Acta Cryst. (2008). E64, o409 [ doi:10.1107/S1600536807068766 ]
Molecules of the title compound, C22H24N2O2S2, lie across centres of inversion. The two thiopyridine N-oxide groups adopt a stepped trans configuration with respect to the benzene ring, by virtue of the symmetry. The oxopyridinium ring forms a dihedral angle of 79.9 (2)° with the benzene ring. The crystal structure is stabilized by a strong ![[pi]](/logos/entities/pi_rmgif.gif)
- interaction between the pyridinium rings of adjacent molecules [ring centroid-centroid distance = 3.464 (3) Å].
A mixture of 1,4-bis(bromomethyl)durene (0.320, 1 mmol) and 1-hydroxypyridine-2-thione sodium salt (0.298,2 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 (0.34 g, 82%). The compound was recrystallized from chloroform-methanol (1:2 v/v).
C-bound H atoms were placed in calculated positions [C—H = 0.95 Å (aromatic), 0.98 Å (methylene), and 0.99 Å (methyl)] and refined in the riding-model approximation, with Uiso(H)=1.2–1.5Ueq(C).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ci2548fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Atoms labelled with the suffix a are generated by the symmetry operations (1 - x, 1 - y, 1 - z). |
| C22H24N2O2S2 | F000 = 436 |
| Mr = 412.55 | Dx = 1.426 Mg m−3 |
| Monoclinic, P21/c | Cu Kα radiation λ = 1.54178 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 11.8431 (13) Å | θ = 15–29.3º |
| b = 9.0108 (9) Å | µ = 2.68 mm−1 |
| c = 9.7551 (10) Å | T = 193 (2) K |
| β = 112.611 (9)º | Block, colourless |
| V = 961.01 (17) Å3 | 0.10 × 0.10 × 0.05 mm |
| Z = 2 |
| Enraf–Nonius CAD-4 diffractometer | θmax = 70º |
| ω/2θ scans | θmin = 4.0º |
| Absorption correction: ψ scan (North et al., 1968) | h = −14→13 |
| Tmin = 0.80, Tmax = 0.87 | k = 0→10 |
| 1929 measured reflections | l = 0→11 |
| 1813 independent reflections | 3 standard reflections |
| 1200 reflections with I > 2σ(I) | every 60 min |
| Rint = 0.077 | intensity decay: 3% |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1008P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.057 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.170 | Δρmax = 0.42 e Å−3 |
| S = 0.99 | Δρmin = −0.41 e Å−3 |
| 1813 reflections | Extinction correction: none |
| 129 parameters |
| C22H24N2O2S2 | V = 961.01 (17) Å3 |
| Mr = 412.55 | Z = 2 |
| Monoclinic, P21/c | Cu Kα |
| a = 11.8431 (13) Å | µ = 2.68 mm−1 |
| b = 9.0108 (9) Å | T = 193 (2) K |
| c = 9.7551 (10) Å | 0.10 × 0.10 × 0.05 mm |
| β = 112.611 (9)º |
| Enraf–Nonius CAD-4 diffractometer | 1200 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.077 |
| Tmin = 0.80, Tmax = 0.87 | 3 standard reflections |
| 1929 measured reflections | every 60 min |
| 1813 independent reflections | intensity decay: 3% |
| R[F2 > 2σ(F2)] = 0.057 | 129 parameters |
| wR(F2) = 0.170 | H-atom parameters constrained |
| S = 0.99 | Δρmax = 0.42 e Å−3 |
| 1813 reflections | Δρmin = −0.41 e Å−3 |
