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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1482.
Published online 2009 June 6. doi:  10.1107/S160053680902073X
PMCID: PMC2969296

2,2′-[o-Phenylenebis(methylenethio)]bis(pyridine N-oxide)

Abstract

In the title compound, C18H16N2O2S2, the benzene ring makes dihedral angles of 7.41 and 86.59° with the two outer pyridine N-oxygen rings. Two short intramolecular C—H(...)S contacts occur. The crystal packing is stabilized by C—H(...)O hydrogen bonds, C—H(...)π inter­actions and weak π–π staking inter­actions [centroid–centroid distance 3.7596 (7) Å].

Related literature

For a related stucture, see: Han et al. (2005 [triangle]). For thio­ether compounds, see: Xie et al. (2005 [triangle]).

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Object name is e-65-o1482-scheme1.jpg

Experimental

Crystal data

  • C18H16N2O2S2
  • M r = 356.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1482-efi1.jpg
  • a = 7.5075 (15) Å
  • b = 17.810 (4) Å
  • c = 12.480 (3) Å
  • β = 105.20 (3)°
  • V = 1610.3 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.34 mm−1
  • T = 293 K
  • 0.34 × 0.28 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 9681 measured reflections
  • 3782 independent reflections
  • 3145 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.083
  • S = 1.02
  • 3782 reflections
  • 225 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902073X/at2798sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902073X/at2798Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported Beijing Municipal Natural Science Foundation (grant No. 2082004).

supplementary crystallographic information

Comment

Thioether-type ligands are attracting great attention as the conformational freedom, flexible multidentate bridging ligands (Xie et al., 2005). In continuation of the structural study of thioether-type ligands (Han et al., 2005), herein, we report the crystal sructure of the title compound.

The title compound (Fig. 1) was obtained by the reaction of 2-mercaptopyridine N-oxide and o-xylylene dibromide. In the asymmetric unit, the central benzene ring makes dihedral angles of 7.44 and 86.52° with the two outer pyridine N-oxygen rings and the crystal packing is stabilized by C—H···O and C—H..S hydrogen bonding, C—H···π interactions (Table 1) and weak π-π staking interactions [centroid-to-centroid distance 3.7596 (7) Å].

Experimental

2-Mercaptopyridine N-oxide (1.2719 g, 10.00 mmol) was added to a stirred solution of KOH (0.6091 g, 10.85 mmol) in ethanol (50 ml). After 30 min, o-xylylene dibromide (1.3206 g, 5.00 mmol) was added and the mixture was heated to 343 K for 6 h with vigorous stirring. The mixture was cooled to room temperature and the precipitate was filtered off and washed with ethanol and water, giving a white powder in 66.0% yield. Then, a solution of the powder in CHCl3/CH3CN with a molar ratio of 1:1 was filtered. Slow diffusion of ether into the filtrate yielded colourless prism crystals.

Refinement

The H atoms H6A and H6B of the C6 atom were found from a difference Fourier map and refined freely. The rest H atoms were fixed geometrically with C—H = 0.93-0.97 Å and treated as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-hydrogen atoms.

Crystal data

C18H16N2O2S2F(000) = 744
Mr = 356.47Dx = 1.470 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9866 reflections
a = 7.5075 (15) Åθ = 2.0–27.9°
b = 17.810 (4) ŵ = 0.34 mm1
c = 12.480 (3) ÅT = 293 K
β = 105.20 (3)°Prism, colourless
V = 1610.3 (7) Å30.34 × 0.28 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3145 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
graphiteθmax = 27.9°, θmin = 2.0°
ω scansh = −8→9
9681 measured reflectionsk = −17→23
3782 independent reflectionsl = −15→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0371P)2 + 0.5053P] where P = (Fo2 + 2Fc2)/3
3782 reflections(Δ/σ)max < 0.001
225 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.20 e Å3

