2-(Benzyl­sulfan­yl)pyridine N-oxide

Ravindran Durai Nayagam, B.; Jebas, S.R.; Johnson Jeyakumar, H.; Schollmeyer, D.

doi:10.1107/S1600536808011446

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o928

doi:10.1107/S1600536808011446

Open

access

2-(Benzylsulfanyl)pyridine N-oxide

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

^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

(Received 19 April 2008; accepted 22 April 2008; online 26 April 2008)

In the title compound, C₁₂H₁₁NOS, the dihedral angle between the oxopyridinium and phenyl rings is 58.40 (1)°. The crystal structure 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

C₁₂H₁₁NOS
M_r = 217.28
Monoclinic, P 2₁ /c
a = 5.7277 (2) Å
b = 15.8760 (3) Å
c = 11.6498 (4) Å
β = 97.816 (2)°
V = 1049.51 (6) Å³
Z = 4
Cu Kα radiation
μ = 2.49 mm⁻¹
T = 298 (2) K
0.6 × 0.32 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: numerical (CORINC; Draeger & Gattow, 1971 ) T_min = 0.423, T_max = 0.676
2183 measured reflections
1979 independent reflections
1865 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections frequency: 60 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.05
1979 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 is the centroid of the ring C1–C5/N6 and Cg2 is the centroid of the ring C10–C15.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011446/ci2583sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011446/ci2583Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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). Cg1 is the centroid of the ring C1–C5/N6 and Cg2 is the centroid of the ring C10–C15.

Experimental top

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).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

2-(Benzylsulfanyl)pyridine N-oxide top

Crystal data top

C₁₂H₁₁NOS	F(000) = 456
M_r = 217.28	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	1865 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.020
Graphite monochromator	θ_max = 69.9°, θ_min = 4.7°
ω/2θ scans	h = 0→6
Absorption correction: numerical (CORINC; Draeger & Gattow, 1971)	k = 0→19
T_min = 0.423, T_max = 0.676	l = −14→14
2183 measured reflections	3 standard reflections every 60 min
1979 independent reflections	intensity decay: 3%

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0468P)² + 0.3205P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.032	(Δ/σ)_max = 0.001
wR(F²) = 0.088	Δρ_max = 0.23 e Å⁻³
S = 1.05	Δρ_min = −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

Crystal data top

C₁₂H₁₁NOS	V = 1049.51 (6) Å³
M_r = 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)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1865 reflections with I > 2σ(I)
Absorption correction: numerical (CORINC; Draeger & Gattow, 1971)	R_int = 0.020
T_min = 0.423, T_max = 0.676	3 standard reflections every 60 min
2183 measured reflections	intensity decay: 3%
1979 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
1979 reflections	Δρ_min = −0.23 e Å⁻³
137 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.423, 0.676
No. of measured, independent and observed [I > 2σ(I)] reflections	2183, 1979, 1865
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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