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 | 0.4444 (3) | 0.6186 (4) | 0.4063 (4) | 0.0220 (8) | |
| C2 | 0.5351 (3) | 0.6459 (4) | 0.5463 (4) | 0.0234 (8) | |
| C3 | 0.4077 (3) | 0.4715 (4) | 0.3606 (4) | 0.0243 (8) | |
| C4 | 0.5706 (4) | 0.8042 (4) | 0.5965 (4) | 0.0305 (9) | |
| H4A | 0.5049 | 0.8714 | 0.5374 | 0.046* | |
| H4B | 0.646 | 0.8299 | 0.583 | 0.046* | |
| H4C | 0.5838 | 0.8136 | 0.7017 | 0.046* | |
| C5 | 0.3044 (4) | 0.4452 (4) | 0.2124 (4) | 0.0347 (10) | |
| H5A | 0.2428 | 0.5233 | 0.1942 | 0.052* | |
| H5B | 0.267 | 0.3484 | 0.2132 | 0.052* | |
| H5C | 0.3365 | 0.447 | 0.1336 | 0.052* | |
| C6 | 0.3835 (3) | 0.7458 (4) | 0.3017 (4) | 0.0258 (8) | |
| H6A | 0.3528 | 0.7114 | 0.1973 | 0.031* | |
| H6B | 0.4429 | 0.827 | 0.3138 | 0.031* | |
| S7 | 0.25697 (9) | 0.81142 (11) | 0.34802 (10) | 0.0290 (3) | |
| C8 | 0.1962 (3) | 0.9526 (4) | 0.2167 (4) | 0.0254 (8) | |
| N9 | 0.1042 (3) | 1.0262 (4) | 0.2392 (4) | 0.0293 (7) | |
| C10 | 0.0488 (4) | 1.1435 (4) | 0.1524 (5) | 0.0340 (10) | |
| H10 | −0.0123 | 1.1969 | 0.1725 | 0.041* | |
| C11 | 0.0792 (4) | 1.1863 (4) | 0.0363 (5) | 0.0347 (9) | |
| H11 | 0.0394 | 1.2683 | −0.0242 | 0.042* | |
| C12 | 0.1688 (4) | 1.1083 (5) | 0.0083 (5) | 0.0358 (10) | |
| H12 | 0.1889 | 1.1346 | −0.0739 | 0.043* | |
| C13 | 0.2287 (4) | 0.9925 (4) | 0.0998 (4) | 0.0287 (9) | |
| H13 | 0.2918 | 0.9405 | 0.0826 | 0.034* | |
| O14 | 0.0730 (3) | 0.9825 (4) | 0.3471 (3) | 0.0443 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.032 (2) | 0.0160 (17) | 0.0218 (18) | 0.0012 (15) | 0.0144 (16) | 0.0009 (14) |
| C2 | 0.0280 (19) | 0.0172 (17) | 0.0262 (19) | −0.0026 (14) | 0.0117 (15) | −0.0053 (15) |
| C3 | 0.0294 (19) | 0.0227 (19) | 0.0217 (17) | −0.0043 (15) | 0.0106 (15) | −0.0028 (15) |
| C4 | 0.038 (2) | 0.0189 (19) | 0.033 (2) | −0.0065 (17) | 0.0124 (18) | −0.0023 (17) |
| C5 | 0.044 (2) | 0.025 (2) | 0.031 (2) | −0.0021 (19) | 0.0101 (19) | −0.0028 (18) |
| C6 | 0.0303 (19) | 0.0221 (17) | 0.026 (2) | 0.0011 (16) | 0.0116 (16) | −0.0001 (16) |
| S7 | 0.0373 (5) | 0.0247 (5) | 0.0282 (5) | 0.0039 (4) | 0.0160 (4) | 0.0041 (4) |
| C8 | 0.028 (2) | 0.0183 (18) | 0.0265 (19) | −0.0018 (15) | 0.0065 (16) | −0.0063 (15) |
| N9 | 0.0308 (17) | 0.0260 (17) | 0.0300 (17) | 0.0000 (14) | 0.0102 (14) | −0.0034 (14) |
| C10 | 0.030 (2) | 0.025 (2) | 0.038 (2) | 0.0035 (16) | 0.0031 (18) | −0.0069 (18) |
| C11 | 0.035 (2) | 0.0224 (19) | 0.037 (2) | −0.0048 (18) | 0.0027 (17) | −0.0011 (19) |
| C12 | 0.039 (2) | 0.031 (2) | 0.034 (2) | −0.0059 (18) | 0.0102 (18) | 0.0004 (18) |
| C13 | 0.035 (2) | 0.0233 (19) | 0.0249 (19) | −0.0011 (16) | 0.0086 (17) | 0.0008 (16) |
| O14 | 0.055 (2) | 0.0477 (19) | 0.0421 (18) | 0.0125 (16) | 0.0316 (16) | 0.0064 (15) |
| C1—C2 | 1.398 (5) | C11—C12 | 1.384 (6) |
| C1—C3 | 1.412 (5) | C12—C13 | 1.379 (6) |
| C1—C6 | 1.520 (5) | C4—H4A | 0.98 |
| C2—C3i | 1.389 (5) | C4—H4B | 0.98 |
| C2—C4 | 1.514 (5) | C4—H4C | 0.98 |
