organic papers
Acta Cryst.(2005). E61, o2677–o2678 doi:10.1107/S1600536805022415 Jebaset al. C
7H7NO3S
o2677
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
2-(Acetylsulfanyl)pyridine
N
-oxide
Samuel Robinson Jebas,a Thailampillai
Balasubramanian,a* Balasingh Raviduraiband Sudalaiandi Kumaresanb
aDepartment of Physics, National Institute of
Technology, Tiruchirappalli 620 015, India, and
b
Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli 629 012, India
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 303 K
Mean(C–C) = 0.006 A˚
Rfactor = 0.052
wRfactor = 0.150
Data-to-parameter ratio = 12.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The title compound, C7H7NO3S, is a simple new
pyridylthio-N-oxide of pharmacological interest. There are two indepen-dent molecules in the asymmetric unit. Strong O—H O hydrogen-bond interactions link the molecules in ribbons lying in the (101) plane.
Comment
N-Oxides and their derivatives show a broad spectrum of biological activity, such as antifungal, antibacterial, anti-microbial and antibiotic activities (Lobana & Bhatia, 1989). These compounds are also found to be involved in the DNA strand scission under physiological conditions (Katsuyuki et al., 1991).In view of the importance ofN-oxide derivatives, the title compound, (I), has been synthesized and the crystal structure determined.
The asymmetric unit of (I) contains two independent mol-ecules with similar geometry. Both molmol-ecules are essentially planar, the maximum deviations from planarity being 0.093 (4) and 0.102 (3) A˚ for atoms C2 and O11, respectively.
The C—C, C—O and C—S bond lengths and angles are normal (Table 1). The N—O bond lengths are in good
[image:1.610.277.388.360.438.2] [image:1.610.208.457.540.720.2]Received 21 June 2005 Accepted 12 July 2005 Online 23 July 2005
Figure 1
agreement with the mean value of 1.335 A˚ reported in the literature for pyridineN-oxides (Allenet al., 1987).
In the crystal structure of (I), the molecules are linked by strong O—H O hydrogen-bond interactions to form ribbons running parallel to the (101) plane (Table 2). In addition, weak C—H O interactions involving the ribbons are observed.
Experimental
The title compound was prepared by heating a mixture of 1-hydroxy-2-pyridinethione sodium salt (0.447 g, 3 mmol) and chloroacetic acid (0.292 g, 3.1 mmol) in methanol at 343 K with magnetic stirring for 1 h. Fine crystals were obtained after a week by slow cooling of the solution (yield 87%).
Crystal data
C7H7NO3S
Mr= 185.20
Monoclinic,P21=c
a= 9.826 (4) A˚
b= 13.596 (2) A˚
c= 11.990 (5) A˚
= 102.06 (4)
V= 1566.6 (10) A˚3
Z= 8
Dx= 1.562 Mg m
3
MoKradiation Cell parameters from 25
reflections
= 2–25
= 0.37 mm1
T= 303 K Prism, white
0.240.200.18 mm
Data collection
Nonius MACH3 four-circle diffractometer
!–2scans
Absorption correction: scan (Northet al., 1968)
Tmin= 0.914,Tmax= 0.935 3186 measured reflections 2751 independent reflections 1546 reflections withI> 2(I)
Rint= 0.060
max= 25.0
h= 0!11
k=1!16
l=14!13 3 standard reflections
frequency: 60 min intensity decay: none
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.052
wR(F2) = 0.150
S= 1.02 2751 reflections 219 parameters
All H-atom parameters refined
w= 1/[2(F
o2) + (0.075P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.34 e A˚ 3
min=0.33 e A˚ 3
Table 1
Selected geometric parameters (A˚ ,).
C2—S8 1.806 (4)
C3—N1 1.359 (5)
C3—S8 1.739 (4)
C7—N1 1.346 (5)
C12—S20 1.802 (4)
C13—N11 1.364 (5)
C13—S20 1.736 (4)
C17—N11 1.340 (5)
N1—O3 1.324 (4)
N11—O13 1.323 (4)
O3—N1—C7 122.0 (3)
O3—N1—C3 116.4 (3)
C7—N1—C3 121.7 (4)
O13—N11—C17 121.4 (3)
O13—N11—C13 116.7 (3) C17—N11—C13 121.9 (3)
C3—S8—C2 101.01 (19)
[image:2.610.315.564.111.216.2]C13—S20—C12 100.62 (19)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O2—H2 O13i
0.82 1.76 2.568 (5) 167
O12—H12 O3ii
0.82 1.74 2.541 (5) 163
C4—H4 O12iii
0.93 2.51 3.325 (6) 147
C14—H14 O2iii
0.93 2.55 3.344 (6) 144
C6—H6 O1iv 0.93 2.51 3.420 (6) 168
C5—H5 O3iv
0.93 2.45 3.250 (5) 144
C7—H7 O11v
0.93 2.41 3.286 (6) 156
C15—H15 O13vi 0.93 2.51 3.347 (5) 149
C16—H16 O11vi
0.93 2.57 3.477 (6) 164
C17—H17 O1vii
0.93 2.40 3.279 (6) 157
Symmetry codes: (i)xþ1;yþ3 2;z
1
2; (ii)x;yþ 3 2;z
1
2; (iii)xþ1;yþ1;z;
(iv) xþ1;y1 2;zþ
1
2; (v) x;yþ 3 2;zþ
1
2; (vi) x;y 1 2;zþ
1 2; (vii)
x1;yþ3 2;zþ
1 2.
