = 217.28 | Dx = 1.375 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 5.7277 (2) Å | θ = 65–70° |
b = 15.8760 (3) Å | µ = 2.49 mm−1 |
c = 11.6498 (4) Å | T = 298 K |
β = 97.816 (2)° | Plate, colourless |
V = 1049.51 (6) Å3 | 0.6 × 0.32 × 0.16 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 1865 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.020 |
Graphite monochromator | θmax = 69.9°, θmin = 4.7° |
ω/2θ scans | h = 0→6 |
Absorption correction: numerical (CORINC; Draeger & Gattow, 1971) | k = 0→19 |
Tmin = 0.423, Tmax = 0.676 | l = −14→14 |
2183 measured reflections | 3 standard reflections every 60 min |
1979 independent reflections | intensity decay: 3% |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0468P)2 + 0.3205P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max = 0.001 |
wR(F2) = 0.088 | Δρmax = 0.23 e Å−3 |
S = 1.05 | Δρmin = −0.23 e Å−3 |
1979 reflections | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
137 parameters | Extinction coefficient: 0.0138 (9) |
0 restraints |
C12H11NOS | V = 1049.51 (6) Å3 |
Mr = 217.28 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 5.7277 (2) Å | µ = 2.49 mm−1 |
b = 15.8760 (3) Å | T = 298 K |
c = 11.6498 (4) Å | 0.6 × 0.32 × 0.16 mm |
β = 97.816 (2)° |
Enraf–Nonius CAD-4 diffractometer | 1865 reflections with I > 2σ(I) |
Absorption correction: numerical (CORINC; Draeger & Gattow, 1971) | Rint = 0.020 |
Tmin = 0.423, Tmax = 0.676 | 3 standard reflections every 60 min |
2183 measured reflections | intensity decay: 3% |
1979 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.23 e Å−3 |
1979 reflections | Δρmin = −0.23 e Å−3 |
137 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0305 (2) | 0.50000 (9) | 0.21475 (12) | 0.0323 (3) | |
C2 | 0.2020 (3) | 0.55970 (10) | 0.20485 (13) | 0.0397 (4) | |
H2 | 0.3446 | 0.5575 | 0.2536 | 0.048* | |
C3 | 0.1620 (3) | 0.62241 (11) | 0.12302 (14) | 0.0462 (4) | |
H3 | 0.2768 | 0.6629 | 0.1165 | 0.055* | |
C4 | −0.0502 (3) | 0.62477 (11) | 0.05064 (14) | 0.0456 (4) | |
H4 | −0.0788 | 0.6668 | −0.005 | 0.055* | |
C5 | −0.2179 (3) | 0.56490 (11) | 0.06128 (13) | 0.0426 (4) | |
H5 | −0.3605 | 0.5664 | 0.0125 | 0.051* | |
N6 | −0.1782 (2) | 0.50342 (8) | 0.14226 (10) | 0.0358 (3) | |
O7 | −0.33607 (19) | 0.44536 (8) | 0.15290 (11) | 0.0507 (3) | |
S8 | 0.04017 (6) | 0.41513 (2) | 0.31047 (3) | 0.03918 (16) | |
C9 | 0.3207 (3) | 0.43634 (10) | 0.39937 (14) | 0.0415 (4) | |
H9A | 0.4475 | 0.4338 | 0.3522 | 0.05* | |
H9B | 0.319 | 0.4923 | 0.4327 | 0.05* | |
C10 | 0.3594 (2) | 0.37147 (9) | 0.49432 (12) | 0.0348 (3) | |
C11 | 0.5483 (3) | 0.31656 (10) | 0.50101 (13) | 0.0404 (4) | |
H11 | 0.6517 | 0.3197 | 0.4462 | 0.049* | |
C12 | 0.5852 (3) | 0.25699 (10) | 0.58820 (15) | 0.0465 (4) | |
H12 | 0.7138 | 0.2208 | 0.5919 | 0.056* | |
C13 | 0.4330 (3) | 0.25101 (11) | 0.66927 (14) | 0.0481 (4) | |
H13 | 0.4565 | 0.2103 | 0.7271 | 0.058* | |
C14 | 0.2452 (3) | 0.30575 (13) | 0.66418 (15) | 0.0527 (4) | |
H14 | 0.1426 | 0.3024 | 0.7194 | 0.063* | |
C15 | 0.2084 (3) | 0.36542 (11) | 0.57771 (14) | 0.0461 (4) | |
H15 | 0.081 | 0.402 | 0.5752 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0293 (7) | 0.0344 (7) | 0.0321 (7) | 0.0014 (5) | −0.0005 (5) | −0.0014 (5) |
C2 | 0.0311 (7) | 0.0454 (8) | 0.0407 (8) | −0.0045 (6) | −0.0019 (6) | 0.0043 (6) |