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 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.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
S10.17377 (5)0.17901 (2)0.34399 (3)0.03675 (11)
S2−0.30419 (5)−0.03050 (2)−0.04963 (3)0.03289 (10)
C7−0.00609 (19)0.04497 (8)0.25080 (11)0.0304 (3)
N1−0.47078 (17)−0.01887 (7)−0.25627 (10)0.0350 (3)
O1−0.48428 (16)−0.09127 (6)−0.24087 (9)0.0458 (3)
C14−0.38096 (18)0.02425 (8)−0.16810 (11)0.0308 (3)
C60.0423 (2)0.12465 (8)0.22786 (12)0.0335 (3)
C10.0008 (2)0.20710 (8)0.40531 (11)0.0324 (3)
C12−0.11785 (18)0.00251 (8)0.16387 (11)0.0301 (3)
C15−0.3632 (2)0.10057 (9)−0.18273 (13)0.0397 (3)
H15A−0.30090.1304−0.12350.048*
N20.06622 (19)0.25129 (7)0.49662 (10)0.0402 (3)
C2−0.1847 (2)0.18976 (9)0.37257 (13)0.0388 (3)
H2A−0.22990.15920.31110.047*
C11−0.1519 (2)−0.07213 (9)0.18381 (13)0.0421 (4)
H11A−0.2260−0.10070.12700.051*
C13−0.19734 (19)0.03928 (8)0.05228 (11)0.0318 (3)
H13A−0.09990.06460.02850.038*
H13B−0.28830.07650.05870.038*
O20.24350 (18)0.26652 (7)0.52668 (10)0.0570 (3)
C80.0643 (2)0.01115 (9)0.35310 (12)0.0402 (3)
H8A0.13670.03920.41120.048*
C90.0293 (3)−0.06342 (10)0.37091 (14)0.0500 (4)
H9A0.0787−0.08520.44010.060*
C18−0.5444 (2)0.01241 (10)−0.35676 (13)0.0456 (4)
H18A−0.6060−0.0178−0.41570.055*
C5−0.0505 (3)0.27874 (9)0.55340 (14)0.0536 (5)
H5A−0.00480.30910.61510.064*
C3−0.3033 (3)0.21749 (10)0.43040 (16)0.0511 (4)
H3A−0.42840.20600.40840.061*
C17−0.5296 (3)0.08746 (11)−0.37289 (14)0.0527 (4)
H17A−0.58070.1085−0.44240.063*
C16−0.4379 (3)0.13227 (10)−0.28521 (14)0.0507 (4)
H16A−0.42690.1836−0.29550.061*
C10−0.0783 (3)−0.10491 (10)0.28622 (14)0.0512 (4)
H10A−0.1019−0.15520.29750.061*
C4−0.2338 (3)0.26248 (10)0.52122 (17)0.0584 (5)
H4A−0.31250.28190.56080.070*
H6A0.125 (2)0.1237 (9)0.1798 (14)0.042 (4)*
H6B−0.062 (2)0.1528 (10)0.1903 (14)0.043 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.03174 (19)0.0384 (2)0.0364 (2)−0.00423 (14)0.00247 (14)−0.00293 (15)
S20.03698 (19)0.03129 (19)0.02808 (18)0.00011 (14)0.00442 (14)−0.00330 (13)
C70.0319 (7)0.0324 (7)0.0271 (7)0.0032 (5)0.0081 (5)−0.0001 (5)
N10.0348 (6)0.0363 (7)0.0308 (6)−0.0028 (5)0.0034 (5)−0.0047 (5)
O10.0547 (7)0.0324 (6)0.0443 (6)−0.0074 (5)0.0022 (5)−0.0070 (5)
C140.0285 (7)0.0351 (7)0.0271 (7)−0.0009 (5)0.0044 (5)−0.0038 (5)
C60.0403 (8)0.0321 (7)0.0267 (7)0.0001 (6)0.0064 (6)−0.0010 (5)
C10.0395 (8)0.0268 (7)0.0277 (7)−0.0026 (6)0.0033 (6)−0.0006 (5)
C120.0308 (7)0.0320 (7)0.0276 (7)0.0021 (5)0.0078 (5)−0.0003 (5)
C150.0450 (9)0.0357 (8)0.0354 (8)−0.0046 (6)0.0054 (6)−0.0039 (6)
N20.0555 (8)0.0280 (6)0.0312 (6)−0.0053 (6)0.0009 (6)−0.0017 (5)
C20.0385 (8)0.0371 (8)0.0390 (8)−0.0029 (6)0.0069 (6)−0.0036 (6)
C110.0507 (9)0.0357 (8)0.0365 (8)−0.0049 (7)0.0053 (7)0.0004 (6)
C130.0333 (7)0.0323 (7)0.0271 (7)−0.0009 (5)0.0031 (5)−0.0019 (5)
O20.0580 (8)0.0494 (7)0.0497 (7)−0.0150 (6)−0.0107 (6)−0.0095 (6)
C80.0462 (9)0.0415 (8)0.0283 (7)0.0008 (7)0.0015 (6)0.0019 (6)
C90.0655 (11)0.0444 (9)0.0351 (9)0.0038 (8)0.0046 (8)0.0130 (7)
C180.0472 (9)0.0530 (10)0.0289 (8)−0.0032 (8)−0.0037 (6)−0.0035 (7)
C50.0920 (15)0.0324 (8)0.0374 (9)0.0016 (9)0.0186 (9)−0.0065 (7)
C30.0484 (10)0.0446 (9)0.0644 (12)0.0024 (8)0.0223 (9)0.0019 (8)
C170.0617 (11)0.0541 (11)0.0348 (9)−0.0003 (9)−0.0004 (7)0.0086 (7)
C160.0653 (11)0.0380 (9)0.0447 (10)−0.0039 (8)0.0071 (8)0.0055 (7)
C100.0695 (12)0.0348 (8)0.0467 (10)−0.0019 (8)0.0104 (8)0.0093 (7)
C40.0828 (14)0.0410 (10)0.0630 (12)0.0088 (9)0.0398 (11)−0.0010 (8)