The H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 A˚ and O—H = 0.82 A˚, and refined using a riding model, with
Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement:CAD-4 EXPRESS; data reduction:XCAD4(Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97
(Sheldrick, 1997); program(s) used to refine structure:SHELXL97
(Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); soft-ware used to prepare material for publication:SHELXL97.
The authors thank Professor R. K. Rajaram, Coordinator, School of Physics, Madurai Kamaraj University, Madurai, India, for carrying out the data collection.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Enraf–Nonius (1994).CAD-4 EXPRESS. Enraf–Nonius, Delft, The Nether-lands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Ger-many.
Katsuyuki, N., Carter, B. J., Xu, J. & Hetch, S. M. (1991).J. Am. Chem. Soc. 113, 5100–5102.
Lobana, T. S. & Bhatia, P. K. (1989).J. Sci. Ind. Res.48, 394–401.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.
supporting information
sup-1 Acta Cryst. (2005). E61, o2677–o2678
supporting information
Acta Cryst. (2005). E61, o2677–o2678 [https://doi.org/10.1107/S1600536805022415]
2-(Acetylsulfanyl)pyridine
N
-oxide
Samuel Robinson Jebas, Thailampillai Balasubramanian, Balasingh Ravidurai and Sudalaiandi
Kumaresan
2-(Acetylsulfanyl)pyridine N-oxide
Crystal data
C7H7NO3S
Mr = 185.20 Monoclinic, P21/c Hall symbol: -P 2ybc
a = 9.826 (4) Å
b = 13.596 (2) Å
c = 11.990 (5) Å
β = 102.06 (4)°
V = 1566.6 (10) Å3
Z = 8
F(000) = 768
Dx = 1.562 Mg m−3 Melting point: 482 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections
θ = 2–25°
µ = 0.37 mm−1
T = 303 K Prism, white
0.24 × 0.20 × 0.18 mm
Data collection
Nonius MACH3 sealed-tube diffractometer
ω–2θ scans
Absorption correction: ψ scan (North et al., 1968)
Tmin = 0.914, Tmax = 0.935 3186 measured reflections 2751 independent reflections
1546 reflections with I > 2σ(I)
Rint = 0.060
θmax = 25.0°, θmin = 2.1°
h = 0→11
k = −1→16
l = −14→13
3 standard reflections every 60 min intensity decay: none
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.052
wR(F2) = 0.150
S = 1.02 2751 reflections 219 parameters
0 restraints
All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.34 e Å−3 Δρmin = −0.33 e Å−3
Special details
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
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
C1 0.7804 (4) 1.0868 (3) 0.0244 (4) 0.0348 (10)
C2 0.6995 (4) 1.0116 (3) 0.0763 (3) 0.0340 (10)
H2A 0.7621 0.9639 0.1202 0.041*
H2B 0.6347 0.9771 0.0171 0.041*
C3 0.5158 (4) 0.9831 (3) 0.2161 (3) 0.0305 (9)