C3 | 0.0422 (9) | 0.0470 (9) | 0.0482 (9) | −0.0091 (7) | 0.0021 (7) | 0.0095 (7) |
C4 | 0.0481 (9) | 0.0473 (9) | 0.0397 (8) | 0.0013 (7) | 0.0004 (7) | 0.0105 (7) |
C5 | 0.0381 (8) | 0.0479 (9) | 0.0382 (8) | 0.0026 (7) | −0.0073 (6) | 0.0031 (7) |
N6 | 0.0298 (6) | 0.0378 (6) | 0.0377 (6) | −0.0022 (5) | −0.0027 (5) | −0.0023 (5) |
O7 | 0.0360 (6) | 0.0504 (7) | 0.0612 (7) | −0.0139 (5) | −0.0092 (5) | 0.0073 (6) |
S8 | 0.0355 (2) | 0.0354 (2) | 0.0437 (2) | −0.00537 (13) | −0.00524 (15) | 0.00604 (14) |
C9 | 0.0362 (8) | 0.0388 (8) | 0.0459 (8) | −0.0033 (6) | −0.0075 (6) | 0.0058 (6) |
C10 | 0.0342 (7) | 0.0324 (7) | 0.0355 (7) | −0.0012 (6) | −0.0035 (5) | −0.0015 (6) |
C11 | 0.0370 (8) | 0.0444 (8) | 0.0397 (7) | 0.0034 (6) | 0.0044 (6) | −0.0004 (6) |
C12 | 0.0460 (9) | 0.0408 (8) | 0.0502 (9) | 0.0109 (7) | −0.0024 (7) | 0.0025 (7) |
C13 | 0.0590 (10) | 0.0445 (9) | 0.0374 (8) | −0.0046 (7) | −0.0054 (7) | 0.0064 (7) |
C14 | 0.0543 (10) | 0.0660 (11) | 0.0393 (8) | −0.0035 (9) | 0.0121 (7) | 0.0004 (8) |
C15 | 0.0421 (9) | 0.0505 (9) | 0.0458 (8) | 0.0107 (7) | 0.0065 (7) | −0.0034 (7) |
C1—N6 | 1.3678 (18) | C9—H9A | 0.97 |
C1—C2 | 1.381 (2) | C9—H9B | 0.97 |
C1—S8 | 1.7450 (14) | C10—C11 | 1.383 (2) |
C2—C3 | 1.376 (2) | C10—C15 | 1.389 (2) |
C2—H2 | 0.93 | C11—C12 | 1.383 (2) |
C3—C4 | 1.382 (2) | C11—H11 | 0.93 |
C3—H3 | 0.93 | C12—C13 | 1.373 (2) |
C4—C5 | 1.369 (2) | C12—H12 | 0.93 |
C4—H4 | 0.93 | C13—C14 | 1.378 (3) |
C5—N6 | 1.355 (2) | C13—H13 | 0.93 |
C5—H5 | 0.93 | C14—C15 | 1.378 (2) |
N6—O7 | 1.3090 (16) | C14—H14 | 0.93 |
S8—C9 | 1.8205 (15) | C15—H15 | 0.93 |
C9—C10 | 1.505 (2) | ||
N6—C1—C2 | 119.53 (13) | C10—C9—H9B | 109.9 |
N6—C1—S8 | 111.98 (10) | S8—C9—H9B | 109.9 |
C2—C1—S8 | 128.49 (11) | H9A—C9—H9B | 108.3 |
C3—C2—C1 | 120.09 (14) | C11—C10—C15 | 118.26 (14) |
C3—C2—H2 | 120 | C11—C10—C9 | 120.56 (14) |
C1—C2—H2 | 120 | C15—C10—C9 | 121.18 (14) |
C2—C3—C4 | 119.47 (15) | C12—C11—C10 | 120.85 (14) |
C2—C3—H3 | 120.3 | C12—C11—H11 | 119.6 |
C4—C3—H3 | 120.3 | C10—C11—H11 | 119.6 |
C5—C4—C3 | 119.71 (15) | C13—C12—C11 | 120.29 (15) |
C5—C4—H4 | 120.1 | C13—C12—H12 | 119.9 |
C3—C4—H4 | 120.1 | C11—C12—H12 | 119.9 |
N6—C5—C4 | 120.65 (14) | C12—C13—C14 | 119.47 (15) |
N6—C5—H5 | 119.7 | C12—C13—H13 | 120.3 |
C4—C5—H5 | 119.7 | C14—C13—H13 | 120.3 |
O7—N6—C5 | 121.37 (12) | C13—C14—C15 | 120.39 (16) |
O7—N6—C1 | 118.08 (12) | C13—C14—H14 | 119.8 |
C5—N6—C1 | 120.55 (12) | C15—C14—H14 | 119.8 |
C1—S8—C9 | 99.76 (7) | C14—C15—C10 | 120.73 (15) |
C10—C9—S8 | 108.78 (10) | C14—C15—H15 | 119.6 |
C10—C9—H9A | 109.9 | C10—C15—H15 | 119.6 |
S8—C9—H9A | 109.9 | ||
N6—C1—C2—C3 | 0.4 (2) | C2—C1—S8—C9 | 5.82 (16) |
S8—C1—C2—C3 | 179.80 (13) | C1—S8—C9—C10 | 177.00 (11) |
C1—C2—C3—C4 | −0.4 (3) | S8—C9—C10—C11 | 117.36 (14) |
C2—C3—C4—C5 | 0.1 (3) | S8—C9—C10—C15 | −63.08 (17) |
C3—C4—C5—N6 | 0.1 (3) | C15—C10—C11—C12 | 0.2 (2) |
C4—C5—N6—O7 | −179.46 (15) | C9—C10—C11—C12 | 179.81 (14) |
C4—C5—N6—C1 | −0.1 (2) | C10—C11—C12—C13 | 0.5 (3) |
C2—C1—N6—O7 | 179.21 (13) | C11—C12—C13—C14 | −1.0 (3) |
S8—C1—N6—O7 | −0.28 (16) | C12—C13—C14—C15 | 0.8 (3) |
C2—C1—N6—C5 | −0.2 (2) | C13—C14—C15—C10 | 0.0 (3) |
S8—C1—N6—C5 | −179.65 (11) | C11—C10—C15—C14 | −0.5 (2) |
N6—C1—S8—C9 | −174.73 (11) | C9—C10—C15—C14 | 179.91 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O7i | 0.93 | 2.42 | 3.323 (2) | 164 |