Geometric parameters (Å, °)

S1—C11.7442 (15)C2—C31.376 (2)
S1—C61.8061 (15)C2—H2A0.9300
S2—C141.7384 (15)C11—C101.382 (2)
S2—C131.8084 (14)C11—H11A0.9300
C7—C81.385 (2)C13—H13A0.9700
C7—C121.4055 (19)C13—H13B0.9700
C7—C61.511 (2)C8—C91.383 (2)
N1—O11.3116 (16)C8—H8A0.9300
N1—C181.351 (2)C9—C101.367 (2)
N1—C141.3660 (17)C9—H9A0.9300
C14—C151.383 (2)C18—C171.361 (3)
C6—H6A0.971 (17)C18—H18A0.9300
C6—H6B0.942 (18)C5—C41.360 (3)
C1—N21.3658 (18)C5—H5A0.9300
C1—C21.380 (2)C3—C41.374 (3)
C12—C111.389 (2)C3—H3A0.9300
C12—C131.5128 (19)C17—C161.383 (2)
C15—C161.376 (2)C17—H17A0.9300
C15—H15A0.9300C16—H16A0.9300
N2—O21.3130 (18)C10—H10A0.9300
N2—C51.355 (2)C4—H4A0.9300
C1—S1—C6101.12 (7)C12—C11—H11A119.3
C14—S2—C13101.52 (7)C12—C13—S2110.19 (10)
C8—C7—C12118.93 (13)C12—C13—H13A109.6
C8—C7—C6122.05 (13)S2—C13—H13A109.6
C12—C7—C6118.93 (12)C12—C13—H13B109.6
O1—N1—C18120.85 (12)S2—C13—H13B109.6
O1—N1—C14118.39 (12)H13A—C13—H13B108.1
C18—N1—C14120.76 (13)C9—C8—C7121.54 (14)
N1—C14—C15119.39 (13)C9—C8—H8A119.2
N1—C14—S2110.69 (10)C7—C8—H8A119.2
C15—C14—S2129.92 (11)C10—C9—C8119.57 (15)
C7—C6—S1117.35 (10)C10—C9—H9A120.2
C7—C6—H6A109.0 (10)C8—C9—H9A120.2
S1—C6—H6A101.6 (10)N1—C18—C17120.86 (15)
C7—C6—H6B112.7 (10)N1—C18—H18A119.6
S1—C6—H6B108.7 (10)C17—C18—H18A119.6
H6A—C6—H6B106.4 (14)N2—C5—C4120.81 (16)
N2—C1—C2119.34 (14)N2—C5—H5A119.6
N2—C1—S1112.67 (11)C4—C5—H5A119.6
C2—C1—S1127.99 (12)C4—C3—C2118.96 (17)
C11—C12—C7118.52 (13)C4—C3—H3A120.5
C11—C12—C13122.19 (13)C2—C3—H3A120.5
C7—C12—C13119.29 (12)C18—C17—C16119.52 (16)
C16—C15—C14119.74 (14)C18—C17—H17A120.2
C16—C15—H15A120.1C16—C17—H17A120.2
C14—C15—H15A120.1C15—C16—C17119.72 (16)
O2—N2—C5121.49 (14)C15—C16—H16A120.1
O2—N2—C1118.23 (13)C17—C16—H16A120.1
C5—N2—C1120.27 (14)C9—C10—C11119.92 (15)
C3—C2—C1120.38 (15)C9—C10—H10A120.0