C4 0.5059 (4) 0.8859 (3) 0.1841 (4) 0.0357 (10)
H4 0.5527 0.863 0.1294 0.043*
C5 0.4262 (5) 0.8225 (3) 0.2333 (4) 0.0435 (12)
H5 0.4169 0.7572 0.2098 0.052*
C6 0.3602 (5) 0.8548 (3) 0.3168 (4) 0.0460 (12)
H6 0.3086 0.8117 0.3518 0.055*
C7 0.3721 (5) 0.9512 (3) 0.3472 (4) 0.0458 (13)
H7 0.3277 0.9743 0.4033 0.055*
C11 0.2918 (4) 0.3235 (3) 0.0317 (4) 0.0355 (10)
C12 0.2326 (5) 0.2477 (3) 0.0999 (4) 0.0356 (10)
H12A 0.3066 0.208 0.1442 0.043*
H12B 0.169 0.2046 0.0495 0.043*
C13 0.0714 (4) 0.2161 (3) 0.2555 (3) 0.0302 (10)
C14 0.0822 (5) 0.1161 (3) 0.2376 (4) 0.0381 (11)
H14 0.1348 0.093 0.187 0.046*
C15 0.0153 (5) 0.0522 (3) 0.2947 (4) 0.0442 (12)
H15 0.0217 −0.015 0.2823 0.053*
C16 −0.0617 (5) 0.0849 (3) 0.3704 (4) 0.0446 (11)
H16 −0.1079 0.0406 0.4086 0.054*
C17 −0.0694 (5) 0.1838 (3) 0.3888 (4) 0.0408 (11)
H17 −0.1218 0.2072 0.4394 0.049*
N1 0.4473 (4) 1.0137 (2) 0.2972 (3) 0.0374 (9)
N11 −0.0016 (4) 0.2469 (2) 0.3341 (3) 0.0352 (9)
O1 0.7865 (3) 1.1724 (2) 0.0509 (3) 0.0518 (9)
O2 0.8412 (4) 1.0477 (2) −0.0519 (3) 0.0489 (9)
H2 0.8866 1.0899 −0.0768 0.073*
O3 0.4564 (4) 1.1086 (2) 0.3228 (3) 0.0598 (11)
O11 0.2770 (3) 0.4108 (2) 0.0426 (3) 0.0486 (9)
O12 0.3582 (4) 0.2836 (2) −0.0398 (3) 0.0475 (9)
H12 0.3901 0.3269 −0.0745 0.071*
O13 −0.0026 (3) 0.3426 (2) 0.3535 (3) 0.0503 (9)
S8 0.60680 (12) 1.07807 (8) 0.16754 (10) 0.0393 (3)
S20 0.14192 (12) 0.31331 (7) 0.19280 (10) 0.0382 (3)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.035 (2) 0.039 (2) 0.034 (2) 0.005 (2) 0.016 (2) 0.001 (2)
C2 0.037 (2) 0.036 (2) 0.032 (2) 0.0010 (19) 0.014 (2) −0.0016 (19)
supporting information
sup-3 Acta Cryst. (2005). E61, o2677–o2678
C4 0.043 (3) 0.031 (2) 0.037 (3) 0.0037 (19) 0.018 (2) −0.0014 (19)
C5 0.052 (3) 0.029 (2) 0.052 (3) 0.001 (2) 0.015 (2) 0.000 (2)
C6 0.052 (3) 0.037 (2) 0.056 (3) −0.005 (2) 0.027 (3) 0.011 (2)
C7 0.053 (3) 0.043 (3) 0.050 (3) −0.001 (2) 0.033 (3) 0.009 (2)
C11 0.035 (2) 0.042 (3) 0.031 (2) 0.001 (2) 0.012 (2) 0.003 (2)
C12 0.038 (3) 0.039 (2) 0.034 (2) 0.002 (2) 0.016 (2) −0.005 (2)
C13 0.029 (2) 0.037 (2) 0.026 (2) −0.0011 (18) 0.0081 (19) 0.0007 (18)
C14 0.040 (3) 0.031 (2) 0.046 (3) 0.0012 (19) 0.016 (2) −0.005 (2)
C15 0.054 (3) 0.031 (2) 0.049 (3) −0.001 (2) 0.011 (2) 0.000 (2)
C16 0.049 (3) 0.042 (3) 0.046 (3) −0.011 (2) 0.017 (2) 0.008 (2)
C17 0.045 (3) 0.044 (3) 0.040 (3) −0.003 (2) 0.025 (2) 0.002 (2)
N1 0.046 (2) 0.0294 (19) 0.042 (2) 0.0046 (16) 0.0237 (19) 0.0026 (17)
N11 0.043 (2) 0.0314 (19) 0.035 (2) −0.0013 (16) 0.0165 (18) 0.0000 (16)
O1 0.069 (2) 0.0386 (19) 0.057 (2) −0.0084 (16) 0.0357 (19) −0.0073 (16)