C14—H14···Cg1ii | 0.93 | 2.92 | 3.560 (2) | 127 |
C4—H4···Cg2iii | 0.93 | 2.99 | 3.777 (2) | 143 |
Symmetry codes: (i) −x−1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H11NOS |
Mr | 217.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 5.7277 (2), 15.8760 (3), 11.6498 (4) |
β (°) | 97.816 (2) |
V (Å3) | 1049.51 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.49 |
Crystal size (mm) | 0.6 × 0.32 × 0.16 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Numerical (CORINC; Draeger & Gattow, 1971) |
Tmin, Tmax | 0.423, 0.676 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2183, 1979, 1865 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.05 |
No. of reflections | 1979 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.23 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Draeger & Gattow, 1971), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O7i | 0.93 | 2.42 | 3.323 (2) | 164 |
C14—H14···Cg1ii | 0.93 | 2.92 | 3.560 (2) | 127 |
C4—H4···Cg2iii | 0.93 | 2.99 | 3.777 (2) | 143 |
Symmetry codes: (i) −x−1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x, y+1/2, −z+1/2. |
Acknowledgements
RDN thanks the University Grants Commission, India, for a Teacher Fellowship.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19. CrossRef Web of Science Google Scholar
Bovin, D. H. R., Crepon, E. & Zard, S. Z. (1992). Bull. Soc. Chim. Fr. 129, 145–150. Google Scholar
Draeger, M. & Gattow, G. (1971). Acta Chem. Scand. 25, 761–762. CAS Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Jebas, S. R., Balasubramanian, T., Ravidurai, B. & Kumaresan, S. (2005). Acta Cryst. E61, o2677–o2678. Web of Science CSD CrossRef IUCr Journals Google Scholar
Katsuyuki, N., Carter, B. J., Xu, J. & Hetch, S. M. (1991). J. Am. Chem. Soc. 113, 5099–5100. Google Scholar
Leonard, F., Barklay, F. A., Brown, E. V., Anderson, F. E. & Green, D. M. (1955). Antibiot. Chemother. pp. 261–264. Google Scholar
Lobana, T. S. & Bhatia, P. K. (1989). J. Sci. Ind. Res. 48, 394–401. CAS Google Scholar
Ravindran Durai Nayagam, B., Jebas, S. R., Grace, S. & Schollmeyer, D. (2008). Acta Cryst. E64, o409. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Symons, M. C. R. & West, D.-X. (1985). J. Chem. Soc. Dalton Trans. pp. 379–381. CrossRef Web of Science Google Scholar
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N-Oxides and their derivatives show a broad spectrum of biological activity, such as antifungal, antibacterial, 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 position 2 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 on these derivatives, we report here the crystal structure of the title compound (Fig. 1).
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 oxopyridinium and benzene rings are planar to within ±0.002 (2) Å and ±0.005 (2) Å, respectively, and they form a dihedral angle of 58.40 (1)°. Atom O7 deviates from the plane of the pyridinium ring by -0.012 (1) Å.
In the crystal structure, inversion related molecules at (x, y, z) and (-1-x, 1-y, -z) are linked by C—H···O hydrogen bonds to form a R22(8) ring (Fig. 2). In addition, the crystal packing is stabilized by a π-π interaction between the pyridinium rings of adjacent molecules at (x, y, z) and (-x, 2-y, -z), with a ring centroid to centroid distance of 3.6891 (9) Å. Weak C—H···π interactions involving the two aromatic rings are also observed.