C3—C2—H2A119.8C11—C10—H10A120.0
C1—C2—H2A119.8C5—C4—C3120.23 (17)
C10—C11—C12121.50 (15)C5—C4—H4A119.9
C10—C11—H11A119.3C3—C4—H4A119.9
O1—N1—C14—C15179.24 (13)S1—C1—C2—C3−179.40 (13)
C18—N1—C14—C15−1.0 (2)C7—C12—C11—C10−0.2 (2)
O1—N1—C14—S2−0.70 (16)C13—C12—C11—C10180.00 (15)
C18—N1—C14—S2179.09 (12)C11—C12—C13—S2−9.11 (17)
C13—S2—C14—N1−178.90 (10)C7—C12—C13—S2171.08 (10)
C13—S2—C14—C151.17 (16)C14—S2—C13—C12−179.41 (9)
C8—C7—C6—S1−7.41 (19)C12—C7—C8—C91.0 (2)
C12—C7—C6—S1176.13 (10)C6—C7—C8—C9−175.47 (15)
C1—S1—C6—C7−80.37 (12)C7—C8—C9—C10−0.5 (3)
C6—S1—C1—N2−178.97 (10)O1—N1—C18—C17−179.67 (16)
C6—S1—C1—C21.27 (15)C14—N1—C18—C170.5 (2)
C8—C7—C12—C11−0.6 (2)O2—N2—C5—C4179.98 (16)
C6—C7—C12—C11175.95 (13)C1—N2—C5—C40.5 (2)
C8—C7—C12—C13179.20 (13)C1—C2—C3—C4−0.1 (3)
C6—C7—C12—C13−4.23 (19)N1—C18—C17—C160.0 (3)
N1—C14—C15—C160.8 (2)C14—C15—C16—C17−0.3 (3)
S2—C14—C15—C16−179.24 (13)C18—C17—C16—C15−0.1 (3)
C2—C1—N2—O2179.46 (13)C8—C9—C10—C11−0.3 (3)
S1—C1—N2—O2−0.33 (17)C12—C11—C10—C90.7 (3)
C2—C1—N2—C5−1.0 (2)N2—C5—C4—C30.2 (3)
S1—C1—N2—C5179.20 (12)C2—C3—C4—C5−0.4 (3)
N2—C1—C2—C30.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.932.423.133 (2)134
C5—H5A···O1ii0.932.383.253 (2)155
C8—H8A···S10.932.673.1105 (18)110
C11—H11A···S20.932.472.9322 (18)111
C15—H15A···O2iii0.932.583.461 (2)158
C9—H9A···Cg2iv0.932.903.645 (2)138

Symmetry codes: (i) −x−1, −y, −z; (ii) −x−1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2798).

References

  • Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Han, L., Wu, B. L., Xu, Y. Q., Wu, M. Y., Gong, Y. Q., Lou, B. Y., Chen, B. Q. & Hong, M. C. (2005). Inorg. Chim. Acta, 358, 2005–2013.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xie, Y. B., Li, J. R. & Bu, X. H. (2005). Polyhedron, 24, 413–418.

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