| C3—C2i | 1.389 (5) | C5—H5A | 0.98 |
| C3—C5 | 1.511 (5) | C5—H5B | 0.98 |
| C6—S7 | 1.822 (4) | C5—H5C | 0.98 |
| S7—C8 | 1.752 (4) | C6—H6A | 0.99 |
| C8—N9 | 1.364 (5) | C6—H6B | 0.99 |
| C8—C13 | 1.384 (5) | C10—H10 | 0.95 |
| N9—O14 | 1.303 (4) | C11—H11 | 0.95 |
| N9—C10 | 1.355 (5) | C12—H12 | 0.95 |
| C10—C11 | 1.369 (6) | C13—H13 | 0.95 |
| C2—C1—C3 | 120.1 (3) | C2—C4—H4C | 109 |
| C2—C1—C6 | 120.8 (3) | H4A—C4—H4B | 109 |
| C3—C1—C6 | 119.2 (3) | H4A—C4—H4C | 109 |
| C3i—C2—C1 | 120.2 (3) | H4B—C4—H4C | 109 |
| C3i—C2—C4 | 120.1 (3) | C3—C5—H5A | 109 |
| C1—C2—C4 | 119.7 (3) | C3—C5—H5B | 110 |
| C2i—C3—C1 | 119.7 (3) | C3—C5—H5C | 109 |
| C2i—C3—C5 | 121.2 (3) | H5A—C5—H5B | 109 |
| C1—C3—C5 | 119.1 (3) | H5A—C5—H5C | 109 |
| C1—C6—S7 | 107.5 (2) | H5B—C5—H5C | 110 |
| C8—S7—C6 | 101.51 (18) | S7—C6—H6A | 110 |
| N9—C8—C13 | 119.9 (4) | S7—C6—H6B | 110 |
| N9—C8—S7 | 111.4 (3) | C1—C6—H6A | 110 |
| C13—C8—S7 | 128.7 (3) | C1—C6—H6B | 110 |
| O14—N9—C10 | 121.4 (4) | H6A—C6—H6B | 108 |
| O14—N9—C8 | 118.4 (3) | N9—C10—H10 | 119 |
| C10—N9—C8 | 120.2 (4) | C11—C10—H10 | 119 |
| N9—C10—C11 | 121.2 (4) | C10—C11—H11 | 120 |
| C10—C11—C12 | 119.1 (4) | C12—C11—H11 | 120 |
| C13—C12—C11 | 119.9 (4) | C11—C12—H12 | 120 |
| C12—C13—C8 | 119.6 (4) | C13—C12—H12 | 120 |
| C2—C4—H4A | 109 | C8—C13—H13 | 120 |
| C2—C4—H4B | 109 | C12—C13—H13 | 120 |
| C3—C1—C2—C3i | 2.0 (6) | C6—S7—C8—C13 | 5.8 (4) |
| C6—C1—C2—C3i | −178.3 (3) | C13—C8—N9—O14 | 177.6 (3) |
| C3—C1—C2—C4 | −177.7 (3) | S7—C8—N9—O14 | −1.6 (4) |
| C6—C1—C2—C4 | 1.9 (5) | C13—C8—N9—C10 | −3.5 (5) |
| C2—C1—C3—C2i | −2.0 (6) | S7—C8—N9—C10 | 177.3 (3) |
| C6—C1—C3—C2i | 178.3 (3) | O14—N9—C10—C11 | −177.9 (4) |
| C2—C1—C3—C5 | 176.5 (3) | C8—N9—C10—C11 | 3.2 (6) |
| C6—C1—C3—C5 | −3.1 (5) | N9—C10—C11—C12 | −0.4 (6) |
| C2—C1—C6—S7 | −86.0 (4) | C10—C11—C12—C13 | −2.1 (6) |
| C3—C1—C6—S7 | 93.6 (4) | C11—C12—C13—C8 | 1.8 (6) |
| C1—C6—S7—C8 | −178.8 (2) | N9—C8—C13—C12 | 1.0 (6) |
| C6—S7—C8—N9 | −175.2 (3) | S7—C8—C13—C12 | −180.0 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
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N-Oxides and their derivatives show a broad spectrum of biological activity, such as antifungal, antibacterial, antimicrobial and antibiotic 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).
The asymmetric unit of the title compound consists of one half of a centrosymmetric molecule. The two thiopyridine-N-oxide groups adopt a stepped trans conformation with respect to the benzene ring, by virtue of the symmetry. The oxopyridinium ring forms a dihedral angle of 79.9 (2)° with the benzene ring. 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). As observed in a similar structure (Hartung et al., 1996), the S atom is bent significantly towards the N-oxide O atom [N9—C8—S7 = 111.4 (3)°].
The crystal packing is stabilized by a strong 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 3.464 (3) Å.