O2 0.063 (2) 0.0405 (17) 0.056 (2) −0.0014 (16) 0.0406 (18) −0.0031 (16)
O3 0.089 (3) 0.0330 (17) 0.075 (3) −0.0089 (17) 0.058 (2) −0.0095 (17)
O11 0.066 (2) 0.0370 (18) 0.051 (2) 0.0020 (16) 0.0319 (18) 0.0016 (15)
O12 0.067 (2) 0.0402 (17) 0.047 (2) 0.0019 (16) 0.0382 (18) −0.0018 (15)
O13 0.071 (2) 0.0296 (16) 0.065 (2) 0.0002 (15) 0.0466 (19) −0.0051 (15)
S8 0.0490 (7) 0.0327 (6) 0.0442 (7) −0.0039 (5) 0.0278 (6) −0.0044 (5)
S20 0.0504 (7) 0.0292 (6) 0.0421 (7) −0.0002 (5) 0.0257 (6) −0.0012 (5)
Geometric parameters (Å, º)
C1—O1 1.205 (5) C11—C12 1.507 (6)
C1—O2 1.306 (5) C12—S20 1.802 (4)
C1—C2 1.508 (6) C12—H12A 0.97
C2—S8 1.806 (4) C12—H12B 0.97
C2—H2A 0.97 C13—N11 1.364 (5)
C2—H2B 0.97 C13—C14 1.383 (5)
C3—N1 1.359 (5) C13—S20 1.736 (4)
C3—C4 1.374 (6) C14—C15 1.360 (6)
C3—S8 1.739 (4) C14—H14 0.93
C4—C5 1.378 (6) C15—C16 1.372 (6)
C4—H4 0.93 C15—H15 0.93
C5—C6 1.373 (6) C16—C17 1.366 (6)
C5—H5 0.93 C16—H16 0.93
C6—C7 1.359 (6) C17—N11 1.340 (5)
C6—H6 0.93 C17—H17 0.93
C7—N1 1.346 (5) N1—O3 1.324 (4)
C7—H7 0.93 N11—O13 1.323 (4)
C11—O11 1.206 (5) O2—H2 0.82
C11—O12 1.299 (5) O12—H12 0.82
O1—C1—O2 125.0 (4) S20—C12—H12A 110.3
O1—C1—C2 123.2 (4) C11—C12—H12B 110.3
O2—C1—C2 111.8 (4) S20—C12—H12B 110.3
C1—C2—H2A 110.4 N11—C13—C14 118.6 (4)
S8—C2—H2A 110.4 N11—C13—S20 112.3 (3)
C1—C2—H2B 110.4 C14—C13—S20 129.1 (3)
S8—C2—H2B 110.4 C15—C14—C13 119.3 (4)
H2A—C2—H2B 108.6 C15—C14—H14 120.4
N1—C3—C4 118.5 (4) C13—C14—H14 120.4
N1—C3—S8 112.2 (3) C14—C15—C16 121.2 (4)
C4—C3—S8 129.2 (3) C14—C15—H15 119.4
C3—C4—C5 119.7 (4) C16—C15—H15 119.4
C3—C4—H4 120.1 C17—C16—C15 118.9 (4)
C5—C4—H4 120.1 C17—C16—H16 120.6
C6—C5—C4 120.6 (4) C15—C16—H16 120.6
C6—C5—H5 119.7 N11—C17—C16 120.1 (4)
C4—C5—H5 119.7 N11—C17—H17 119.9
C7—C6—C5 118.5 (4) C16—C17—H17 119.9
C7—C6—H6 120.8 O3—N1—C7 122.0 (3)
C5—C6—H6 120.8 O3—N1—C3 116.4 (3)
N1—C7—C6 121.0 (4) C7—N1—C3 121.7 (4)
N1—C7—H7 119.5 O13—N11—C17 121.4 (3)
C6—C7—H7 119.5 O13—N11—C13 116.7 (3)
O11—C11—O12 124.9 (4) C17—N11—C13 121.9 (3)
O11—C11—C12 123.0 (4) C1—O2—H2 109.5
O12—C11—C12 112.1 (4) C11—O12—H12 109.5
C11—C12—S20 107.1 (3) C3—S8—C2 101.01 (19)
C11—C12—H12A 110.3 C13—S20—C12 100.62 (19)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O2—H2···O13i 0.82 1.76 2.568 (5) 167
O12—H12···O3ii 0.82 1.74 2.541 (5) 163
C4—H4···O12iii 0.93 2.51 3.325 (6) 147
C14—H14···O2iii 0.93 2.55 3.344 (6) 144
C6—H6···O1iv 0.93 2.51 3.420 (6) 168
C5—H5···O3iv 0.93 2.45 3.250 (5) 144
C7—H7···O11v 0.93 2.41 3.286 (6) 156
C15—H15···O13vi 0.93 2.51 3.347 (5) 149
C16—H16···O11vi 0.93 2.57 3.477 (6) 164
C17—H17···O1vii 0.93 2.40 3.279 (6) 157
